Ink film constructions.
Abstract
An ink film construction including: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate, a commodity coated fibrous printing substrate, and a plastic printing substrate; and (b) an ink dot set contained within a square geometric projection projecting on the first printing substrate, the ink dot set containing at least 10 distinct ink dots, fixedly adhered to a surface of the first printing substrate, all the ink dots within the square geometric projection being counted as individual members of the set, each of the ink dots containing at least one colorant dispersed in an organic polymeric resin, each of the dots having an average thickness of less than 2,000nm, and a diameter of 5 to 300 micrometers; each ink dot of the ink dots having a generally convex shape in which a deviation from convexity, (DCdot), is defined by: DCdot = 1 - AA/CSA, AA being a calculated projected area of the dot, the area disposed generally parallel to the first fibrous printing substrate; and CSA being a surface area of a convex shape that minimally bounds a contour of the projected area; wherein a mean deviation from convexity (DCdot mean) of the ink dot set is at most 0.05.

Term
6.4 yearsleft in the term
Expires 5 March 2033.
- Priority
- Filed
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- Today
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45 claims: 21 independent, 24 dependent
- 1CLAIMS REIVINDICACIONES 1. Una estructura de película de tinta que comprende:one. An ink film structure comprising: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate, a commodity coated fibrous printing substrate, and a plastic printing substrate;and (b) a set of ink dots contained within a square geometric projection protruding on said first printing substrate, said set of ink dots containing at least 10 different ink dots, fixedly adhered to a surface of said first printing substrate, all said ink dots within said geometric projection counted as individual members of said set, each of said ink dots contains at least one colorant dispersed in an organic polymeric resin, each of said dots having an average thickness of less than 2,000 nm, and a diameter of 5 to 300 microns;(a) un primer sustrato de impresión seleccionado del grupo que consiste de un sustrato de impresión fibroso no recubierto, un sustrato de impresión fibroso recubierto de productos básicos, y un sustrato de impresión de plástico;y (b) un conjunto de puntos de tinta contenido dentro de una proyección geométrica cuadrada que sobresale sobre dicho primer sustrato de impresión, dicho conjunto de puntos de tinta contiene por lo menos 10 puntos de tinta distintos, fijamente adheridos a una superficie de dicho primer sustrato de impresión, todos dichos puntos de tinta dentro de dicha proyección geométrica contados como miembros individuales de dicho conjunto, cada uno de dichos puntos de tinta contiene por lo menos un colorante disperso en una resina polimérica orgánica, cada uno de dichos puntos teniendo un espesor medio de menos de 2,000 nm, y un diámetro de 5 a 300 micrómetros;cada punto de tinta de dichos puntos de tinta tiene una forma generalmente convexa en la que una desviación de la convexidad, (DCdot) - se define por: each ink point of said ink points has a generally convex shape in which a deviation from convexity, (DCdot) - is defined by: 191 191 DCd ,, t = 1-AA / CSA. DCd,,t =1-AA/CSA. AA being a calculated projected dot area, said area generally disposed parallel to the first fibrous printing substrate;and AA siendo un área del punto proyectada calculada, dicha área dispuesta generalmente paralela al primer sustrato de impresión fibroso;y CSA being a surface area of a convex shape that minimally limits an outline of the projected area;CSA siendo un área de superficie de una forma convexa que limita mínimamente un contorno del área proyectada;en donde la desviación media de la convexidad (DCdot mean) es a lo sumo 0.05. where the mean deviation of convexity (DCdot mean) is at most 0.05.
- 5The ink film structure of any one of claims 1 to 4, said diameter 5. La estructura de película de tinta de cualquiera de las reivindicaciones 1 a 4, dicho diámetro 192 being at least 7, at least 10, at least 12, at least 15, at least 18, or at least 20 micrometers. 192 siendo de por lo menos 7, por lo menos 10, por lo menos 12, por lo menos 15, por lo menos 18, o por lo menos 20 micrómetros.
- 6The ink film structure of any one of claims 1 to 5, wherein said first printing substrate is an uncoated fibrous printing substrate. 6. La estructura de película de tinta de cualquiera de las reivindicaciones 1 a 5, en donde dicho primer sustrato de impresión es un sustrato de impresión fibroso no recubierto.
- 7The ink film structure of any one of claims 1 to 5, wherein said first printing substrate is a commodity coated fibrous printing substrate. 7. La estructura de película de tinta de cualquiera de las reivindicaciones 1 a 5, en donde dicho primer sustrato de impresión es un sustrato de impresión fibroso recubierto de productos básicos.
- 13The ink film structure of any one of claims 1 to 12, said set of ink dots having at least 20, at least 50, or at least 200 of said distinct ink dots. 13 . La estructura de película de tinta de cualquiera de las reivindicaciones 1 a 12, dicho conjunto de puntos de tinta teniendo por lo menos 20, por lo menos 50, o por lo menos 200 de dichos puntos de tinta distintos.
- 14The ink film structure of any one of claims 1 to 13, said DCdot mean being at least 0.0005, at least 0.001, at least 0.0015, at least 0.002, at least 0.0025, at least 0.003, at least 0.004, at least 0.005, at least 0.006, at least minus 0.008, at least 0.010, at least 0.012, or at least 0.013. 14. La estructura de película de tinta de cualquiera de las reivindicaciones 1 a 13, dicha DCdot mean siendo por lo menos 0.0005, por lo menos 0.001, por lo menos 0.0015, por lo menos 0.002, por lo menos 0.0025, por lo menos 0.003, por lo menos 0.004, por lo menos 0.005, por lo menos 0.006, por lo menos 0.008, por lo menos 0.010, por lo menos 0.012, o por lo menos 0.013.
- 15La estructura de película de tinta de cualquiera de las reivindicaciones 1 a 14, dicho espesor medio estando dentro de un rango de 100-1, 200 nm, 200-1, fifteen. The ink film structure of any one of claims 1 to 14, said average thickness being within a range of 100-1, 200nm, 200-1, 200 nm, 200-1, OOOnm, 100-800nm, 100-600nm, 100-500nm, 100-450nm, 100-400nm, 100-350nm, 100-300nm, 200-450nm, 200400nm or 200-350nm. 200 nm, 200-1, OOOnm, 100-800nm, 100-600 nm, 100-500nm, 100-450nm, 100-400nm, 100-350nm, 100-300nm, 200-450nm, 200400nm o 200-350 nm. 194 194 average being at least lOOnm, at least 150nm, at least 17.5 nanometers, at least 2 00nm, at least 250nm, at least 300nm, or at least 350nm. promedio siendo por lo menos de lOOnm, por lo menos 150nm, por lo menos 17 5 nanómetros, por lo menos 2 00 nm, por lo menos 250nm, por lo menos 300 nm, o por lo menos 350nm.
- 1618. An ink film structure comprising:18. Una estructura de película de tinta que comprende: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate and a commodity coated fibrous printing substrate;and (b) at least a first ink dot, fixedly adhered to a surface of said first printing substrate, said ink dot contains at least one colorant dispersed in an organic polymeric resin, said dot having an average thickness of less than 2,000 nm, and a diameter of 5 to 300 microns;(a) un primer sustrato de impresión seleccionado del grupo que consiste de un sustrato de impresión fibroso no recubierto y un sustrato de impresión fibroso recubierto de productos básicos;y (b) al menos un primer punto de tinta, fijamente adheridos a una superficie de dicho primer sustrato de impresión, dicho punto de tinta contiene por lo menos un colorante disperso en una resina polimérica orgánica, dicho punto teniendo un espesor medio de menos de 2,000 nm, y un diámetro de 5 a 300 micrómetros;Said ink dot has a generally convex shape in which a convex deviation, (DCdot), is defined by: dicho punto de tinta tiene una forma generalmente convexa en la que una desviación de la convexidad, (DCdot) , se define por: 195 195 DCd..t = 1 - AA / CSA, DCd..t = 1 - AA/CSA, AA being a calculated projected dot area, said area generally disposed parallel to said first fibrous printing substrate;and AA siendo un área del punto proyectada calculada, dicha área dispuesta generalmente paralela a dicho primer sustrato de impresión fibroso;y CSA being a surface area of a convex shape that minimally limits an outline of said projected area;CSA siendo un área de superficie de una forma convexa que limita mínimamente un contorno de dicha área proyectada;dicha desviación de la convexidad (DCaot) siendo a lo sumo 0.05, para dicho sustrato sin recubrir;said convex deviation (DCaot) being at most 0.05, for said uncoated substrate;dicha desviación de la convexidad (DCdot) siendo a lo sumo 0.025 para dicho sustrato recubierto de productos básicos. said deviation from convexity (DCdot) being at most 0.025 for said substrate covered with basic products.
- 202. 3. The ink film structure of any one of claims 18 to 22, said average thickness being at most 1,800 nm, at most 1,500 nm, at most 1,200 nm, at most 1,000 nm, at most 800 nm, at at most 500, at most 450 nm, or at most 400 nm. 23. La estructura de película de tinta de cualquiera de las reivindicaciones 18 a 22, dicho espesor medio siendo a lo sumo 1,800 nm, a lo sumo 1,500 nm, a lo sumo 1,200 nm, a lo sumo 1,000 nm, a lo sumo 800 nm, a lo sumo 500, a lo sumo 450 nm, o a lo sumo 400 nm.
- 2124. The ink film structure of any one of claims 18 to 23, said average thickness being within a range of 100-1, 200nm, 200-1, 24. La estructura de película de tinta de cualquiera de las reivindicaciones 18 a 23, dicho espesor medio estando dentro de un rango de 100-1, 200 nm, 200-1, 200 nm, 200-1, OOOnm, 100-800nm, 100-600nm, 100-500nm, 200 nm, 200-1, OOOnm, 100-800nm, 100-600 nm, 100-500nm, 100-450nm, 100-400nm, 100-350nm, 100-300nm, 200-450nm, 200400nm o 200-350 nm. 100-450nm, 100-400nm, 100-350nm, 100-300nm, 200-450nm, 200400nm or 200-350nm.
- 2225. The structure of ink film 25. La estructura de película de tinta de 197 any one of claims 18 to 23, said average thickness being at least 50nm, at least 100nm, at least 150nm, at least 200nm, at least 250nm, at least 300nm, or at least 350 nm. 197 cualquiera de las reivindicaciones 18 a 23, dicho espesor medio siendo de por lo menos 50 nm, por lo menos 100 nm, por lo menos 150 nm, por lo menos 200 nm, por lo menos 250 nm, por lo menos 300 nm, o por lo menos 350 nm.
- 2326. An ink film structure comprising:26. Una estructura de película de tinta que comprende: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate and a commodity coated fibrous printing substrate;and (b) at least a first ink dot, fixedly adhered to a surface of said first printing substrate, said ink dot contains at least one colorant dispersed in an organic polymeric resin, said dot having an average thickness of less than 2,000 nm;(a) un primer sustrato de impresión seleccionado del grupo que consiste de un sustrato de impresión fibroso no recubierto y un sustrato de impresión fibroso recubierto de productos básicos;y (b) al menos un primer punto de tinta, fijamente adheridos a una superficie de dicho primer sustrato de impresión, dicho punto de tinta contiene por lo menos un colorante disperso en una resina polimérica orgánica, dicho punto teniendo un espesor medio de menos de 2,000 nm;dicho punto de tinta tiene una forma generalmente convexa en la que una desviación de la convexidad, (DCdot) , se define por: said ink dot has a generally convex shape in which a deviation from convexity, (DCdot), is defined by: DCdut = 1-AA / CSA, DCdut =1-AA/CSA, AA being a calculated projected dot area, said area generally disposed parallel to said first fibrous printing substrate;and AA siendo un área del punto proyectada calculada, dicha área dispuesta generalmente paralela a dicho primer sustrato de impresión fibroso;y CSA being a surface area of a convex shape that minimally limits an outline of said projected area;CSA siendo un área de superficie de una forma convexa que limita mínimamente un contorno de dicha área proyectada;198 said deviation from convexity (DC <jort) being at most 0.04;198 dicha desviación de la convexidad (DC<jot) siendo a lo sumo 0.04;la estructura de película de tinta siendo demás definida por: the ink film structure with others being defined by: DCd „t <K · RDC, DCd„t < K· RDC, K being a coefficient;K siendo un coeficiente;RDC being a deviation from the reference convexity of a reference ink dot in a reference ink film structure including said reference ink film disposed on a reference fibrous substrate substantially identical to said first fibrous printing substrate, said reference deviation defined by: RDC siendo una desviación de la convexidad de referencia de un punto de tinta de referencia en una estructura de película de tinta de referencia que incluye dicha película de tinta de referencia dispuesta sobre un sustrato fibroso de referencia sustancialmente idéntico a dicho primer sustrato de impresión fibroso, dicha desviación de referencia definida por: RDC = 1 - AAr ^ CSArer, RDC = 1 - AAr^CSArer, AAref being a calculated projected reference point area, said area generally arranged parallel to the reference substrate;and AAref siendo un área de dicho punto de referencia proyectada calculada, dicha área dispuesta generalmente paralela al sustrato de referencia;y CSAref being a surface area of a convex shape that minimally leaves a contour of said projected area of said reference point, said coefficient (K) being at most 0.25. CSAref siendo un área de superficie de una forma convexa que sale mínimamente un contorno de dicha área proyectada de dicho punto de referencia, dicho coeficiente (K) siendo a lo sumo 0.25.
- 2832. The ink film structure of any one of claims 28 to 31, said set of ink dots having at least 20, at least 32. La estructura de película de tinta de cualquiera de las reivindicaciones 28 a 31, dicho conjunto de puntos de tinta teniendo por lo menos 20, por lo menos 201 201 50, o por lo menos 200 de dichos puntos de tinta distintos. 50, or at least 200 of said different ink dots.
- 2933. The ink film structure of any one of claims 28 to 32, said mean deviation (DRaot mean) being at least 0.02, at least 0.04, at least 0.06, or at least 0.08. 33. La estructura de película de tinta de cualquiera de las reivindicaciones 28 a 32, dicha desviación media (DRaot mean) siendo por lo menos de 0.02, por lo menos 0.04, por lo menos 0.06, o por lo menos 0.08.
- 303. 4. An ink film structure comprising:34. Una estructura de película de tinta que comprende: (a) a first fibrous printing substrate selected from the group consisting of an uncoated fibrous printing substrate and a commodity coated fibrous printing substrate;and (b) at least a first ink dot, fixedly adhered to a surface of said first printing substrate, said ink dot contains at least one colorant dispersed in an organic polymeric resin, said dot having an average thickness of less of (a) un primer sustrato de impresión fibroso seleccionado del grupo que consiste de un sustrato de impresión fibroso no recubierto y un sustrato de impresión fibroso recubierto de productos básicos;y (b) por lo menos un primer punto de tinta, fijamente adherido a una superficie de dicho primer sustrato de impresión, dicho punto de tinta contiene por lo menos un colorante disperso en una resina polimérica orgánica, dicho punto tiene un espesor medio de menos de 2,000 nm;2,000 nm;dicho punto de tinta tiene una desviación de una forma circular lisa, (DRdot) , representada por: said ink dot has a deviation from a smooth circular shape, (DRdot), represented by: representada por: represented by: DRdot = | Ρ2/ (4π · Α) 1 -1, DRdot = |Ρ2/(4π·Α)1 -1, P being a perimeter of said measured or calculated ink dot;P siendo un perímetro de dicho punto de tinta medido o calculado;Ά being a maximum area measured or contained by said perimeter;Ά siendo un área máxima medida o contenida por dicho perímetro;202 said deviation (DRaort) for said uncoated fibrous printing substrate, being at most 1.5, at most 1.25, at most 1.1, at most 1.0, at most 0.9, at most 0.8, at most 0.7, at most 0.6, at most 0.5, at most 0.4, at most 0.3, or at most 0.25;202 dicha desviación (DRaot) para dicho sustrato de impresión fibroso no recubierto, siendo a lo sumo 1.5, a lo sumo 1.25, a lo sumo 1.1, a lo sumo 1.0, a lo sumo 0.9, a lo sumo 0.8, a lo sumo 0.7, a lo sumo 0.6, a lo sumo 0.5, a lo sumo 0.4, a lo sumo 0.3, o a lo sumo 0.25;dicha desviación (DRaot) para dicho sustrato de impresión fibroso recubierto de producto básico siendo a lo sumo 0.5, a lo sumo 0.4, a lo sumo 0.3, a lo sumo 0.25, a lo sumo 0.2, a lo sumo 0.15, a lo sumo 0.10, a lo sumo said deviation (DRaot) for said basic product coated fibrous printing substrate being at most 0.5, at most 0.4, at most 0.3, at most 0.25, at most 0.2, at most 0.15, at most 0.10, at most 0.08, a lo sumo 0.06 , o a lo sumo 0.05. 0.08, at most 0.06, or at most 0.05.
- 3338. An ink film structure comprising:38. Una estructura de película de tinta que comprende: (a) a printing substrate;and (b) a plurality of continuous ink films, fixedly adhered to a surface of said printing substrate, said plurality of said films containing a plurality of colorants dispersed in at least one organic polymeric resin, said films (a) un sustrato de impresión;y (b) una pluralidad de películas de tinta continuas, fijamente adheridas a una superficie de dicho sustrato de impresión, dicha pluralidad de dichas películas conteniendo una pluralidad de colorantes dispersos en por lo menos una resina polimérica orgánica, dichas películas 205 at most 1,600 nm, at most 1,500 nm, or at most 1,400 nm;205 sumo 1,600 nm, a lo sumo 1,500 nm, o a lo sumo 1,400 nm;en donde, dentro de dicha área, la estructura de la película de tinta muestra un volumen de gama de colores de por lo menos 425 kilo(AE)3, por lo menos 440 kilo(AE)3, por lo menos 460 kilo(AE)3, por lo menos 480 kilo(AE)3, o por lo menos 500 kilo(AE)3. where, within said area, the structure of the ink film shows a color gamut volume of at least 425 kilograms (AE)3, at least 440 kilo (AE)3, at least 460 kilo (AE)3, at least 480 kilo (AE)3, or at least 500 kilo (AE)3.
- 3944. The ink film structure of the 44. La estructura de película de tinta de la 206 Claim 42 or Claim 43, wherein said volume of color gamut shown by the ink film structure is at least 520 kilograms (AE)3, at least 540 kilo (AE)3, at least kilo (AE)3, or at least kilo (ΔΕ)3. 206 reivindicación 42 o la reivindicación 43, en donde dicho volumen de gama de colores mostrado por la estructura de película de tinta es de por lo menos 520 kilo(AE)3, por lo menos 540 kilo(AE)3, por lo menos kilo(AE)3, o por lo menos kilo(ΔΕ)3.
- 4045. La estructura de película de tinta de cualquiera de las reivindicaciones 38-44, dicha pluralidad de películas de tinta continuas teniendo una pluralidad de puntos de tinta individuales, dichos puntos de tinta dispuestos por encima de dicha área y teniendo un espesor Four. Five. The ink film structure of any of claims 38-44, said plurality of continuous ink films having a plurality of individual ink dots, said ink dots arranged above said area and having a thickness nanometers. nanómetros.
- 4146. The ink film structure of any of claims 38-44, said plurality of continuous ink films including a plurality of individual ink dots having a first thickness disposed above said area and a second thickness disposed below said area, within said substrate, a total of said first thickness and said second thickness being at most 900 nanometers, at most 800 nanometers, at most 7 00 nanometers, or at most 600 nanometers. 46. La estructura de película de tinta de cualquiera de las reivindicaciones 38-44, dicha pluralidad de películas de tinta continuas incluyendo una pluralidad de puntos de tinta individuales que tienen un primer espesor dispuesto por encima de dicha área y un segundo espesor dispuesto por debajo de dicha área, dentro de dicho sustrato, un total de dicho primer espesor y dicho segundo espesor siendo a lo sumo de 900 nanómetros, a lo sumo 800 nanómetros, a lo sumo 7 00 nanómetros, o a lo sumo 600 nanómetros. 207 207
- 4551. The ink film structure of any of claims 48-50, said plurality of continuous ink films having a plurality of individual ink dots, said ink dots disposed above said area and having a thickness 51. La estructura de película de tinta de cualquiera de las reivindicaciones 48-50, dicha pluralidad de películas de tinta continuas teniendo una pluralidad de puntos de tinta individuales, dichos puntos de tinta dispuestos por encima de dicha área y teniendo un espesor any one of claims 48-50, said plurality of continuous ink films having an average thickness of at most 2,500 nanometers, at most 2,300 nanometers, at most 2,100 nanometers, at most 2,000 nanometers, at most 1,900 nanometers, at most 1,800 nanometers, at most 1,700 nanometers, at most 1,600 nanometers, or at most 1,500 nanometers. cualquiera de las reivindicaciones 48-50, dicha pluralidad de películas de tinta continuas teniendo un espesor medio de a lo sumo 2,500 nanómetros, a lo sumo 2,300 nanómetros, a lo sumo 2,100 nanómetros, a lo sumo 2,000 nanómetros, a lo sumo 1,900 nanómetros, a lo sumo 1,800 nanómetros, a lo sumo 1,700 nanómetros, a lo sumo 1,600 nanómetros, o a lo sumo 1,500 nanómetros. 209 209
Independent claims21
1,050 paragraphs in 20 sections, as filed
(54) Title: INK FILM STRUCTURES.
(54) Title: INK FILM CONSTRUCTIONS.
(57) Summary
An ink film structure including: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate, a commodity coated fibrous printing substrate, and a plastic printing substrate; and (b) a set of ink dots contained within a square geometric projection protruding on the first printing substrate, the set of ink dots containing at least 10 different ink dots, fixedly adhered to a surface of the first substrate print, all the ink dots within the geometric projection counted as individual members of the set, each of the ink dots contains at least one colorant dispersed in an organic polymeric ream, each of the dots having an average thickness of less than 2,000 nm, and a diameter of 5 to 300 microns; each ink dot of the ink dots having a generally convex shape in which a convex deviation, (DCdot), is defined by: DCdot = 1-AA / CSA, AA being a calculated projected dot area, the area generally arranged parallel to the first fibrous printing substrate; and CSA being a surface area of a convex shape that minimally limits an outline of the projected area; where a mean deviation of the convexity (DCdot mean) of the set of ink dots is at most 0. 05.
(57) Abstract
An ink film construction including: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate, a commodity coated fibrous printing substrate, and a plastic printing substrate; and (b) an ink dot set contained within a square geometric projection projecting on the first printing substrate, the ink dot set containing at least 10 distinct ink dots, fixedly adhered to a surface of the first printing substrate, all the ink dots within the square geometric projection being counted as individual members of the set, each of the ink dots containing at least one colorant dispersed in an organic polymeric resin, each of the dots having an average thickness of less than 2,000nm, and a diameter of 5 to 300 micrometers; each ink dot of the ink dots having a generally convex shape in which a deviation from convexity, (DCdot), is defined by: DCdot = 1 - AA / CSA, AA being a calculated projected area of the dot, the area disposed generally parallel to the first fibrous printing substrate; and CSA being a surface area of a convex shape that minimally bounds a contour of the projected area; Where a mean deviation from convexity (DCdot mean) of the ink dot set is at most 0.05.
INK FILM STRUCTURES
FIELD AND BACKGROUND OF DISCLOSURE
The present invention relates to ink film structures and, more particularly, to ink dots adhering to printing substrates. In particular, the ink film structures comprise continuous ink dots, which can be obtained by way of example using inkjet technology.
Lithographic printing is currently the most common process in use for newspaper and magazine production. Lithographic printing involves the preparation of plates that carry the image to be printed, these plates are mounted on a plate cylinder. An image of ink produced in the plate cylinder is transferred to a photo-printing (offset) cylinder bearing a rubber rubber holder. From the rubber holder, the image is applied to the paper, cardboard, or other printing medium, called the substrate, which is fed between the photo-printing cylinder and a printing cylinder. For a wide variety of well-known reasons, offset litho printing is suitable, and economically viable, only for long print runs.
More recently, digital printing techniques have been developed to allow a printing device to receive instructions directly from a computer without the need to prepare printing plates. These include color laser printers that use the xerographic process. Color laser printers using dry toners are suitable for certain applications, but do not produce images of acceptable quality for publications such as magazines.
A process that is best suited for high-quality short-run digital printing is used in the HP-indigo digital printing press. In this process, an electrostatic image is produced in an electrically charged image support cylinder by exposure to laser light. The electrostatic charge attracts oil-based inks to form a color ink image on the image support cylinder. The ink image is then transferred by means of a rubber holder cylinder onto the substrate.
Various printing devices that use an indirect inkjet printing process have also been previously proposed, this being a process in which an inkjet print head is used to print an image onto the surface of a transfer member. intermediate, which is then used to transfer the image to a substrate. The intermediate transfer member may be a rigid drum or a flexible belt, also referred to herein as a roller-guided rubber holder.
The use of an indirect printing technique overcomes many of the problems associated with inkjet printing directly on the substrate. For example, the injection of ink that is printed directly on porous paper, or other fibrous material, results in a poor quality image due to the variation in the distance between the print head and the substrate surface, and by the substrate that acts as a wick. Fibrous substrates, such as paper, generally require specific coatings designed to absorb liquid ink in a controlled manner or to prevent its penetration below the substrate surface. The use of substrates with a special coating is, however, an expensive option that is not suitable for certain printing applications. Also, the use of coated substrates creates its own problems because the substrate surface remains damp and additional costly steps are needed to dry the ink so that it does not smear later when the substrate is being handled, for example by stacking or winding on a roll.
Furthermore, excessive wetting of the substrate causes deformation and makes printing on arabic sides of the substrate (also called refined or duplex printing) a difficult, if not impossible, task.
The use of an indirect technique, on the other hand, allows the distance between the image transfer surface and the inkjet print head to be kept constant, reduces the wetting of the substrate since the ink can dry on the surface of Image transfer before being applied to the substrate. Consequently, the quality of the final image of the ink film on the substrate is less affected by the physical properties of the substrate.
Although there are various quality ink film structures, it is believed that there is a need for further improvements in ink film structures, such as inkjet print structures.
BRIEF DESCRIPTION OF THE INVENTION
In accordance with some teachings of the present invention, an ink film structure is provided including: (a) a printing substrate; and (b) a plurality of continuous ink films, fixedly adhered to a surface of the printing substrate, said ink films containing at least one colorant dispersed in an organic polymeric resin; said ink films having a first dynamic viscosity within a range of 10<sup>6</sup> cP at 3 · 10<sup>8</sup> cP during at least a first temperature within a first range of 90 ° C to 195 ° C, the ink films having a second dynamic viscosity of at least 8 · 10<sup>7</sup> cP, during at least a second temperature within a second range of 50 ° C to 85 ° C.
In accordance with another aspect of the present invention, an ink dot structure is provided including: (a) a first fibrous print substrate selected from the group consisting of an uncoated fibrous print substrate and a coated fibrous print substrate of basic products; and (b) at least one continuous ink dot, fixedly adhered to a surface of the first printing substrate, the ink dot containing at least one colorant dispersed in an organic polymeric resin, the ink dot coating an area of the upper surface; the ink point fulfilling a structural condition in which, with respect to a normal direction to the surface over the entire area, the ink spot is arranged entirely above the area, an average or characteristic thickness of the single point of ink being at most 1,
800 nm.
In accordance with yet another aspect of the present invention, there is provided an ink film structure including: (a) a first fibrous printing substrate selected from the group consisting of an uncoated fibrous printing substrate and a fibrous printing substrate coated with basic products; and (b) at least a first continuous ink dot, fixedly adhered to a first surface of the first printing substrate, the ink dot containing at least one colorant dispersed in an organic, polymeric resin, the dot having an average thickness less than 2,000 nm; the point being generally disposed above a particular surface of the surface; a point penetration below the particular surface, relative to a normal direction to the first surface, is less than lOOnm; the ink dot has a generally convex shape in which a deviation from convexity, (DCdot)> is defined by:
DCdot = 1-AA / CSA,
AA being a calculated projected dot area, the area generally disposed parallel to the first fibrous printing substrate; and CSA being a surface area of a convex shape that minimally limits an outline of the projected area; the convex deviation (DCdot) is at most 0.03.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a printing substrate; and (b) at least one ink film, fixedly adhered to a top surface of the printing substrate, the ink film having a top film surface distal to the top surface of the substrate, where a surface concentration of nitrogen at the surface of the upper film exceeds a volumetric concentration of nitrogen within the film, the volumetric concentration is measured at a depth of at least 30 nanometers, at least 50 nanometers, at least 100 nanometers, at least 200 nanometers, or at least 300 nanometers below the surface of the top film, and the ratio of surface concentration to mass concentration is at least less
1.1 to 1.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a printing substrate; and (b ) at least one ink film, fixedly adhered to an upper surface of the printing substrate, the ink film containing at least one colorant dispersed in an organic polymeric resin, the ink film having a film upper surface distal to the top surface of the substrate, where a surface nitrogen concentration on the top film surface exceeds a volumetric concentration of nitrogen within the film, the highest concentration is measured at a depth of at least 30 nanometers below the surface of the top film, and where a ratio of the surface concentration to the mass concentration is at least 1.1 to 1.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate, a coated product, and a printing substrate of plastic; and (b) a set of ink dots contained within a square geometric projection protruding on the first printing substrate, the set of ink dots contains at least 10 different ink dots, fixedly adhered to a surface of the first print substrate, all ink dots within the square geometric projection are counted as individual members of the set, each of the ink dots contains at least one colorant dispersed in an organic polymeric resin, each of the dots has an average thickness of less than 2,000 nm, and a diameter of 5 to 300 microns; each of the ink dots has a generally convex shape in which a deviation from convexity, (DCdot), is defined by:
DC, iot = 1 - AA / CSA,
AA being a calculated projected dot area, the area generally disposed parallel to the first fibrous printing substrate; and CSA being a surface area of a convex shape that minimally limits an outline of the projected area; the convex deviation (DCdot mean) is at most 0.05.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate, a coated product, and a printing substrate of plastic; and (b) a set of ink dots contained within a square geometric projection protruding on the first printing substrate, the set of ink dots containing at least 10 different ink dots, fixedly adhered to a surface of the first substrate print, all ink dots within the square geometric projection are counted as individual members of the set, each of the ink dots contains at least one colorant dispersed in an organic polymeric resin, each of the dots has an average thickness of less than 2,000 nm, and a diameter of 5 to 300 microns; each of the ink dots has a deviation from a smooth circular shape, (DRdot), represented by:
DR<sub>det</sub>= (P<sup>2</sup>/ (4n * A)] - l,
P being a measured or calculated perimeter of the ink dot; A being a maximum area measured or contained by the calculated perimeter; a mean deviation (DR<sub>dot</sub> mean) of the set ink point being at most 0.60.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a first fibrous print substrate selected from the group consisting of an uncoated fibrous print substrate and a product coated fibrous print substrate basic; and (b) at least a first ink dot, fixedly adhered to a surface of the first printing substrate, the ink dot contains at least one colorant dispersed in an organic, polymeric resin, the dot having an average thickness less than 2,000 nm, and a diameter of 5 to 300 micrometers; the ink dot has a generally convex shape in which a deviation from convexity, (DCaot) <is defined by:
DCd „<sub>t</sub> = 1 - AA / CSA.
AA being a calculated projected dot area, the area generally disposed parallel to the first fibrous printing substrate; and CSA being a surface area of a convex shape that minimally limits an outline of the projected area; the convex deviation (DCaot) is at most 0.025, for the coated commodity substrate.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a first fibrous print substrate selected from the group consisting of an uncoated fibrous print substrate and a fibrous product coated print substrate basic; and (b) at least a first ink dot, fixedly adhered to a surface of the first printing substrate, the ink dot contains at least one colorant dispersed in an organic, polymeric resin, the dot having an average thickness of less 2,000 mn; the ink dot has a generally convex shape in which a convex deviation (DCaot) is defined by:
DC<sub>d</sub>„, = L - AA / CSA,
AA being a calculated projected dot area, the area generally disposed parallel to the first fibrous printing substrate; and CSA being a surface area of a convex shape that minimally limits an outline of the projected area; convex deviation (DC<sub>Doc</sub>) is at most 0.04; the ink film structure with others being defined by:
DCdot <K · RDC,
K being a coefficient; RDC being a reference deviation of the convexity of a reference ink dot in a reference ink film structure that includes the reference ink film disposed on a reference fibrous substrate substantially identical to the first fibrous printing substrate, the reference deviation defined by:
RDC = 1 - AA ^ CSA ^ r,
AA<sub>re</sub>f being a calculated projected reference point area, the area generally disposed parallel to the reference substrate; and CSA<sub>re</sub>f being a surface area of a convex shape that minimally leaves a contour of the projected area of the reference point, the coefficient (K) is at most 0.25.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a first printing substrate selected from the group consisting of an uncoated fibrous printing substrate, a coated product, and a printing substrate of plastic; and (b) a set of ink dots contained within a square geometric projection protruding on the first printing substrate, the set of ink dots containing at least 10 different ink dots, fixedly adhered to a surface of the first substrate print, all ink dots within the square geometric projection count as individual members of the set, each of the ink dots contains at least one colorant dispersed in an organic polymeric resin, each of the dots has an average thickness of less than 2,000 nm, and a diameter of 5 to 300 microns; each ink point of the ink points has a deviation from a smooth circular shape (DR<sub>dot</sub>) represented by:
DR ,,, „= [P<sup>2</sup>/ (4n * A)] - l,
P being a measured or calculated ink point perimeter; A being a maximum area measured or contained by the calculated perimeter; where a mean deviation (DRdot mean) of the set of ink dots is at most 0.60.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a first fibrous print substrate selected from the group consisting of an uncoated fibrous print substrate and a product coated fibrous print substrate basic; and (b) at least a first ink dot, fixedly adhered to a surface of the first printing substrate, the ink dot contains at least one colorant dispersed in an organic, polymeric resin, the dot having an average thickness of less 2,000 nm; the ink dot has a deviation from a smooth circular shape (DR<sub>dot</sub>), represented <sup>by:</sup> DR<sub>dot</sub> = | Ρ<sup>2</sup>/ (4π · Α)] - 1,
P being a measured or calculated ink point perimeter; A being a maximum area measured or contained by the calculated perimeter; the deviation (DRdot) for the uncoated fibrous printing substrate, being at most 1.5, at most 1.25, at most 1.1, at most 1.0, at most 0.9, at most 0.8, at most 0.7, at most 0.6, at most 0.5, at most 0.4, at most 0.3, or at most 0.25; deviation (DR<sub>dot</sub>) for the basic product coated fibrous printing substrate at most 0.5, at most 0.4, at most 0.3, at most 0.25, at most 0.2, at most 0.15, at most 0.10, at most 0.08, at most 0.06, or at most 0.05.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a first fibrous print substrate selected from the group consisting of an uncoated fibrous print substrate and a product coated fibrous print substrate basic; and (b) at least a first ink dot, fixedly adhered to a surface of the first printing substrate, the ink dot contains at least one colorant dispersed in an organic, polymeric resin, the dot having a medium thickness less than 2,000nm, the average thickness being at least 50nm, at least 100nm, at least 150nm, at least 175nm, at least 200nm, at least 225nm, or at least 250nm; the ink dot has a deviation from a smooth circular shape (DR<sub>dot</sub>) represented by: ,
DRdot = (Ρ<sup>2</sup>/ (4π · Α) 1 - l,
P being a measured or calculated ink point perimeter; A being a maximum area measured or contained by the calculated perimeter; deviation (DR<sub>dot</sub>) is at most 0.5, at most 0.4, at most 0.35, at most 0.3, or at most 0.25; the ink dot structure is further defined by:
DRdot <Kl · RDR,
Kl being a coefficient; RDR being a reference deviation from the roundness of a reference ink dot on a reference ink film structure including the reference ink film arranged on a reference fibrous substrate substantially identical to the first fibrous printing substrate, the defined reference deviation<sup>by:</sup> RDR = [PnT / (4n «Arvf) I -1>
P<sub>re</sub>f being a measured or calculated reference ink point perimeter; TO<sub>re</sub>f being a maximum measured or calculated area contained by P<sub>re</sub>F; the coefficient (Kl) being at most 0.25.
In accordance with yet another aspect of the present invention, an ink film structure is provided including: (a) a printing substrate; and (b) a plurality of continuous ink films, fixedly adhered to a surface of the printing substrate, the plurality of the films contain a plurality of dyes dispersed in at least one organic polymeric resin, the ink films cover an area of the
<td>surface,</td><td>the</td><td>plurality of movies</td><td>they have a</td><td>thickness</td>
<td>middle of a</td><td>the</td><td>2,200nm at most</td><td>2,100nm, at</td><td>the most</td>
<td>2,000 nm, at</td><td>the</td><td>at most 1,900 nm, at most</td><td>1,800 nm, at</td><td>the most</td>
<td>1,700 nm, at</td><td>the</td><td colspan="2">l, 600nm, at most 1,500nm,</td><td>or what</td>
sumo 1,400 nm; where, within the area, the ink film structure displays a color gamut volume of at least 425 kilograms (AE)<sup>3</sup>, at least 440 kilo (AE)<sup>3</sup>, at least 460 kilo (AE)<sup>3</sup>, at least 480 kilo (AE)<sup>3</sup>, or at least 500 kilo (AE)<sup>3</sup>.
According to still other characteristics in the described preferred embodiments, the first dynamic viscosity is at most 25-10<sup>7</sup> cP, at most 20 · 10<sup>7</sup> cP, at most 15 · 10<sup>7</sup> cP, at most 12 · 10<sup>7</sup> cP, at most 10Ί0<sup>7</sup> cP, at most 9 · 10<sup>7</sup> cP, at most 8-10<sup>7</sup> cP, or at most 7 · 10<sup>7</sup>.
In accordance with still other characteristics in the described preferred embodiments, the first dynamic viscosity first dynamic viscosity is within a range of 10<sup>6</sup> cP at 2.5-10<sup>8</sup> cp, 10<sup>6</sup> cP to 2.010<sup>8</sup> cp, 10<sup>6</sup> cP a
2.5-10<sup>8</sup> cp, 10<sup>6</sup> cP to 10<sup>8</sup> cp, 3-10<sup>6</sup> cp at 10<sup>8</sup> cp, 5-10<sup>6</sup> cp a
<td> 3-10<sup>8</sup></td><td>cp,</td><td> 5-10<sup>6</sup> cp at 3-10<sup>8</sup> cp, 8-10<sup>6</sup> cp</td><td>to 3</td><td> • 10<sup>8</sup></td><td>cp,</td><td> 8-10<sup>6</sup> cp</td>
<td>to 10<sup>8</sup></td><td>cp,</td><td> 10<sup>7</sup> cp at 3 · 10<sup>8</sup> cp, 10<sup>7</sup> cp to 2</td><td> • 10<sup>8</sup></td><td>cp,</td><td> 10<sup>7</sup></td><td>cp at 10<sup>8</sup></td>
<td>cp, 2</td><td> • 10<sup>7</sup></td><td>cp at 3 · 10<sup>8</sup> cp, 2 · 10<sup>7</sup> cp to 2</td><td> 10<sup>8</sup></td><td>cp,</td><td>or 2</td><td> 10<sup>7</sup> cp a</td>
10<sup>8</sup> cp.
In accordance with still other characteristics in the described preferred embodiments, the first dynamic viscosity is at least 2-10<sup>6</sup> cP, at least 4 · 10<sup>6</sup> cP cP, at least 7-10<sup>6</sup> cP cP, at least 10<sup>7</sup> cP, at least 2.5-10<sup>7</sup> cP, or at least 4 · 10<sup>7</sup> cP.
In accordance with still other characteristics in the described preferred embodiments, the second dynamic viscosity is at least 9-10<sup>7</sup> cP, at least 10<sup>8</sup> cp, at least 1.2 · 10<sup>8</sup> cP, at least 1.5 · 10<sup>8</sup> cP, at least 2.0 · 10<sup>θ</sup> cP, at least 2.5-10<sup>8</sup> cP, at least 3.0-10<sup>8</sup> cP, at least 3.5-10<sup>8</sup> cP, at least 4 · 10<sup>8</sup> cP, at least 5.0-10<sup>8</sup> cP, at least 7.5-10<sup>8</sup> cP, at least 10<sup>9</sup> cP, at least 2-10<sup>9</sup> cP, at least 4-10<sup>9</sup> cP, or at least 6-10<sup>9</sup> cP.
In accordance with still other characteristics of the described preferred embodiments, the ratio of the second dynamic viscosity, at 90 ° C, to the first dynamic viscosity, at 60 ° C, is at least 1.2, at least 1.3, so minus 1.5, at least 1.7, at least 2, at least 2.5, at least 3, at least 4, at least 4.5, at least 5, at least 6, at least 7, or by at least 8.
In accordance with still other characteristics of the described preferred embodiments, this viscosity ratio is at most 30, at most 25, at most 20, at most 15, at most 12 or at most 10.
In accordance with still other characteristics of the described preferred embodiments, the ink films have a glass transition temperature (T<sub>g</sub>) at most 50 ° C, at most 44 ° C, at most 42 ° C, at most 39 ° C, at most 37 ° C, at most 35 ° C, at most 32 ° C , at most 30 ° C, or at most 28 ° C.
In accordance with still other characteristics of the described preferred embodiments, the plurality of ink films contains at least one dispersible or water-soluble material.
In accordance with still other features of the disclosed preferred embodiments, the water soluble material includes at least one aqueous dispersant.
In accordance with still other characteristics of the described preferred embodiments, the ink films contain at least 30%, at least 40%, at least 50%, at least 60%, or at least 7 0% by weight , of the material soluble or dispersible in water.
In accordance with still other characteristics of the described preferred embodiments, the ink films contain at most 5%, at most 3%, at most 2%, at most 1%, or at most 0.5% particles of inorganic fillers (such as silica or titania), by weight.
<td>In accordance with</td><td colspan="2">still others</td><td colspan="2">characteristics</td><td>of</td>
<td colspan="2">the preferred modalities</td><td>described,</td><td>the</td><td>films</td><td>of</td>
<td>ink are laminated over</td><td>the</td><td>surface</td><td>of the</td><td>substratum</td><td>of</td>
Print.
In accordance with still other characteristics of the described preferred embodiments, the ink films contain at least 1.2%, at least 1.5%, at least 2%, at least 3%, at least 4%, at least 6%, at least 8%, or at least 10% of the dye, by weight.
In accordance with still other characteristics of the described preferred embodiments, the ink films contain at least 5%, at least 7%, at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the resin, by weight.
In accordance with still other characteristics of the described preferred embodiments, the colorant includes at least one pigment.
In accordance with still other characteristics of the described preferred embodiments, the weight ratio of resin to dye within the plurality of ink films is at least 1: 1, at least
<td>1.25: 1, at least</td><td>1.5: 1, for</td><td>the</td><td>minus 1.75: 1,</td><td>by</td><td>the</td>
<td colspan="2">minus 2: 1, at least 2.5: 1,</td><td>by</td><td>at least 3: 1,</td><td>by</td><td>the</td>
<td>minus 3.5: 1, so</td><td>minus 4: 1,</td><td>by</td><td>at least 5: 1,</td><td>by</td><td>the</td>
<td colspan="2">minus 7: 1, or at least 10: 1.</td><td></td><td></td><td></td><td></td>
<td>Agree</td><td>with still</td><td colspan="3">Other features</td><td>of</td>
In the preferred embodiments described, the solubility of the resin in water, at a temperature within a temperature range of 20 ° C to 60 ° C, and at a pH within a pH range of 8.5 to 10, is at least 3%, at least 5%, at least 8%, at least 12%, at least 18%, or at least 2 5%, by weight of the resin dissolved by the weight of the solution.
In accordance with still other features of the described preferred embodiments, the ink films fixedly adhered to the surface are adhered primarily, or substantially exclusively, by a physical bond between each of the ink films and the surface.
In accordance with still other characteristics of the described preferred embodiments, the adhesion of the ink films to the surface is substantially devoid of an ionic character.
In accordance with still other characteristics of the described preferred embodiments, the adhesion of the ink films to the surface is substantially devoid of a chemical bonding character.
In accordance with still other characteristics of the described preferred embodiments, the ink dot has a glass transition temperature (T<sub>g</sub>) at most 47 ° C, at most 40 ° C, at most 35 ° C, or at most
30 ° C.
In accordance with still other characteristics of the described preferred embodiments, the ink dot contains less than 2%, less than 1%, less than 0.5%, or less than 0.1% of one or more charge managers, or is substantially devoid of Cargo managers.
In accordance with still other characteristics of the described preferred embodiments, the ink dot contains less than 5%, less than 3%, less than 2%, or less than
0.5% of one or more hydrocarbons or oils, or is substantially devoid of such hydrocarbons or oils.
In accordance with still other characteristics of the described preferred embodiments, the fibers of the fibrous printing substrate directly contact the ink dot.
In accordance with still other features of the disclosed preferred embodiments, the commodity coated fibrous printing substrate contains a coating having less than 10%, less than 5%, less than 3%, or less than 1%, by weight, of a water absorbent polymer.
In accordance with still other characteristics of the described preferred embodiments, the first fibrous printing substrate is a paper.
In accordance with still other characteristics of the described preferred embodiments, the printing substrate is a fibrous paper selected from the group of papers consisting of bond paper, uncoated offset (photo-printing) paper, coated offset (photo-printing) paper, paper. copy paper, mechanical pulp paper, shredded coated paper, freesheet paper, coated freesheet paper, and laser paper.
In accordance with still other characteristics of the described preferred embodiments, an average thickness of the ink film or single ink dot is at
<td>sumo</td><td>1,600 nm, at</td><td>the</td><td>sumo</td><td> 1.200</td><td>nm,</td><td>900 nm at</td><td>the</td><td>at the most</td>
<td>sumo</td><td>800nm, 700</td><td>nm</td><td>to what</td><td>sumo,</td><td>to what</td><td>sumo 650</td><td>nm</td><td>, at most</td>
<td> 600</td><td>nm, 500nm to</td><td>the</td><td>sumo,</td><td>to what</td><td>sumo</td><td>450 nm, or</td><td>to</td><td>at most 400</td>
nm.
In accordance with still other characteristics of the described preferred embodiments, the average thickness of the single ink dot is within a range of 100-800nm, 100-600nm, 100-500nm, 100-450nm, 100-400nm, 100350nm, 100 -300nm, 200-450nm, 200-400nm, or 200-350nm.
In accordance with still other characteristics of the described preferred embodiments, the average thickness of the single ink dot is at least 50 nm, at least 100 nm, at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, or at least 350 nm.
In accordance with still other characteristics of the described preferred embodiments, the ink dot is laminated onto the surface of the printing substrate.
In accordance with still other characteristics of the described preferred embodiments, the total concentration of the dye and resin within the ink point is at least 7%, at least 10%, at least 15%, at least 2 0 %, at least 3 0%, at least 40%, at least 50%, at least 60%, at least 70%, or at least 85%.
In accordance with still other characteristics of the described preferred embodiments, the ratio of the surface nitrogen concentration at the top surface of the film to the volumetric nitrogen concentration within the film is at least 1.2: 1,
<td>for the</td><td>minus 1.3: 1,</td><td>by</td><td>the</td><td>minus 1.5: 1,</td><td>by</td><td>the</td><td>less</td>
<td> 1.75:1,</td><td>at least</td><td> 1.2</td><td> :1,</td><td>at least</td><td> 1.3:1</td><td>z</td><td>for the</td>
<td>Minus 1.</td><td colspan="2">5: 1, at least</td><td> 2:1</td><td>, at least</td><td> 3:1,</td><td>or</td><td>for the</td>
<td>minus 5:</td><td> 1.</td><td></td><td></td><td></td><td></td><td></td><td></td>
In accordance with still other characteristics of the described preferred embodiments, the ratio of concentration of the atomic surface of nitrogen to carbon (N / C) on the upper surface of the film to the atomic ratio of the volumetric concentration of nitrogen to carbon (N / C) at depth, it is at least 1.1: 1, at least 1.2: 1, at least 1.3: 1, at least 1.5: 1, at least 1.75: 1, or at least 2: one.
In accordance with still other characteristics of the described preferred embodiments, the ink film contains at least one colorant dispersed in an organic polymeric resin.
In accordance with still other characteristics of the described preferred embodiments, the surface concentration of secondary amines, tertiary amines, and / or ammonium group on the surface of the top film exceeds their respective volumetric concentrations at a depth of at least 30 nanometers below of the film surface.
In accordance with still other characteristics of the described preferred embodiments, the surface of the top film contains at least one polyethylene imine (PEI).
Consistent with still other features of the disclosed preferred embodiments, the top film surface contains a secondary amine that exhibits a peak X-ray photoelectron spectroscopy (XPS) at 402.0 ± 0.4 eV, 402.0 ± 0.3 eV, or 402.0 ±
0.2 eV.
In accordance with still other characteristics of the described preferred embodiments, the surface of the top film exhibits a peak of X-ray photoelectron spectroscopy (XPS) at 402.0 ± 0.4 eV, 402.0 ± 0.3 eV, or 402.0 ± 0.2 eV. In accordance with still other features of the described preferred embodiments, the surface of the top film contains a poly quaternium cationic guar.
In accordance with still other features of the disclosed preferred embodiments, the poly quaternium cationic guar includes at least one of a guar hydroxypropyltrimonium chloride and a guar hydroxypropyltrimonium hydroxypropyltrimonium chloride. In accordance with still other characteristics of the described preferred embodiments, the surface of the top film contains a polymer which has at least one quaternary amine group.
In accordance with still other characteristics of the described preferred embodiments, the ammonium group includes a salt of a primary amine.
In accordance with still other characteristics of the described preferred embodiments, the salt includes, or consists of, an HCl salt.
In accordance with still other characteristics of the described preferred embodiments, the top film surface contains a polymer or compound selected from the group consisting of poly (diallyldimethylammonium chloride), poly (4-vinylpyridine), polyallylamine, co-polymer of vinyl pyrrolidone-dimethylaminopropyl methacrylamide, a vinyl methacrylate copolymer caprolactam-dimethylaminopropyl methacrylamide hydroxyethyl, a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate.
In accordance with still other characteristics of the described preferred embodiments, the ink film
<td>has</td><td>medium thickness</td><td>at most</td><td>5,000 nanometers,</td><td>to</td><td>the</td>
<td>sumo</td><td>4,000 nanometers,</td><td>at most 3</td><td>500 nanometers</td><td>to</td><td>the</td>
<td>sumo</td><td>3,000 nanometers,</td><td>at most 2</td><td>500 nanometers</td><td>to</td><td>the</td>
<td>sumo</td><td>2,000 nanometers,</td><td>at most 1</td><td>, 500 nanometers.</td><td>to</td><td>the</td>
<td>sumo</td><td>1,200 nanometers,</td><td>at most 1</td><td>, 000 nanometers.</td><td>to</td><td>the</td>
at most 800 nanometers, or at most 650 nanometers.
In accordance with still other characteristics of the described preferred embodiments, the ink film has an average thickness of at least 100 nanometers, at least 150 nanometers, or at least 175 nanometers.
According to still other characteristics of the described preferred modalities, the mean deviation of convexity is at most 0.04, at most 0.03, at most 0.025, at most 0.022, at most 0.02, at most 0.018, at most 0.017, at most 0.016, at most 0.015, or at most 0.014.
In accordance with still other characteristics of the described preferred embodiments, the square geometric projection has a lateral length within a range of 0.5 mm to 15 mm.
In accordance with still other characteristics of the described preferred embodiments, the square geometric projection has a lateral length of approximately 10mm, 5mm, 2mm, 1mm, 0.8mm, or 0.6mm.
In accordance with still other characteristics of the described preferred embodiments, the diameter of the ink jet point is at least 7, at least 10, at least 12, at least 15, at least 18, or at least minus 20 micrometers.
In accordance with still other characteristics of the described preferred modalities, the mean deviation of convexity is at most 0.013, at most 0.012, at most 0.010, at most 0.009, or at most 0.008.
In accordance with still other characteristics of the described preferred modalities, the mean convex deviation for plastic substrates is at most 0.013, at most 0.012, at most 0.010, at most 0.009, or at most 0.008.
In accordance with still other characteristics of the described preferred embodiments, the plurality of ink dots shows on the plastic printing substrate an adhesive failure of at most 10%, or at most 5%, when subjected to a test of standard tape.
In accordance with still other features of the described preferred embodiments, the plurality of ink dots is substantially free of adhesive failure when subjected to a standard tape test.
In accordance with still other characteristics of the described preferred embodiments, the set of ink dots has at least 20, at least 50, or at least 200 of the different ink dots.
In accordance with still other characteristics of the described preferred modalities, DC<sub>do</sub>t mean is at least 0.0005, at least 0.001, at least 0.0015, at least 0.002, at least 0.0025, at least 0.003, at least 0.004, at least 0.005, at least 0.006, by at least 0.008, at least 0.010, at least 0.012, or at least 0.013.
In accordance with still other characteristics of the described preferred embodiments, the average thickness is within a range of 100-1,200nm, 200-1,200nm, 200-1,000nm, 100-800nm, 100-600nm, 100-500nm, 100-450nm, 100400nm, 100-350nm, 100-300nm, 200-450nm, 200-400nm or 200-350nm.
In accordance with still other characteristics of the described preferred embodiments, the average thickness is at most 1,800 nm, at most 1,500 nm, at most 1,200 nm, at most 1,000nm, at most 800nm, at most 500nm , at most 450 nm, or at most 400 nm.
In accordance with still other characteristics of the described preferred embodiments, the average thickness is at least lOOnm, at least 150nm, at least 175 nanometers, at least 200nm, at least 250nm, at least 300nm, or at least 350nm.
In accordance with still other characteristics of the described preferred modalities, the mean roundness deviation (DRdot mean) is at most 0.60, at most 0.60, at most 0.50, at most 0.45, at most 0.40, at most
0.35, at most 0.30, at most 0.25, or at most 0.20.
According to still other characteristics of the described preferred modalities, DCaot is at most 0.04, at most 0.03, at most 0.025, at most 0.022, at most 0.02, at most 0.018, at most 0.017, at the most
0.016, at most 0.015, at most 0.014, at most 0.013, at most 0.012, at most 0.011, or at most 0.010, for an uncoated substrate.
In accordance with still other characteristics of the described preferred modalities, DC<sub>do</sub>t is at least 0.0005, at least 0.001, at least 0.0015, at least 0.002, at least 0.0025, at least 0.003, at least 0.004, at least 0.005, at least 0.006, or at least minus 0.008, for an uncoated substrate.
In accordance with still other characteristics of the described preferred modalities, DC<sub>do</sub>t is at most 0.022, at most 0.02, at most 0.018, at most 0.016, at most 0.014, at most 0.012, at most 0.010, at most 0.008, at most 0.006, at most 0.005, or at most 0.004, for a commodity coated substrate.
In accordance with still other characteristics of the described preferred modalities, DC<sub>dot</sub> is at least 0.0005, at least 0.001, at least 0.0015, at least 0.002, at least 0.0025, at least 0.003, or at least 0.0035, for the commodity coated substrate.
In accordance with still other characteristics of the described preferred embodiments, the uncoated printing substrate is a coated substrate or an uncoated offset substrate.
In accordance with still other features in the preferred embodiments described, the fibrous printing substrate is a commodity coated printing substrate.
In accordance with still other characteristics of the described preferred embodiments, the volume of color gamut shown by the ink film structure is at least 520 kilograms (AE)<sup>3</sup>, at least 540 kilo (AE)<sup>3</sup>, at least 560 kilo (AE)<sup>3</sup>, or at least 580 kilo (ΔΕ)<sup>3</sup>.
In accordance with still other characteristics of the described preferred embodiments, the plurality of continuous ink films has a plurality of individual ink dots, arranged above a surface of the substrate, the ink dots have an average thickness of at most 900 nanometers, at most 800 nanometers, at most 700 nanometers, at most 650 nanometers, at most 600 nanometers, at most 550 nanometers, or at most 500 nanometers.
In accordance with still other features of the described preferred embodiments, the plurality of continuous ink films includes a plurality of individual ink dots having a first thickness disposed above the zone and a second thickness disposed below the zone, within of the substrate, of a total of the first thickness and the second thickness being at most 900 nanometers, at most 800 nanometers, at most 700 nanometers, or at most 600 nanometers.
In accordance with still other characteristics of the preferred described modalities, the first thickness, or the total thickness, is at most 0.8 microns, at most 0.7 microns, at most 0.65 microns, at most 0.6 microns, at most 0.55 micrometers, at most 0.5 microns, at most 0.45 microns, or at most 0.4 microns.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be further described, by way of example, with reference to the accompanying drawings, in which:
Figure 1A shows a top view of an enlarged image of a plurality of inkjet ink droplets arranged on a paper substrate, in accordance with prior art inkjet printing technology;
Figure IB shows a top view of an enlarged image of a plurality of inkjet layers arranged on a paper substrate, in accordance with the inkjet printing technology of the present invention;
Figures 2A-2C show three-dimensional amplified images acquired by laser microscope of ink stains or films on paper substrates, obtained using different printing technologies, in which: Figure 2A is an enlarged image of an offset stain; Figure 2B is an enlarged image of a liquid offset stain (LEP); and Figure 2C is an enlarged image of an inkjet film structure of the invention;
Figure 2D shows a two-dimensional shape that has the mathematical property of a convex set;
Figure 2E shows a two-dimensional shape that has the mathematical property of a non-convex set;
Figure 2F is a schematic top view of an ink film having a tributary and an inlet, the schematic view showing a smoothed view of the ink image;
Figures 3A, 3B, and 3C show surface roughness and surface height measurements for the offset inkblot structure, the LEP inkblot structure, and the inkjet film structure of the invention. provided in Figures 2A-2C;
Figures 3D and 3E provide respective schematic cross-sectional views of an ink film structure of the invention and a prior art ink jet dot structure, wherein the substrate is a fibrous paper substrate;
Figure 3F shows a graph depicting the atomic concentration of copper at the ink point and within the fibrous paper substrate, as a function of depth, within a first technique cyan color inkjet ink film structure previous;
Figure 3G shows a graph depicting the atomic concentration of copper at the ink point and within the fibrous paper substrate, as a function of depth, within a second art cyan color inkjet film structure. previous;
Figure 3H shows a graph depicting the atomic concentration of copper at the ink point and within the fibrous paper substrate, as a function of depth, within a cyan color ink film structure of the present invention;
Figures 4a and 4C each show an image of the surface of the outer layer of an intermediate transfer member; Figures 4B and 4D are images of the surface of the corresponding ink films produced using said outer layers, in accordance with the present invention;
Figure 5A shows images of ink stains or films obtained using different printing technologies on coated paper, along with the corresponding image processor computerized contours and their convex projections;
Figure 5B shows images of ink stains or films obtained using different printing technologies on uncoated paper, along with the corresponding image processor computerized contours and their convex projections;
Figure 5C shows bar graphs of the roundness deviation for the ink dots on each of the 19 fibrous substrates, in accordance with some embodiments of the present invention, and for the ink dots produced by an inkjet printing technology. prior art ink;
Figure 5D provides bar graphs of the convex deviation for the ink dots on each of the 19 fibrous substrates, in accordance with some embodiments of the present invention, and for the ink dots produced by inkjet printing technology. prior art ink;
Figure 5E-1 provides comparative bar charts of roundness deviation for ink dot structures produced in accordance with some embodiments of the present invention, versus ink dots produced using a reference printing ink method and formulation. , for each of the 10 fibrous substrates;
Figure 5E-2 provides comparative bar graphs of the convex deviation of the ink dot structures of Figure 5E-1, for each of the fibrous substrates;
Figure 5F-1 provides an enlarged view of an ink dot field on a commodity coated fibrous substrate produced using a commercially available aqueous direct inkjet printer;
Figure 5F-2 provides an enlarged view of a field having an ink dot structure according to the present invention, wherein the commodity coated substrate is identical to that of Figure 5F-1;
Figure 5G-1 provides an enlarged view of an ink dot field on an uncoated fibrous substrate, produced using a commercially available aqueous direct inkjet printer;
Figure 5G-2 provides an enlarged view of a field of an ink dot structure according to the present invention, wherein the uncoated substrate is identical to that of Figure 5G-1;
Figures 5H-1 to 5H-3 provide enlarged views of the ink dot structures in accordance with the present invention, where an ink dot is printed on each of several plastic substrates;
Figure 5H-4 shows an enlarged top view and an instrumental cross-sectional view of an ink film structure of the invention having an ink dot arranged on a plastic substrate;
Figures 5H-5 through 5H-7 each provide an enlarged view of a field having an ink dot structure in accordance with the present invention, each field containing the ink dots printed on a respective plastic substrate;
Figures 6A-1 through 6J-2 provide images of ink stains or films obtained using different printing technologies on uncoated (6A-6E-1 to 1) and coated (6F-1 to 6J-1) paper, and optical uniformity profiles (6A-2 to 6J-2) therefor;
Figure 7 is a deceleration temperature sweep of dynamic viscosity as a function of temperature, for various ink formulations of the present invention;
Figure 8 is a temperature sweep in deceleration of dynamic viscosity as a function of temperature, for various ink formulations of the present invention, versus various commercially available inkjet inks;
Figure 9 is an enlarged view of the graph of Figure 8, for lower viscosities;
Figure 10 shows the viscosity as a function of temperature for an ink residue recovered from printed films produced from the ink formulations of the present invention;
Figure 11 provides a graphical representation of high temperature dynamic viscosity measurements for: a dry ink residue from a prior art black inkjet formulation; a dry ink residue recovered from the printed images of the prior art inkjet formulation; a dry ink residue from a black ink formulation of the present invention; and a dry ink residue recovered from the printed images of said ink formulation;
Figure 12 shows optical density measurements, along with a fitted curve (the lowest curve) of the optical density obtained as a function of film thickness, for a particular ink formulation;
Figure 13 provides the optical density measurements of Figure 12, plotted as a function of the calculated pigment content or pigment thickness;
Figure 14A provides a graph showing seven representations of color gamut according to ISO 15339; and
Figure 14B graphically represents a color gamut representation according to an embodiment of the present invention versus a # 6 color gamut representation according to the standard.
ISO 15339.
DETAILED DESCRIPTION OF THE ILLUSTRATED MODALITIES
The ink film structures according to the present invention can be better understood with reference to the drawings and the accompanying description.
Before explaining at least one embodiment of the invention in detail, it should be understood that the invention is not limited in its application to the details of the structure and arrangement of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments or of being practiced or carried out in various ways. Also, it should be understood that the phraseology and terminology used herein is for the purpose of description and should not be construed as limiting.
Description of the printing process and system
The present invention relates to ink film structures that can be obtained, in particular, by the following printing process or the use of any printing system that applies said process. A suitable printing process for the preparation of the ink films according to the invention includes directing drops of an ink onto an intermediate transfer member to form an ink image, the ink includes an organic polymeric resin and a colorant (for example , a pigment or dye) in an aqueous vehicle, and the transfer member has a hydrophobic outer surface, each ink drop in the ink image on the diffusion impinges on the intermediate transfer member to form an ink film (for example, a thin film that preserves a significant part of the flattening and horizontal extent of the drop present on impact or covering an area that depends on the mass of ink in the drop). The ink dries while the ink image is being transported by the intermediate transfer member by evaporation of the aqueous vehicle from the ink image to leave a residue of resin film and dye. The film residue is then transferred to a substrate (eg, by pressing the intermediate transfer member against the substrate to print the film residue thereon). The chemical compositions of the ink and the surface of the intermediate transfer member are selected such that the intermolecular attractive forces between the molecules on the outer skin of each drop and on the surface of the intermediate transfer member counteract the tendency of the ink film produced by each droplet run under the action of the surface tension of the aqueous vehicle, without causing each drop to diffuse by wetting the surface of the intermediate transfer member.
The printing process sets out to preserve, or freeze, the thin pancake shape of each aqueous ink drop, which is caused by flattening of the ink drop by impacting the surface of the intermediate transfer member (also called the layer of release), despite the hydrophobicity of said layer. To achieve this goal, this new procedure relies on electrostatic interactions between the molecules in the ink and on the outer surface of the transfer member, the molecules being either charged in their respective medium or mutually chargeable, becoming charge opposite to the interaction between ink and release layer. Further details on the printing processes and related systems suitable for the preparation of the ink structures according to the present invention are described in PCT Applications numbers PCT / IB2013 / 051716 (Attorney LIP reference 5/001 PCT); PCT / IB2013 / 051717 (Lawyer's reference LIP 5/003 PCT); and PCT / IB2013 / 051718 (attorney's reference LIP 5/006 PCT).
For example, a conventional hydrophobic surface, such as a silicone coated surface, will easily give up electrons and is considered negatively charged. Polymeric resins in an aqueous vehicle are also generally negatively charged. Therefore, in the absence of additional measures, the adoption of the net intermolecular forces will cause the intermediate transfer member to repel the ink and the droplets will tend to run into spherical globules.
In the novel printing process suitable for the preparation of ink film structures according to the invention, the chemical composition of the surface of the intermediate transfer member is modified to provide a positive charge. This can be accomplished, for example, by including on the surface of the intermediate transfer member (eg, embedded in the release layer) molecules that have one or more Bronsted base functional groups and, in particular, that comprise nitrogen molecules. Suitable positively charged or chargeable groups include primary amines, secondary amines, and tertiary amines. Such groups may be covalently attached to polymeric backbones, and, for example, the outer surface of the intermediate transfer member may include amino silicones. Further details on intermediate transfer members, including basic functional groups in their Bronsted release layers, suitable for the preparation of ink film structures according to the present invention are described in PCT Application N<sup>2</sup> PCT / IB2013 / 051751 (lawyer reference
LIP 10/005 PCT).
Such positively chargeable functional groups on the release layer molecules can interact with Bronsted acid functional groups on the ink molecules. Suitable negatively charged or chargeable groups include carboxylated acids such as those having carboxylic acid groups (COOH), acrylic acid groups (CH<sub>2</sub>= CH-COOH), methacrylic acid groups (CH<sub>2</sub>= C (CH<sub>3</sub>) -COOH) and sulfonates such as those with sulfonic acid groups (-SO<sub>3</sub>H). Such groups can be covalently attached to main polymer chains and preferably be soluble or dispersible. Suitable ink molecules can for example comprise acrylic based resins, such as an acrylic polymer and an acrylic-styrene copolymer having carboxylic acid functional groups. More details on ink compositions that can be used to achieve the ink film structures according to the present invention are described in PCT Application N<sup>2</sup>
PCT / IB2013 / 051755 (reference from Lawyer LIP 11/001 PCT).
An alternative to avoid repelling ink droplets by the hydrophobic surface of the negatively charged intermediate transfer member is to apply a conditioning or pretreatment solution to the surface of the intermediate transfer member to reverse its polarity to positive. One can observe such treatment of the transfer member by applying a very thin layer of a positive charge that is itself adsorbed on the surface of the release layer, but has a net positive charge on its opposite side with which the charged molecules negatively in the ink can interact. Intermediate transfer members susceptible to this treatment may, for example, comprise in their release layer silicones modified with silanol-, silyl- or silane- or terminated in polydialkyl-siloxane and further details on suitable insecticide-treated materials are described in the PCT Application N<sup>to</sup> PCT / IB2013 / 051743 (reference of
Lawyer LIP 10/002 PCT).
Chemical agents suitable for the preparation of this type of conditioning solutions, if necessary, have relatively high charge density and can be polymers containing nitrogen amine atoms in a plurality of functional groups, which need not be the same and they can be combined (eg, primary, secondary, tertiary amine, or quaternary ammonium salts). Although macromolecules having a molecular weight from a few hundred to a few thousand copolymer may be suitable conditioning agents, it is believed that polymers having a high molecular weight of 10,000 g / mol or more are preferable. Suitable conditioning agents include guar hydroxypropyltrimonium chloride, guar-hydroxypropyl hydroxypropyl trimonium chloride, linear or branched polyethylene imine, modified polyethylene imine, vinyl pyrrolidone dimethylaminopropyl methacrylamide methacrylamide copolymer, vinyl dimethylaminopropyl methacrylamide, caprolactam quaternized vinyl pyrrolidone dimethylaminoethyl, poly (diallyldimethyl ammonium chloride), poly (4-vinylpyridine) and polyallylamine. Further details on suitable elective conditioning solutions for the preparation of ink film structures according to the present invention are described in PCT Application N<sup>s</sup> PCT / IB2013 / _ (lawyer reference LIP 12/001 PCT).
The disclosure of the aforementioned same applicant applications, which are incorporated by reference in their entirety as set forth herein, may overlap with the current disclosure, but it should be clear that the present invention is not limited to such a process, using the intermediate transfer members, elective conditioning solutions, and ink compositions exemplified therein. The pertinent parts of the description of these applications are included herein for the convenience of the reader.
Ink Description
The inventors have found that the ink film structures of the invention, if obtained for example by the above-described printing system and process, may require an ink or inkjet ink having particular chemical and physical properties. These physical properties can include one or more thermo-rheological properties.
In accordance with an embodiment of the invention, there is provided an exemplary inkjet formulation (Example 1) containing:
Pigment: Jet Magenta DMQ (BASF) 2%
Joncryl HPD 296 (35.5% solution in water) (BASF) 30% Glycerol (Aldrich) 20% polydimethylsiloxane polyether modified
BYK 345 (BYK) 0.5%
Water (distilled) Balance at 100%
Nominally, the resin solution may be, or include, a styrene acrylic co-polymer (or co (methacrylic acid ethyl acrylate) solution. The average molecular weight may be less than 20,000 g / mol.
Preparation procedure:
A pigment concentrate, containing pigment (10%), distilled water (70%) and resin, in the present case, Joncryl HPD 296 (20%), was made from the components described above. The pigment, water, and resin were mixed and ground using a home router. Alternatively, milling can be performed using any of the many commercially available milling machines deemed suitable by one of ordinary skill in the art. The progress of grinding was monitored by measurement of particle size (Malvern, Nanosizer). Grinding stopped when the average particle size (d<sub>50</sub>) came to about 70 nanometers (nm). The remainder of the components were then added to the pigment concentrate to produce the exemplary inkjet ink formulation described above. After mixing, the ink was filtered through a 0.5-micron (pm) filter.
The viscosity of the solution was approximately 9 cP at 25 ° C. The surface tension at 25 ° C was approximately 25 mN / m.
Various other grinding procedures and grinding apparatus will be apparent to those of ordinary skill in the art. Various commercially available nano-pigments can be used in the ink formulations of the invention. These include pigment preparations such as Hostajet Magenta E5B-PT and Hostajet Black O-PT, both from Clariant, as well as pigments that demand post-dispersion processes, such as Cromophtal Jet Magenta DMQ and Irgalite Blue GLO, both from BASF.
One of skill in the art can readily recognize that various known dyes and dye formulations can be used in the ink or inkjet formulations of the invention. In one embodiment, said pigments and pigment formulations may include, or consist essentially of, ink dyes and inkjet ink formulations.
Alternatively or additionally, the colorant may be a dye. Examples of colorants suitable for use in the ink formulations of the present invention include: Duasyn Yellow 3CF-SF Liquid, Duasyn Acid Yellow XX-SF, Duasyn Red 3B-SF Liquid, Duasynjet Cyan FRL-SF Liquid (all manufactured by Clariant ); Basovit Yellow 133, Fastusol Yellow 30 L, Basacid Red 495, Basacid Red 510 Liquid, Basacid Blue 762 Liquid, Basacid Black X34 Liquid, Basacid Black X38 Liquid, Basacid Black X40
Liquid (all manufactured by BASF).
The following examples illustrate some ink compositions according to embodiments of the invention. Print tests employing such ink compositions in the method described in co-pending PCT application N<sup>to</sup> PCT / IB2013 / 051716 (Lawyer's reference LIP 5/001 PCT) show good transfer to various paper and plastic substrates.
Example 2
An injection ink formulation was prepared containing:
<td>Ingredient</td><td>Function</td><td>% in weigh</td>
<td>PV Fast Blue BG (Clariant)</td><td>Pigment</td><td> 2.3</td>
<td>Neocryl BT-9 (40% dispersion in water) (DSM resins)</td><td>Resin</td><td> 16.5</td>
<td>Glycerol (Aldrich)</td><td>Co-solvent miscible in water</td><td> 3.3</td>
<td>Capstone FS-65 (DuPont)</td><td>Nonionic Fluorosurfactant</td><td> 0.1</td>
<td>Distilled water)</td><td> -</td><td>100% balance</td>
<td>Joncryl HPD 296 (solution 35.5% in water) (BASF)</td><td>Dispersing</td><td>3.2 (solid resin)</td>
<td>Dietllenglicol (Aldrich)</td><td>Co-solvent miscible in water</td><td> 20</td>
<td>Diethyl amine (Aldrich)</td><td>PH adjustment (basic)</td><td> 1</td>
Preparation procedure:
A pigment concentrate, containing pigment (14%), water (79%), and Joncryl HPD 296 (7%), was mixed and ground. Milling progress is monitored based on particle size measurements {Malvern, Nanosizer).
Grinding stopped when the average particle size (d<sub>50</sub>) reached 70 nm. The remaining materials were then added to the pigment concentrate and mixed. After mixing, the ink was filtered through a 0.5 pm filter.
At 25 ° C, the ink viscosity thus obtained was approximately 13 cP, the surface tension around 27 mN / m, and the pH 9-10.
Example 3
An injection ink formulation was prepared containing:
<td>Ingredient</td><td>Function</td><td>% in weigh</td>
<td>Jet Magenta DMQ (BASF)</td><td>Pigment</td><td> 2.3</td>
<td>Neocryl BT-9 (40% dispersion in water) (DSM resins)</td><td>Resin</td><td> 17.5</td>
<td>Monoethanol amine</td><td>pH adjustment (basic)</td><td> 1.5</td>
<td>Propylene glycol</td><td>Co-solvent miscible in water</td><td> 20</td>
<td>N-methylpyrrolidone</td><td>Co-solvent miscible in water</td><td> 10</td>
<td>BYK 349 (BYK)</td><td>Surfactant (silicone)</td><td> 0.5</td>
<td>Distilled water)</td><td> -</td><td>100% balance</td>
Preparation procedure:
The pigment (10%), water (69%), Neocryl BT-26 (20%), and monoethanolamine (1%) were mixed and ground until the average particle size (d<sub>5</sub>o) reached 7 0 nm as described in Example 2. The rest of the materials were then added to the pigment concentrate and mixed. After mixing, the ink was filtered through a 0.5 μιη filter.
At 25 ° C, the ink viscosity thus obtained was approximately 8 cP, the surface tension was approximately 24 mN / m, and the pH was 9-10.
Example 4
An injection ink formulation was prepared containing:
<td>Ingredient</td><td>Function</td><td>% in weigh</td>
<td>Jet Magenta DMQ (BASF)</td><td>Pigment</td><td> 2.2</td>
<td>Joncryl 6S3 Neutralized with KOH (BASF)</td><td>Dispersing</td><td>0.6 (solid resin)</td>
<td>Neocryl BT-9 (40% dispersion in water) (DSM resins)</td><td>Resin</td><td> 25</td>
<td>Ethyl in glycol</td><td>Co-solvent miscible in water</td><td> 25</td>
<td>Propylene glycol</td><td>Co-solvent miscible in water</td><td> 10</td>
<td>PEG 400</td><td>Co-solvent miscible in water</td><td> 2</td>
<td>Glycerol</td><td>Co-solvent miscible in water</td><td> 3</td>
<td>BYK</td><td>surfactant (silicone)</td><td> 0.5</td>
<td>Distilled water)</td><td> -</td><td>100% balance</td>
Preparation procedure:
The pigment (12.3%), Joncryl 683 (3.3%) totally neutralized with a 30% solution of KOH (7.9%) and water (equilibrium) were mixed and ground until the average particle size (D<sub>50</sub>) reached 70 nm as described in Example 2. The rest of the materials below were added to the pigment concentrate and mixed. After mixing, the ink was filtered through a 0.5 μιη filter.
At 25 ° C, the ink viscosity thus obtained was approximately 7 cP, the surface tension was approximately 24 mN / m, and the pH was 7-8.
Ex empl o 5
An injection ink formulation was prepared containing:
<td>Ingredient</td><td>Function</td><td>% in weigh</td>
<td>Carbon Black Mogul L (Cabot)</td><td>Pigment</td><td> 2.2</td>
<td>Joncryl 671 Neutralized with KOH (BASF)</td><td>Dispersing</td><td>0.6 (solid resin)</td>
<td>NeoRad R-440 (40% emulsion in water) (DSM resins (</td><td>Resin</td><td> 30</td>
<td>Propylene glycol</td><td>Co-solvent miscible in water</td><td> 40</td>
<td>2-amino-2-methyl-l-propanol</td><td>pH adjustment (basic)</td><td> 1</td>
<td>Glycerol</td><td>Co-solvent miscible in water</td><td> 5</td>
<td>BYK 349 (BYK)</td><td>surfactant (silicone)</td><td> 0.5</td>
<td>Distilled water)</td><td> -</td><td>100% balance</td>
The pigment (14.6%), Joncryl 671 (3.9%) fully neutralized with a 3 0% solution of KOH (9.4%) and water (balance) were mixed and ground as described in Example 2, until the size particle medium (D<sub>50</sub>) reached 70 nm. The rest of the materials were then added to the pigment concentrate and mixed. After mixing, the ink was filtered through a 0.5 pm filter.
At 25 ° C, the ink viscosity thus obtained was approximately 10 cP, the surface tension was approximately 26 mN / m, and the pH was 9-10.
With respect to the previous examples, various other grinding procedures will be apparent to those of ordinary skill in the art.
Example 6
An injection ink formulation was prepared containing:
<td>Ingredient</td><td>% in weigh</td>
<td>Hostajet Black O-PT (Clariant)</td><td> 2.4</td>
<td>Neocryl BT-26, 40% dispersion in water (DSM resin {</td><td> 18.0</td>
<td>Monoethanol amine</td><td> 1.5</td>
<td>Propylene glycol</td><td> 20</td>
<td>N-methypyrrolidone</td><td> 10</td>
<td>BYK 349 (BYK)</td><td> 0.5</td>
<td>Water</td><td>100% balance</td>
The formulation provided above contains approximately 9.6% ink solids, of which 25% (2.4% of the total formulation) is pigment, and about 75% (40% * 18% = 7.2% of the total formulation) is resin, by weight.
Example 7
An injection ink formulation was prepared containing
Duasyn Red 3B-SF Liquid (Clariant)
4%
Joncryl 236 HPD (35.5% solution in water) 20% Diethylene glycol 20% N-methylpyrrolidone 10%
BYK 333 0.5%
Water (distilled balance at 100%
Example 8
An injection ink formulation was prepared containing:
<td>Ingredient</td><td>Function</td><td>% in weigh</td>
<td>Jet Magenta DMQ</td><td>Pigment</td><td> 2</td>
<td>Neocryl BT-102 (Dispersion 40% in water) (DSM resins)</td><td>Resin</td><td>twenty (8 ~ solid resin)</td>
<td>Propylene glycol (Aldrich)</td><td>Co-solvent miscible in water</td><td> 20</td>
<td>BYK 34S</td><td>Non-ionic Inflammatory Fluoros</td><td> 0/2</td>
<td>Disperbyk 198</td><td>Dispersing</td><td> 2</td>
<td>Distilled water)</td><td> -</td><td>100% balance</td>
Preparation procedure:
A pigment concentrate, containing pigment (14%), water (72%), and Disperbyk 198 (14%) were mixed and ground. The progress of the grinding was monitored based on the particle size measurements (Malvern, Nanosizer). Grinding was stopped when the mean particle size (dso) reached 70 nm. The remaining materials were then added to the pigment concentrate and mixed. After mixing, the ink was filtered through a 0.5 μιη filter.
At 25 ° C, the ink viscosity thus obtained was 5.5 cP, the surface tension of approximately 25 mN / m, and pH 6.5.
Example 9
An injection ink formulation was prepared containing:
<td>Ingredient</td><td>Function</td><td>% in weigh</td>
<td>Novoperm Yellow P-HG (Clariant)</td><td>Pigment</td><td> 1.1</td>
<td>Paliotol Yellow L1155 (BASF)</td><td>Pigment</td><td> 1.1</td>
<td>Joncryl 671 neutralized with KOH (BASF)</td><td>Dispersing</td><td>0.6 (solid resin)</td>
<td>NeoRad R-440 (40% emulsion in water) (DSM resins)</td><td>Resin</td><td> 30</td>
<td>Propylene glycol</td><td>Co-solvent miscible in water</td><td> 40</td>
<td>2-amino-2-methyl ol-pro panol</td><td>PH adjustment (basic)</td><td> 1</td>
<td>BK 349 (BYK)</td><td>Surfactant (silicone)</td><td> 0.5</td>
<td>Distilled water)</td><td> -</td><td>100% balance</td>
Preparation procedure:
The pigment (14.6%), Joncryl 671 (3.9%), fully neutralized with a 30% solution of KOH (9.4%), and water (balance) were mixed and ground as described in Example 2, until the mean particle size (d<sub>50</sub>) reached 70 nm. The rest of the materials were then added to the pigment concentrate and mixed. After mixing, the ink was filtered through a 0.5 pm filter.
At 25 ° C, the ink viscosity thus obtained was approximately 9 cP, the surface tension was approximately 26 mN / m, and the pH was 9-10.
Ink film structures
Referring now to the drawings, FIG. 1A is an enlarged image of a plurality of inkjet ink droplets arranged near an upper surface of a fibrous substrate (paper), in accordance with prior art technology. In this prior art ink and substrate structure, inkjet ink droplets penetrate the surface of the paper. Such a structure can be typical of various types of paper, including uncoated paper, where the paper can pull the ink carrier solvent and pigment into the matrix of the paper fibers.
Figure IB is an enlarged image of a plurality of exemplary ink film structures, such as inkjet film structures, in accordance with an embodiment of the present l
invention. In contrast to the prior art ink and substrate structure provided in Figure 1A, the structure of the inkjet ink film of the invention can be characterized by well-defined individual ink films, generally arranged above , and adhered to, the fibrous substrate. The single-drop inkjet films shown in Figure IB show superior optical density. These characteristics are particularly noticeable when compared to the characteristics of the ink structure and the prior art substrate, which shows inkjet ink droplets or smudges having a low optical density.
A microscope laser was used to produce comparative images of prior art greatly enlarged ink spots arranged on an upper surface of a sheet of paper. Figures 2A, 2B and 2C are respective three-dimensional magnified images of a lithographic offset inkblot offset (Figure 2A), an HPIndigo inkblot liquid electro-photograph (LEP) (Figure 2B), and a a single drop of ink for injection (Figure 2C) produced in accordance with an embodiment of the present invention.
The ink film of a single inkjet ink drop (or individual ink dots) was produced using the system and apparatus of the invention described herein, using the inventive ink formulation provided herein.
The prior art ink spots referenced above are commercially available. The offset sample is produced by a press
Ryobi 755, using Tiger Roller's BestACK process ink (Toka Shikiso Chemical Industry). The LEP sample was produced by an HP Indigo 7500 digital press, using HP Indigo ink. With reference to the substrates, the uncoated substrates were 170 gsm Mondy paper; the coated substrates were 170 gsm APP paper.
Imaging by laser microscopy was performed using an Olympus LEXT 3D laser measurement microscope, model OLS4000. The height of the film (spot, drop, or stain) was greater than each substrate and the surface roughness of each film or stain analyzed was calculated by the microscope system in a semi-automatic way.
The perimeter of the offset ink stain and the perimeter of the LEP ink stain have a plurality of overhangs or tributaries, and a plurality of inlets or gaps. These forms of ink can be irregular, and / or discontinuous. In contrast, the inkjet ink dot (Figure 2C) produced in accordance with the present invention has a manifestly rounded, convex shape. The perimeter of the ink film is relatively smooth, regular, continuous and well defined.
More particularly, the projections of the ink film of the invention against the surface of the substrate (i.e. the projections from a top view) tend to be rounded, convex projections forming a convex set, i.e. for each pair of dots within the projection, each point on the straight line segment that joins them is also within the projection. Such a convex set is shown in Figure 2D. In contrast, the tributaries and inputs to the projections of several of the prior techniques define those projections as non-convex sets, that is, for at least one straight line segment within a particular projection, a portion of that straight line segment the projection is arranged outside, as illustrated in Figure
2E.
It should be noted that the ink images can contain an extremely large amount of a plurality of single or double ink layers. For example, a 5mm by 5mm ink image, at 600 dpi, can contain more than 10,000 such individual ink films. Therefore, it may be appropriate to statistically define the ink film structures of the present invention: at least 10%, at least 20%, or at least 30%, and more typically, at least 50%, by at least 7 0%, or at least 90%, of the individual ink dots, or projections thereof, may be convex assemblies. These ink dots are preferably selected randomly.
It should also be noted that ink images may not have clear boundaries, particularly when those limits are viewed at high magnification. Therefore, it may be appropriate to relax the definition of the convex set where the non-convexities (tributaries or inlets) having a radial length L<sub>r</sub> (as shown in Figure 2F) up to 3000nm, up to 1,500nm, up to 1,000nm, up to 700nm, up to 500nm, up to 300nm, or up to 200nm, are ignored, excluded, or smoothed, so the ink film or ink film projection is considered to be a convex set. Radial length L<sub>r</sub> it is measured by drawing a radial line L from the center point C of the ink film image, through a particular tributary or inlet. Radial length L<sub>r</sub> is the distance between the actual boundary of the tributary or inlet, and a smoothed projection P<sub>B</sub> of the ink image, lacking tributary or input, and matching the contour of the ink film image.
Relatively speaking, it may be appropriate to relax the definition of the convex set where non-convexities (tributaries or inlets) that have a radial length of up to 15% of the average film / drop / stain diameter, up to 10%, and more typically, up to 5%, up to 3%, up to 2%, or up to 1%), are ignored, excluded, or smoothed, as above, so the ink film or projection film of the ink is considered to be a convex set.
Figures 3A, 3B, and 3C show surface roughness and surface height measurements for the offset inkblot, the LEP inkblot, and the inkjet film provided in Figures 2A-2C. The instrumentally measured heights (H) or thickness of the three samples were 7 62 nm for the offset ink drop and 1104 nm for the LEP ink drop. In contrast, the instrumentally measured height of the inventive inkjet film (Hfii<sub>m</sub>) is 355 nm.
Repeating the comparative study before described several times, using additional ink film samples, seems to confirm these results for prior art ink films. LEP specimens typically had a height or thickness within a range of 900-1150 nm, while offset lithographic specimens typically had a height or thickness within a range of 750-1200 nm.
Regarding the ink spots or films produced from inkjet ink droplets, we have found that the maximum average supra-substrate thickness of the ink spot can be calculated from the following equation:
Tavg (max) <sup>=</sup> Vdrop / [Afilm * Rvol] (I) where:
Tavgimax) is the maximum average supra-substrate thickness;
Vdrop is the volume of the injection drop, or a nominal or characteristic volume of an injection drop (for example, a nominal volume provided by the manufacturer or distributor of the inkjet head);
Afilm is the measured or calculated area of the ink dot; and
R<sub>V</sub>ol is a dimensionless ratio of the volume of original ink to the volume of the dry ink residue produced from said ink.
By way of example, an ink dot arranged on a plastic printing substrate has a surface area of 1075 square micrometers. The nominal size of the injection drop is 10.0 ± 0.3 picoliters. R<sub>V</sub>ol was experimentally determined: a container containing 20.0 ml of the ink was heated to 130 ° C until a dry residue was obtained. The residue had a volume of 1.8 ml.
Resulting in Equation (I), T<sub>AVG (MA</sub>x) = 10 picoliters / [1075μιη<sup>2</sup> * (20.0 / 1.8)] = 837 nanometers.
For generally round ink spots, the area of the ink spot can be calculated from the diameter of the ink spots. Furthermore, we have found that the dimensionless relation of R<sub>V</sub>ol is generally about 10 for a wide variety of inkjet inks.
While for inks penetrating the substrate the actual average thickness may be somewhat less than Tavg (max) / this calculation can reliably serve as an upper limit for the average thickness. On the other hand, in the case of several plastic substrates, and in the case of several premium coated substrates, the maximum average super-substrate thickness can be substantially equal to the average supra-substrate thickness. For multiple commodity coated substrates, the maximum average supra-substrate thickness can approximate the average supra-substrate thickness, often within 100 nanometers, 200 nanometers, or 300 nanometers.
Regarding the ink spots or films produced from inkjet ink droplets, we have found that the maximum average supra-substrate thickness of the ink spot can be calculated from the following equation:
Tavg (max) <sup>=</sup> [Vdrop * Pink * Fdresidue] / [Afilm * Pfiim] (II) where:
Pink is the specific gravity of the ink;
FnREsiDUE is the weight of the dry ink residue, divided by the weight of the original ink;
AND
Pfilm is the specific gravity of the ink.
Typically, the ratio of Ptinta to Pfilm is approximately 1, such that equation (II) can be simplified to:
TavG (MAX) = [VdROP * FnRESIDUE] / Afilm (ΠΙ)
For a wide variety of aqueous inkjet inks, Fiiresidue is equal to plus or minus the weight fraction of solids in the inkjet ink.
Using the Olympus LEXT 3D laser measurement microscope described above, the height above the substrate surface was measured for various ink structures.
Atomic Force Microscopy (AFM) is another high-precision measurement technique for measuring height and determining the thickness of the ink dot on a substrate. AFM measurements can be performed using commercially available devices such as Park Scientific Instruments Model AutoProbe CP, Probe Scanning Microscopy equipped with ProScan software version 1.3 (or later). The use of AFM is described in detail in the literature, for example, by Renmei Xu, et al., The Effect of INk Jet PApers Roughness on Print Gloss and Ink Film Thickness [Department of Paper Engineering, Chemical Engineering, and Imaging Center for Ink and Printability, Western Michigan University) (Kalamazoo, MI)].
With respect to the ink film structures of the present invention, the inventors have found that the thickness of the dry ink film on the substrate can be adjusted by modifying the injection ink formulation. To obtain a lower point thickness, such a modification may involve at least one of the following:
• reduction of the resin to pigment ratio;
• select a resin or resins that allow adequate film transfer, even with a reduced resin to pigment ratio;
• the use of finer pigment particles;
• reduction of the absolute amount of pigment.
To obtain thicker spots, at least one of the opposite modifications can be made (for example, increasing the resin to pigment ratio).
Such formulation changes may require or make various advantageous modifications to the operating conditions of the process. The inventors have found that lower resin to pigment ratios may require a relatively high transfer temperature. For a given inkjet ink formulation, a high transfer temperature can reduce the thickness of the ink film. Increasing the pressure of the pressure roller or cylinder towards the printing cylinder during transfer of the film residue to a substrate at the printing station can also reduce the thickness of the ink film. Furthermore, the thickness of the ink film can be reduced by increasing the contact time between the substrate and the intermediate transfer member, interchangeably referred to herein as an image transfer member and both abbreviated as ITM.
Despite all this, a minimum practical characteristic thickness (i.e., average) or average thickness for ink films produced in accordance with the present invention may be approximately 100nm. More typically, such ink films can have a thickness of at least 125nm, at least 150nm, so
<td>minus 175nm,</td><td>by</td><td>at least 200</td><td>nm,</td><td>at least 250</td><td>nm, for</td>
<td>at least 300</td><td>nm,</td><td>at least</td><td> 350</td><td>nm, at least</td><td>400nm,</td>
<td>at least</td><td> 450</td><td>nm, or so</td><td colspan="2">minus 500nm.</td><td></td>
<td colspan="2">Using</td><td>the guides</td><td>of</td><td>thickness of</td><td>movie</td>
Provided above, the inventors are capable of obtaining the film structures of the invention having a characteristic thickness or average thickness of at least 600 nm, at least 700 nm, at least 800 nm, at least 1,000 nm, at least minus 1,200 nm, or at least 1,500 nm. The characteristic thickness or average film thickness of a single drop (or a single ink dot) can be at most around 2,000 nm, at most 1,800 nm, at most 1,500 nm, at most 1,200 nm, at most at most 1,000 nm, or at most 900 nm. More typically, the characteristic thickness or average film thickness of a single drop may be at most 800nm, at most 700nm, at most 650nm, at most 600nm, at most 500nm, 450nm at at most, at most
400 nm, or at most 350 nm.
Using the film thickness guides outlined above, the inventors are able to obtain the film structures of the invention in which a characteristic thickness or average thickness of the ink film can be within a range of lOOnm, 125nm or 150nm up to 1,800nm, 1,500nm, 1,200nm, l, 000nm, 800nm, 700nm, 600nm, 550nm, 500nm, 450nm, 400nm or 350nm.
More typically, the characteristic thickness or average thickness of the ink film may be within a range of 175nm, 200nm, 225nm, or 250nm to 800nm, 700nm, 550nm, 600nm, 550nm, 500nm, 450nm, or 400nm. Adequate optical density and optical uniformity can be obtained using the ink systems, processes, and formulations of the present invention.
Aspect Ratio
The inventors have found that the diameter of an individual ink dot in the ink film structures of the present invention can be adjusted, among other things, by the selection of a suitable ink supply system for applying the ink {eg , injection) at the ITM, and by adjusting the properties of the ink formulation (eg, surface tension) to the requirements of the particular ink head.
This ink film diameter, D<sub>dot</sub>, or the average spot diameter at the substrate surface, D<sub>dot</sub>
<td>average; can be for</td><td>least</td><td>of</td><td> 10</td><td>micrometers,</td><td>by</td><td>the</td>
<td>minus 15 pm, or so</td><td>minus 20</td><td>p.m,</td><td colspan="3">and more typically</td><td>by</td>
<td>at least 30 pm, so</td><td>minus 40</td><td>p.m,</td><td>by</td><td>at least 50</td><td>p.m,</td><td>by</td>
at least 60 pm, or at least 75 pm. D<sub>dot</sub> or D<sub>do</sub>t average can be at most 300 micrometers, at most 250 pm, or at most 200 pm, and more typically, at most 175 pm, at most 150 pm, at most 120 pm, or at most 100 pm .
Generally D<sub>dot</sub> or D<sub>dot</sub> Average can be in the range of 10 to 300 micrometers, 10-250 pm, 15-250 pm, 15-200 pm, 15-150 pm, 15-120 pm, or 15-100 pm. More typically, with the currently used ink formulations, and a particular ink head, D<sub>dot</sub> or D<sub>do</sub>t average can be in the range of 20-120 pm, 25-120 pm, 30-120 pm, 30-100 pm, 40120 pm, 40-100 pm, or 40-80 pm.
Each single drop ink film or individual ink dot film is characterized by a dimensionless aspect ratio defined by:
Raspect - Ddot / Hdot where R<sub>aspec</sub>t is the aspect ratio; D<sub>dot</sub> it is a diameter, characteristic diameter, average diameter, or the longest diameter of the point; and H<sub>dot</sub> it is a thickness, the characteristic thickness, or average thickness of the point, or the height of the top surface of the point with respect to the substrate.
The aspect ratio may be at least 15, at least 20, at least 25, or at least 30, and more typically, at least 40, at least 50, at least 60, at least 75. In many cases, the aspect ratio can be at least 95, at least 110, or at least 12 0. The aspect ratio is typically less than 200 or less than 175.
Penetration
In the ink film structures of the present invention, the ink dot can be laminated essentially onto an upper surface of the printing substrate. As described here, the shape of the spot can be largely determined or determined prior to the transfer operation, and the spot is transferred as an integral unit to the substrate. This integral unit may be substantially solvent-free, so that there may be no penetration of any material from the transfer member of the rubber holder, or between the fibers of the substrate. The continuous dot, which may largely contain organic polymeric resin and colorant, adheres to, or forms a laminated layer on, the upper surface of the fibrous printing substrate.
Such continuous dots are typically produced by various inkjet technologies, such as on-demand dot and continuous inkjet technologies.
Organic polymeric resins used in conjunction with the present invention are typically water soluble or water dispersible.
Figures 3D and 3E provide schematic cross-sectional views of an inventive ink film structure (300) and a prior art ink ink film stain or structure (370), respectively. Referring now to Figure 3E, the inkjet film structure (370) includes a single drop ink spot (305) adhered to, or laminated to, a plurality of substrate fibers (320) in one area particular web of a fibrous printing substrate (350). The fibrous printing substrate 350 can be, by way of example, an uncoated paper, such as bond, copy or offset paper. The fibrous printing substrate 350 can also be one of several commodity coated fibrous printing substrates, such as coated offset paper.
An ink stain portion (305) is disposed below the top surface of the substrate (350), between the fibers (320). Various components of the ink, including a portion of the dye, can penetrate the top surface together with the ink dissolving vehicle to, at least partially, fill a volume (380) disposed between the fibers (320). As shown, a portion of the dye can diffuse or migrate the lower fibers (320), to a volume (390) disposed below the fibers (320). In some cases (not shown), some of the dyes can penetrate the fibers.
In contrast, the inventive ink film structure (300) (in Figure 3D) includes an integral continuous ink dot such as a single ink dot (310), disposed on, and fixedly attached to (or laminated to) ) a, an upper surface of a plurality of substrate fibers (320), in a particular continuous area of the fibrous printing substrate (350). The adhesion or lamination can be, mainly or substantially, a physical bond. The adhesion or lamination may have little or substantially no chemical bonding character or, more specifically, no ionic bonding character.
Ink dot 310 contains at least one colorant dispersed in an organic polymeric resin. Within the particular continuous zone of the fibrous substrate (350), there is at least one direction (as shown by arrows 360 - various directions) perpendicular to the top surface of the printing substrate (350). With respect to all directions normal to this top surface over the entire dotted area, the ink dot 310 is arranged entirely above the area. The volume 380 between the fibers 320 and the volume 390 below the fibers 320 lacks, or is substantially devoid of, colorant, resin, and any and all components of the ink.
Thickness (H<sub>dot</sub>) of the single drop ink film or individual ink dots (310) can be at most 1,800 nm, at most 1,500 nm, at most 1,200 nm, at most 1,000 nm, or at most 800nm, and more typically at most 650nm, 600nm at most, at most 550nm, 500nm at most, at most 450nm, or at most 400nm. Thickness (H<sub>do</sub>t) a single ink drop (310) can be at least 50nm, at least 100nm, or at least 125nm, and more typically, at least 150nm, at least 175nm, at least 200 nm, or at least 250nm. The degree of penetration of an ink into a printing substrate can be quantitatively determined using various analytical techniques, many of which will be known to those of ordinary skill in the art. Such a quantitative determination of the degree of penetration can be made by various commercial analytical laboratories.
These analysis techniques include the use of different staining techniques, such as osmium tetraoxide staining (see Patrick Echlin, Handbook of Sample Preparation for Scanning Electron Microscopy and X75
Ray Microanalysis (Springer Science + Business Media, LLC 2009, pp. 140-143).
An alternative to staining techniques may be particularly suitable for inks that contain metals such as copper. The Secondary Ion Time of Flight Mass Spectrometry (SIMS-TOF) was performed with a TOF-SIMS V Spectrometer [Ion-TOF (Münster, Germany)]. This apparatus provides elemental and molecular information regarding the top layer of organic and inorganic surfaces, and also provides depth and imaging profiles that have depth resolution on the nano scale, submicron lateral resolution, and chemical sensitivity of the order of 1 ppm.
The translation of the raw TOF-SIMS data into concentration can be performed by normalizing the signals obtained to the concentration (C +) measured by carbon X-ray photoelectron (XPS) spectroscopy in the sample. XPS data was obtained using a Thermo VG Scientific Sigma Probe (England). Analysis of small chemical areas of solid surfaces with chemical bonding information was obtained using a microcentrated monochromatic X-ray source (15 to 400 μιη). The resolved angle information is obtained with and without tilting the sample.
This allows depth profiles with good depth resolution.
For reference, the atomic concentration of copper within a fibrous paper substrate was measured as a function of depth. The atomic concentration of copper was found to be substantially zero at the surface, down to a depth of several micrometers. This procedure was repeated for two prior art cyan inkjet film structures, and for a cyan inkjet film structure of the present invention.
Figure 3F shows a graph representing the atomic concentration of copper [Cu] at the ink point and within the fibrous paper substrate, as a function of approximate depth, within a first color inkjet ink film structure cyan of the prior art. The initial [Cu], measured near the top surface of the cyan-containing ink film structure, was approximately 0.8 atomic%. Within a depth of about 100nm, [Cu] was steadily reduced to about 0.1 atomic%. In the depth range of about 100nm - 1,000nm, [Cu] was reduced from about 0.1 atomic% to about zero. Therefore, it is evident that the inkjet pigment that has penetrated the fibrous paper substrate, possibly reaches a penetration depth of at least 700nm, at least 800nm, or at least 900nm .
Figure 3G shows a graph representing the atomic concentration of copper within the ink dot structure, as a function of approximate depth, within a second prior art cyan color inkjet film structure. The initial atomic concentration of copper [Cu] within the ink dot structure, measured near the top surface, was approximately 0.02 atomic%. This concentration is generally maintained at a depth of around 3,000 nm. In the depth range of about 3,000nm to almost 6,000nm, [Cu] very gradually decreased to about 0.01 atomic%. It appears that this prior art structure has little or no ink film on the surface of the substrate, and that the penetration of the pigment into the substrate was pronounced (at least 5-6 microns).
Figure 3H shows graphs representing the atomic concentration of copper at the ink point and within the fibrous paper substrate, as a function of approximate depth, within a cyan color ink film structure of the present invention.
The two graphs represent measurements made at two different positions (Sample 1 and Sample 2) on the inventive ink dot structure. The initial atomic concentration of copper [Cu], measured near the top surface, was approximately 0.2 or 0.4 atomic% for Sample 1 and Sample 2, respectively. At more than a depth of about 75 to about 100 nm, the [Cu] steadily increased to about 0.5 or 0.7 atomic% for the respective samples. At a depth of about 100nm to about 175nm, [Cu] began to drop, achieving a copper concentration of substantially zero at a depth of 200-250nm, for both samples. It would appear that the structure of the invention is the only one arranged on the surface of the substrate, and that the penetration of the pigment into the substrate was negligible or substantially minimal, both in terms of depth of penetration and in terms of the amount or fraction of penetration.
Without wishing to be bound by theory, the inventors believe that the initial increase in [Cu] to the depth of 75-100nm can be attributed to the orientation of the ink dot due to the micro-contours of the substrate, and to the roughness of the surface of the ink point itself. Similarly, the drop from [Cu] to substantially zero at a depth of 200-250 nm can be attributed to the micro-contours of the substrate: for a given cross section within, and generally parallel to, the upper face or surface of the substrate, some of the ink spots may be present (see dotted line in Figure 3D). Despite this, the ink dot is fully disposed above the substrate, with respect to a direction perpendicular to the surface of the substrate.
Surface roughness
Using laser microscopy imaging and other techniques, the inventors have observed that the upper surface of the ink spots on the ink film structures of the present invention can be characterized by low surface roughness, particularly when the substrates of those Structures have a high-gloss paper (or substrate).
Without wishing to be bound by theory, the inventors believe that the relative flatness or smoothness of the ink film structures of the present invention can be largely attributed to the smoothness of the release layer on the surface of the ITM, and to the system of and process the invention in which the surface of the emerging ink film substantially complements that of said surface layer, and wherein the image of the developing ink film can substantially retain or fully maintain the complementary topography through transfer onto the printing substrate.
Referring now to Figure 4A, Figure 4A is an image of the surface of a release layer of an ITM or rubber holder used in accordance with the present invention. While the surface may be nominally flat, different marks (undercuts) and bumps can be observed, typically on the order of 1-5 pm. Many of these marks have irregular, sharp features. An image of an ink surface produced using this rubber holder, provided in Figure 4B, shows topographic features that are strikingly similar in nature to those shown in Figure 4A. The dotted surface is dotted with a large plurality of markings that have irregular, strong features that strongly resemble (and are within the same size range as) the irregular markings on the surface of the rubber holder.
A softer rubber holder was installed; Figure 4C provides an image of the release layer of this rubber holder. The irregular markings in Figure 4A are absent. Scattered on the highly smooth surface are highly circular surface defects, perhaps made by air bubbles, typically having a diameter of about 1-2 yim. An image of an ink surface produced using this rubber holder, provided in Figure 4D, shows topographic features that are strikingly similar in nature to those shown in Figure 4C. This image has virtually no distinctive markings, but it does have a number of highly circular surface imperfections that are strikingly similar in size and shape to those shown on the surface of the rubber holder.
Point Perimeter Characterization
The perimeter of various prior art ink films or dots may characteristically have a plurality of overhangs or tributaries, and a plurality of inlets or voids. These forms of ink can be irregular, and / or discontinuous. In contrast, the inkjet ink dot produced in accordance with the present invention has a distinctively round, convex, circular shape. The perimeter of the ink point of the invention can be relatively smooth, regular, continuous and well defined. The roundness, convexity, and edge irregularity of the ink dot are structural parameters used to evaluate or characterize shapes or optical representations of the same.
It can be easily seen by comparing the enlarged images of the prior art ink forms of Figure 1A with the ink dots of the invention of Figure IB, or by comparing the enlarged images of the prior art prior art ink of Figures 2A and 2B with the ink dots of the invention of Figure 2C, that the appearance of the ink dots of the present invention is manifestly different from the prior art ink forms. What is easily observed by the human eye can be quantified using image processing techniques. Various characterizations of the ink shapes are described below, after a description of the image acquisition method.
Acquisition Method (1) For each of the known printing technologies to be compared in the study, individual dots, spots, or film images printed on coated and uncoated paper were used. In the initial tests, the coated paper used was Condat Gloss® 135 gsm, or similar; the uncoated paper used was 130 gsm Uncoated Multi Fine, or the like. Subsequently, a wide variety of substrates were used, including numerous coated and uncoated fibrous substrates, and various plastic printing substrates.
(2) As for the printing technology according to the Applicant's invention, the single dot images were printed on coated paper and uncoated paper. Care was taken to select substrates having characteristics similar to the substrates of the known ink dot structures used in (1).
(3) The acquisition of the dot images was performed using an OLS4000 microscope (Olympus). Those of ordinary skill in the art know how to adjust the microscope to achieve the required focus, brightness, and contrast so that image details will be highly visible. These image details include the dot outline, the color variation within the dot area, and the fibrous structure of the substrate surface.
(4) The images were taken with an X100 optical zoom lens that has a resolution of 129 microns X 129 microns. This high resolution may be essential in obtaining fine point details and the fibrous structure of the substrate surface.
(5) Images are saved in uncompressed format (TIFF) with a resolution of 1024x1024 pixels. Compression formats can lose image data.
(6) In general, a single spot or stain was evaluated for each printing technology. From a statistical point of view, however, it may be advantageous to obtain 15 dot images (at least) for each type of print copy being scanned, and to manually select the (at least) 10 most representative dot images for image processing. The selected point images must be representative in terms of the point shape, contour, and color variation within the point area. Another approach to printing spot sampling, called the field of view, is described below.
Point Contour Computation
The dot images were loaded with the image processing software (ImageXpert). Each image was loaded into each of the red, green, and blue channels. The processing channel is selected based on maximum visibility criteria. For example, for cyan dots, the Red channel typically gave the best dot feature visibility, and was therefore selected for the image processing stage; the Green channel was typically best suited for a magenta point. The point edge contour was detected (automatically computerized), based on a single threshold. Using a full screen view mode on a 21.5 screen, this threshold is manually chosen for each image, so that the calculated edge contour better matches the actual and visible point edge. Because a single image was processed per channel, the threshold was a gray value (0 to 255, the gray value being a colorless value).
A computerized perimeter value was obtained from the image processing software (eg ImageXpert), the perimeter value is the sum of all the distances between adjacent pixels, connected at the edge of the point or spot. If, for example, the XY coordinates for the adjacent pixels (xl, yl) and (x2, y2), the distance is j [(x2-xl)<sup>2</sup>+ (y2-yl)<sup>2</sup>], while the perimeter is equal to £ {j (xí + xí) <sup>2</sup>+ (yi + yi)<sup>2</sup>] } .
In various embodiments of the invention, it is desired to measure the length of the perimeter of an ink dot. An alternative method of measuring the length of the perimeter will now be described. As a first step, an image comprising an ink dot is used as input for an algorithm that outputs the perimeter length. The MxN dimension of the image pixel can be stored in an array of two elements or an ordered pair of image pixel size. An example of the image pixel size value is 1280,760 - in this example M = 1280 and N = 760. This corresponds to an image of 1280 pixels on the horizontal axis and 760 pixels on the vertical axis. Subsequently, the magnification ratio or scale of the image is obtained and stored in variable image magnification. An example of variable image magnification is 500. When comparing the perimeters between the ink dots in the first and second images, it is mandatory that the variables of image pixel size and the image magnification of the two images are the same. It is now possible to calculate the corresponding length of a square pixel - that is, the lateral length in units of length for real-world images (for example, microns) or one pixel. This value is stored in a variable pixel pitch. An example of the variable pixel pitch is 0.05 μπι. The image is now converted to grayscale by methods known to the person skilled in the art. One proposed method is to convert the input image, the typical image in an sRGB color space, to the L * a * b color space. Once the image is in the Lab color space, the values of variables a and b are changed to zero. An edge detection operator can now be applied to the image. The preferred operator is a Canny edge detection operator. However, any operator known in the art can apply. Operators are not limited to first-order derivatives, like the Canny operator, but rather open to second derivatives as well. Also, a combination of operators can be used to obtain results that can be compared between operators and subsequently eliminate unwanted edges. It may be helpful to apply a smoothing operator such as a Gaussian blur before applying the edge detection operator. The threshold level applied when applying the edge detection operator is such that an edge that forms an endless loop is first obtained in the area between the previously described minimum ink dots surrounding the circle circumference and the maximum closed circle circumference of ink dots. A thinning operator is now implemented to make the endless loop edge substantially one pixel wide. Any pixel that is not a part of the endless loop edge has its value change from L * to zero, while any pixel that is part of the endless loop edge has its value change from L * to 100. The edge Endless loop is defined as the perimeter of the ink volume. A pixel link is defined as a straight line connecting the pixels. Each pixel along the perimeter incorporates two pixel links, a first pixel link and a second pixel link. These two pixel links define a path of the pixel link within a single pixel. In this method of calculating the perimeter length, each pixel is a square pixel. Therefore, each pixel link can form a line from the center of the pixel to one of the eight possible nodes. Possible nodes are the corners of the pixel or a midpoint between two neighboring corners of the pixel. The nodes at the corners of the pixels are of type one node_l, the nodes at the midpoint between two corners are of type node_2. As such, there are six possibilities of pixel link paths within a pixel. These can be classified into three groups. Group A, B, and C. Each group has its own corresponding coefficient, that is, coefficient_A, coefficient_B, and coefficient_C. The value of the coefficient_A is 1, the value of the coefficient_B is sqrt (2), and the value of the coefficient is_C (1 + sqrt (2)) / 2. Group A contains pixels whose pixel link path matches nodes of type node_2. Group B contains pixels with a pixel link path that matches nodes of type node_l. Group C contains pixels whose pixel link path matches the nodes of type node_l and type node_2. It is now possible to calculate the pixel length of the perimeter. The pixel length of the perimeter is calculated by adding all the pixels in the perimeter multiplied by their corresponding coefficient. This value is stored in the variable perimeter pixel length. It is now possible to calculate the actual length of the ink perimeter. This is done by multiplying the pixel perimeter length by the pixel pitch.
Roundness
A dimensionless roundness factor (ER), can be defined by:
ER = P<sup>2</sup>/ (4π · Α) where P is the measured or calculated perimeter, and A is the measured or calculated area within the ink, spot, or ink film. For a perfectly smooth, circular ink dot, ER equals 1.
The deviation from a round, smooth shape can be represented by the expression (ER - 1). For a perfectly circular idealized ink dot, this expression equals zero.
The R-square of the roundness factor can be calculated for each of the 10 most representative dot images selected for each type of printing technology, and averaged over a single value.
For ink film structures in which the fibrous substrate (eg paper) is not coated, or for ink film structures in which the fibrous substrate is coated with a coating such as product coating basic on coated offset paper (or coatings that allow the traditional water-based inkjet vehicle to reach the paper fibers), the deviation from a smooth round shape [(ER-l), hereafter, deviation] for the ink dots of the present invention is not ideal, and will exceed 0.
Exemplary ink film images arranged on coated (Figure 5A) and uncoated (Figure 5B) substrates are provided for the following printers: HP Deskjet 9000 (1); HP Indigo 7500 Digital Press (2); Offset Lithograph: Ryobi 755 (3); and (4) Xerox DC8000, and for the digital printing technology of the invention (5). These ink film images were generally obtained according to the image acquisition method detailed earlier in this document. Next to each original image, a corresponding processed black-and-white image is provided where the image on the processor calculates the highlighted ink spot, film, or smudge outline, and where the calculated contours are manifestly similar to the contours of the original images.
For all tested fibrous coated substrates (paper), the individual typical ink dots of the invention showed a deviation from a round, smooth shape (ER-1) of 0.16 to 0.27. In contrast, the roundness deviation of the coated impressions of the different prior art technologies ranged from 1.65 to 7.13. For all the uncoated fibrous substrates tested (paper), the typical individual ink dots of the invention showed a deviation (ER-1) of 0.28-0.89. On each of these substrates, some of the ink dots of the invention show a deviation (ER-1) of at most 0.7, at most 0.6, at most 0.5, at most 0.4, at most 0.35, at most 0.3, at most 0.25, or at most 0.20.
In contrast, the roundness deviation of the ink films on the uncoated prints of the various prior art technologies ranged from
2.93 to 14.87.
A further study was performed on 19 fibrous substrates of different physical and chemical properties. Substrates include coated and uncoated substrates and mechanical and wood free substrates. Substrates are characterized by differences in thickness, density, roughness (for example, Bendtsen number) or smoothness (gloss), etc. These substrates are identified and partially characterized in Table 1.
In the case of various substrates, the roundness deviation of the ink dot structures of the invention is compared with the ink images produced by a commercial inkjet printer (using compatible ink cartridges provided by the manufacturer) in the bar graphs provided in Figure 5C.
It should be noted that in this further study, the ink film structures of the present invention were produced on a pilot semi-automatic digital printing press of the invention, where the transfer of the ink dots from the ITM to the printing substrate manually, and consequently with a printing pressure that may be somewhat lower, and more variable, than the previously described commercial prototype of a fully automatic digital printing press of the present invention.
For example, substrate number 6, Condat Gloss 135, is the same substrate used previously for the ink dot of the invention shown in Figure 5A. However, the roundness deviation achieved by a typical ink dot was 0.362, representing a deviation greater than the deviations (0.16 to 0.27) of all the ink dots of the invention printed by the commercial prototype of the inkjet printer. inventive digital press. However, a part (albeit minor) of the ink dots of the invention produced in the semi-automatic pilot digital printing press achieved deviations as low as or less than the lowest standard deviation (0.16) obtained in the prototype of commercial digital press printer.
TABLE 1
<td rowspan="2"> #</td><td rowspan="2">Substrate Name</td><td rowspan="2">GSM (g / m *)</td><td rowspan="2">Kind</td><td colspan="2">Points of the Invention</td>
<td>Roundness Deviation (ER-1)</td><td>No- Convexity (1-CX)</td>
<td> 1</td><td>Chromo MAtte 300</td><td> 300</td><td>Covered</td><td> 0.361</td><td> 0.006</td>
<td> 2</td><td>Chromo Matte Garda 130</td><td> 130</td><td>Wood-free coated</td><td> 0.656</td><td> 0.009</td>
<td> 3</td><td>Chromo Matte Graphic 130</td><td> 130</td><td>Covered</td><td> 0.305</td><td> 0.008</td>
<td> 4</td><td>Chromo Matte Graphic 170</td><td> 170</td><td>Covered</td><td> 0.395</td><td> 0.011</td>
<td> 5</td><td>Condat Gloss 90</td><td> 90</td><td>Covered</td><td> 0.218</td><td> 0.005</td>
<td> 6</td><td>Condat Gloss 135</td><td> 135</td><td>Covered</td><td> 0.362</td><td> 0.006</td>
<td> 7</td><td>Condat Gloss 225</td><td> 225</td><td>Covered</td><td> 0.229</td><td> 0.004</td>
<td> 8</td><td>EJalum Glossy recycled</td><td> 250</td><td>Covered recycling</td><td> 0.357</td><td> 0.008</td>
<td> 9</td><td>Gruppo Cordenons Ivo Digital laser</td><td> 120</td><td>Uncoated</td><td> 0.120</td><td> 0.007</td>
<td> 10</td><td>Holmen Plus</td><td> 49</td><td>Uncoated Mechanical</td><td> 0.621</td><td> 0.021</td>
<td> 11</td><td>Holmen XLNT</td><td> 55</td><td>Uncoated Mechanical</td><td> 0.515</td><td> 0.020</td>
<td> 12</td><td>Invercote G</td><td> 300</td><td>S5S cardboard<sub>r</sub> C1S</td><td> 0.393</td><td> 0.008</td>
<td> 13</td><td>Lelpa Ultra LUX Semi Gloss</td><td> 90</td><td>Low Coated Weight</td><td> 0.449</td><td> 0.009</td>
<td> 14</td><td>Norske Skog NorCote Bruck H</td><td> 70</td><td>LWC Coated</td><td> 0.548</td><td> 0.011</td>
<td> 15</td><td>Sappi Magno Satín</td><td> 170</td><td>Coated Wood Udder</td><td> 0.174</td><td> 0.007</td>
<td> 16</td><td>Sappi Magno Star</td><td> 250</td><td>Coated Wood Udder</td><td> 0.406</td><td> 0.006</td>
<td> 17</td><td>Matras 90 towers</td><td> 90</td><td>Covered</td><td> 0.410</td><td> 0.014</td>
<td> 18</td><td>Matras 130 towers</td><td> 130</td><td>Covered</td><td> 0.404</td><td> 0.015</td>
<td> 19</td><td>Torras Matte 170</td><td> 170</td><td>Covered</td><td> 0.078</td><td> 0.004</td>
Considering the coated and uncoated fibrous substrates (paper) to each other, the roundness deviation of the ink dots of the invention is greater than zero, and can be at least 0.01, at least 0.02, or at least 0.03 . For each of the 19 tested fibrous substrates provided in Table 1, at least some of the ink dots of the invention show a roundness deviation (on both coated and uncoated fibrous substrates) of at most 0.30, at at most 0.25, at most 0.20, at most 0.15, or at most 0.12.
The ink dots of the invention, when adhered to fibrous coated substrates (or coated with baisian products), can typically have a deviation of at most 0.20, at most 0.18, at most
0.16, at most 0.14, at most 0.12, or at most 0.10.
For each of the coated substrates provided in Table 1, at least some of the ink dots of the invention show a roundness deviation of at most 0.25, at most 0.20, at most 0.15, at most 0.12 , at most 0.10, at most 0.09, at most 0.08, at most
0.07, or at most 0.06.
Because, as noted above, ink images can contain an extremely large amount of a plurality of individual ink dots or single dot ink films, it may be statistically significant to define the ink film structures of the invention in those that at least 2 0% or at least 3 0%, and in some cases, at least 50%, at least 70%, or at least 90%, of the ink dots of the invention (or single-drop ink dots of the invention), arranged on any uncoated or coated fibrous substrate (or coated with a basic product), and selected randomly, may have a roundness deviation that it is at least 0.01 or at least 0.02, and can be at most 0.8, at most 0.65, at most 0.5, at most 0.35, at most
0.3, at most 0.25, s at most 0.2, at most 0.15, at most 0.12, or at most 0.10.
As with a single ink dot or a single single drop ink dot, at least 2 0% or at least 3 0%, and more typically at least 50%, at least 70%, or at least 90%, of the ink dots of the invention (or the single drop ink dots of the invention), arranged on any fibrous coated (or commodity coated) substrate, and randomly selected, they can have a roundness deviation that is at least 0.01 or at least 0.02, and can be at most 0.8, at most 0.65, at most 0.5, at most 0.35, or at most 0.3, and more typically , at most 0.25, at most 0.2, at most 0.15, at most 0.12, at most 0.10, at most 0.08, at most
0.07, or at most 0.06.
Additional characterizations regarding roundness deviation are provided below.
Convexity
As described above, prior art ink or film dots may characteristically have a plurality of overhangs or tributaries, and a plurality of inlets or voids. These forms of ink can be irregular, and / or discontinuous. In contrast, the inkjet film produced in accordance with the present invention characteristically has a circular, convex, manifestly rounded shape. Point convexity, or point deviation, is a structural parameter that can be used to evaluate or characterize shapes or optical representations of points. The image acquisition method can be substantially identical to that previously described.
Convex Measurement
The dot images were loaded with the image processing software (ImageXpert). Each image was loaded into each of the red, green, and blue channels. The processing channel is selected based on maximum visibility criteria. For example, for cyan dots, the Red channel typically gave the best dot characteristic visibility, and was therefore selected for the image processing stage; the Green channel was typically best suited for a magenta point. The point edge contour was detected (automatically computerized), based on a single threshold. Using a full screen view mode on a 21.5 screen, this threshold is manually chosen for each image, so that the calculated edge contour better matches the actual and visible point edge. Because a single image was processed per channel, the threshold was a gray value (0 to 255, the gray value being a colorless value).
A MATLAB script was created to calculate the relationship between the area of the minimal convex shape that limits the point outline and the actual area of the point. For each ink dot image, the dot edge outline set (X, Y) of dots, created by ImageXpert, was uploaded to MATLAB.
In order to reduce the sensitivity of the noise measurement, the point border was passed through a Savitzky-Golay filter (low-pass image processing filter) to slightly soften the border contour, but without appreciably modifying the characteristic irregularity of the same. A window frame size of 5 pixels was generally adequate.
Subsequently, a minimal area convex shape was produced to delimit the contour of the smoothed edge.
The ratio between the convex shape convex area (CSA) and the actual (calculated) spot or film area (AA) is calculated as follows:
CX = AA / CSA
The deviation from this convexity, or non-convexity, relationship is represented by 1-CX, or DC<sub>dot</sub>.
For the previously described images of ink dots arranged on coated (Figure 5A) and uncoated (Figure 5B) substrates, the convex shaped area (CSA) is shown surrounding the actual dot area (AA), and the ratio of convexity is provided in form percentage.
In the ink film images of Figure 5A, arranged on the coated substrates, the convexity of the printing images of the various prior art technologies ranged from 87.91% to 94.97% (-0.879 to 0.950 fractionally) , corresponding to a convex deviation of 0.050 to 0.121. In contrast, the ink dot of the invention showed a convexity of 99.48% (-0.995), corresponding to a convex deviation of approximately 0.005.
100
This deviation is approximately 1/10 to 1/25 of the deviation shown by the various prior art technologies. In absolute terms, the deviation is at least 0.04 less than the deviation shown by the various prior art technologies.
The difference between the dot images of the invention and those of the various prior art technologies may be more striking on uncoated substrates. In the images of the ink film of Figure 5B, arranged on uncoated substrates, the convexity of the print images of the various prior art technologies ranged from 65.58% to 9O.i9% (-0.656 to 0.902 as fractional), corresponding to a convex deviation of 0.344 to 0.098. In contrast, the ink dot of the invention showed a convexity of 98.45% (-0.985), corresponding to a convex deviation of approximately 0.015. This deviation is at least 1/6 to 1/2 0 of the deviation shown by the various prior art technologies. In absolute terms, the deviation is at least 0.08 to less than the deviation shown by the various prior art technologies.
Another study described above was performed, in which the ink film structures of the present invention were produced on i9 different substrates
101 fibrous. In Table 1, the non-convexity of typical points of the invention is provided. The non-convexity of the ink dots in the ink film structures is graphically presented in the bar graphs provided in Figure 5D.
Because in the roundness deviation study, the printed dots of the present invention show superior convexity over prior art images, for any given substrate, coated or uncoated.
For all 19 fibrous substrates tested, the typical ink dots of the invention show a non-convexity of 0.004 to 0.021. For each of the 19 fibrous substrates tested, at least some of the ink dots of the invention show a non-convexity of at most 0.018, at most 0.016, at most 0.015, at most 0.014, or at most I add 0.013.
For all tested commodity coated fibrous substrates, typical inventive ink dots showed non-convexity of 0.004 to 0.015.
For each of these fibrous coated substrates, at least some of the ink dots of the invention showed non-convexity of at most 0.014, at most
0.012, at most 0.010, at most 0.009, at most 0.008, or at most 0.007.
102
For each of the uncoated substrates, at least some of the ink dots of the invention show a non-convexity of at most 0.03, at most
0.025, at most 0.022, at most 0.020, at most 0.018, at most 0.016, at most 0.015, at most 0.014, or at most 0.013.
Because, as noted above, ink images can contain an extremely large amount of a plurality of individual dots or single ink drop films (at least 20, at least 100, or at least 1,000) , it may be statistically significant to define the ink film structures of the invention where at least 10%, at least 2 0%, or at least 3 0%, and in some cases, at least 50%, by at least 7 0%, or at least 90%, of the ink dots of the invention (or single-drop ink dots of the invention), arranged on any coated or uncoated (or coated commodity) fibrous substrate, and selected at random, may show non-convexity not more than 0.04, not more than 0.035, not more than 0.03, not more than 0.025, not more than 0.020, not more than 0.017, not more than 0.014, not more than 0.012, not more than 0.010, not more than 0.009 , at most 0.008, or at most 0.007.
At least 10%, at least 2 0%, or at least
103 minus 3 0%, and in some cases, at least 50%, at least 70%, or at least 90%, of these inventive ink dots (or inventive single-drop ink dots) can show a non-convexity of at least 0.001, at least 0.002, or at least 0.0025.
As with a single ink dot or a single single drop ink dot, at least 10%, at least 20%, or at least 30%, and more typically, at least 50%, per at least 70%, or at least 9 0%, of the ink dots of the invention (or the single-drop ink dots of the invention), arranged on any uncoated or coated fibrous substrate (coated with commodities ), and selected at random, can show non-convexity within a range of 0.001- 0.002 to 0.05, 0.001-0.002 to
0.04, 0.001-0.002 to 0.035, 0.001-0.002 to 0.030, 0.0010.002 to 0.025, 0.001-0.002 to 0.020, 0.001-0.002 to 0.015,
0.001-0.002 to 0.012, or 0.001-0.010.
For any commodity coated or coated fibrous print substrate, these same dots may show lower non-convexity, within a range of 0.001-0.002 to 0.020, 0.001-0.002 to 0.015, 0.001-0.002 to 0.012, 0.001-0.002 to 0.010, 0.0010.008, 0.001 to 0.007, 0.001 to 0.006, 0.001 to 0.005, or 0.001 to 0.004.
104
For any uncoated fibrous printing substrate, these same dots can show nonconvexity within a range of 0.001-0.002 to 0.05, 0.0010.002 to 0.04, 0.001-0.002 to 0.035, 0.001-0.002 to 0.030,
0.001-0.002 to 0.025, 0.001-0.002 to 0.020, 0.001-0.002 to
0.015, 0.001-0.002 to 0.012, or 0.001 to 0.010.
Additional characterizations regarding ink dot convexity are provided below.
Reference Ink
The ink dots in the ink dot structures of the present invention can show
<td>constantly</td><td>good</td><td>properties of</td><td>shape</td><td>(for example,</td>
<td colspan="2">convexity, roundness,</td><td>irregularity of</td><td>edge</td><td>, and the like),</td>
<td>Anyone that</td><td>be,</td><td>to a large degree,</td><td>of</td><td>characteristics</td>
<td>topographic</td><td colspan="2">private, local</td><td>of the</td><td>substrate, e</td>
regardless, to some degree, of the type of print media (for example, commodity coated or uncoated print substrates). However, the ink dot shape properties of the ink dot structures of the present invention are not completely independent of the type of printing substrate, as evidenced by the lower frames of the
105
Figure 5A (coated fibrous substrate) versus lower frames of Figure 5B (uncoated fibrous substrate). The quality of ink dots in different known printing technologies, and in aqueous direct injection ink technologies, in particular, can vary substantially more with the type of printing substrate.
A reference inkjet ink, together with a reference printing method therefor, can be used to structurally define the various optical properties of ink dot structures on a substrate to a base substrate, by normalizing those properties to the printing substrate.
The reference ink contained 15% Basacid
Liquid Black X34 (BASF), 60% propylene glycol, and 25% distilled water. The dye was added to a mixture of water and propylene glycol. After 5 minutes of stirring, the ink was passed through a 0.2 micron filter. The reference ink composition is simple, and the components are generic, or at least commercially available. In the event that liquid Basacid Black X34 (BASF) is not available, a similar black inkjet dye can replace it. In either case, a supply of the reference ink may
106 Obtained from Landa Corporation, POB 2418, Rehovot 7612301,
Israel.
The reference ink was printed using a FUJIFILM Dimatix media printer, DMP-2800, equipped with a 10 pL print head, DMC-11610. The printing parameters were adjusted as follows:
Ink temperature: Substrate temperature:
Trigger Voltage:
Meniscus fixed point: Distance from the print head to the substrate:
25 ° C
25 ° C
V
2.0 (inches of water) mm.
The apparatus commercially.
functionally f une i onalment and printing is available
If not available, an equivalent (or substantially equivalent) printer can be used.
Alternatively, such a printing apparatus may be obtained from Landa Corporation, POB 2418, Rehovot 7612301,
Israel.
The reference inkjet ink was prepared and printed on various printing substrates, as described earlier in this document. The printed dots were subjected to image processing to
107 the characterization of roundness and convexity.
Figure 5E-1 provides comparative bar graphs of the roundness deviation of the ink dots produced in accordance with some embodiments of the present invention, versus ink dots produced using the reference ink formulation and printing method. previously described. The comparative study was carried out with 10 fibrous substrates of different physical and chemical properties; These include coated and uncoated substrates. The substrates are identified and partially characterized in Table 2, which also provides the deviation of the roundness results of the comparative study, for each of the fibrous substrates.
It is evident that for all fibrous substrates, coated (basic products) and uncoated, the point structures of the invention have smaller roundness deviations (ER-1 or DRa<sub>ot</sub>). The highest DRa value<sub>ot</sub>, obtained for an uncoated substrate (Hadar Top), is still less than a fifth of the lowest roundness deviation value of the reference ink points (RDR), 1.16, obtained for a silk-coated substrate (Sappi Magno Satin).
108
TABLE 2
<td rowspan="2"> #</td><td rowspan="2">Name of Substratum</td><td rowspan="2">GSM (g / m<sup>z</sup>j</td><td rowspan="2">Kind</td><td colspan="4">Roundness deviation</td>
<td>Points of Reference (RDR)</td><td>Points of the Invention (DRaJ</td><td>Relationship lnv./Ref. (DR ^ t / RD RÓKÍ ')</td><td>DELTA (RDR- DRaJ</td>
<td> 1</td><td>Iggesund Silk 300</td><td> 300</td><td>Covered</td><td> 2.85</td><td> 0.063</td><td> 0.022</td><td> 2.78</td>
<td> 2</td><td>Arjowiggins (Dalum) Cydus</td><td> 170</td><td>Uncoated</td><td> 3.05</td><td> 0.124</td><td> 0.041</td><td> 2.92</td>
<td> 3</td><td>Invercote Creato 300</td><td> 300</td><td>Coated (SBS, C2S)</td><td> 2.57</td><td> 0.052</td><td> 0.020</td><td> 2.52</td>
<td> 4</td><td>Arjowiggins Gloss</td><td> 170</td><td>Covered Sparkly, Recycling</td><td> 1.49</td><td> 0.035</td><td> 0.024</td><td> 1.45</td>
<td> 5</td><td>Dalum Gloss recycled</td><td> 170</td><td>Covered Sparkly, Recycling</td><td> 1.42</td><td> 0.073</td><td> 0.051</td><td> 1.35</td>
<td> 6</td><td>Sappi Magno Satin</td><td> 170</td><td>Covered Silk</td><td> 1.16</td><td> 0.049</td><td> 0.043</td><td> 1.11</td>
<td> 7</td><td>Sappi Magno Star</td><td> 250</td><td>Covered Sparkly</td><td> 1.51</td><td> 0.032</td><td> 0.021</td><td> 1.47</td>
<td> 8</td><td>Invercote G</td><td> 300</td><td>Coated (SBS, C1S)</td><td> 2.41</td><td> 0.087</td><td> 0.036</td><td> 2.33</td>
<td> 9</td><td>Stora Enso</td><td> 275</td><td>Coated (WLC, C1S)</td><td> 1.44</td><td> 0.044</td><td> 0.031</td><td> 1.39</td>
<td> 10</td><td>Hadar Top</td><td> 170</td><td>Covered offset</td><td> 2.64</td><td> 0.187</td><td> 0.071</td><td> 2.45</td>
On a per-substrate basis, the difference between DRdot and RDR is even more pronounced. The DRa ratio<sub>or</sub>t / RDR, also referred to as the Kl coefficient, ranges from about 0.02 to about 0.07, which corresponds to a factor of 14: 1 to 50: 1, on a per substrate basis.
Thus, according to some modalities of the present invention, the Kl coefficient can be at most 0.25, at most 0.22, at most 0.20, at most 0.17,
109 at most 0.15, at most 0.12, at most 0.10, at most 0.09, or at most 0.08, for both commodity (coated) and uncoated substrates, and in some cases, at most 0.070, at most
0.065, at most 0.060, at most 0.055, at most 0.050, at most 0.045, or at most about 0.04.
The Kl coefficient can be at least 0.010, at least 0.015, at least 0.180, or at least about 0.020. In some cases, the Kl coefficient can be at least 0.03, at least 0.04, at least 0.05, at least 0.06, at least about 0.07, at least about 0.075, at least about 0.08, at least minus about 0.09, at least about 0.10.
For coated substrates, the Kl coefficient can be at most 0.070, at most 0.065, at most 0.060, or at most 0.055, and in some cases, at most
0.050, at most 0.045, at most 0.040, at most 0.035, at most 0.030, at most 0.025, or at most 0.022.
Figure 5E-2 provides comparative ink dot convexity bar graphs of the ink dot structures of Figure 5E-1, for each of the 10 fibrous substrates described above.
Table 3 contains the non-convexity results of the comparative study, for each of the substrates.
110 fibrous.
TABLE 3
<td rowspan="2">g</td><td rowspan="2">Name of Substratum</td><td rowspan="2">GSM (g / m<sup>2</sup>)</td><td rowspan="2">Kind</td><td colspan="4">Non-convex (1-CX)</td>
<td>Reference Points (RDR)</td><td>Points of the Invention (DReot)</td><td>Relationship Inv / Ref. (DRat / RD RÓ'Kl)</td><td>DELTA (RDR- DRoot)</td>
<td> 1</td><td>Iggesund Silk 300</td><td> 300</td><td>Covered</td><td> 0.053</td><td> 0.0058</td><td> 0.109</td><td> 0.048</td>
<td> 2</td><td>Arjowiggins (Dalum) Cyclus</td><td> 170</td><td>Uncoated</td><td> 0.107</td><td> 0.0077</td><td> 0.072</td><td> 0.099</td>
<td> 3</td><td>Invercote Creato 300</td><td> 300</td><td>Coated (SBS, C2S)</td><td> 0.047</td><td> 0.0050</td><td> 0.107</td><td> 0.042</td>
<td> 4</td><td>Arjowiggins Gloss</td><td> 170</td><td>Covered Sparkly, Recycling</td><td> 0.026</td><td> 0.0043</td><td> 0.0167</td><td> 0.022</td>
<td> 5</td><td>Dalum Gloss recycled</td><td> 170</td><td>Covered Sparkly, Recycling</td><td> 0.044</td><td> 0.0047</td><td> 0.106</td><td> 0.040</td>
<td> 6</td><td>Sappi Magno Satin</td><td> 170</td><td>Covered Silk</td><td> 0.035</td><td> 0.0049</td><td> 0.139</td><td> 0.030</td>
<td> 7</td><td>Sappi Magno Star</td><td> 250</td><td>Covered Sparkly</td><td> 0.044</td><td> 0.0042</td><td> 0.0966</td><td> 0.040</td>
<td> 8</td><td>Invercote G</td><td> 300</td><td>Coated (SBS, C1S)</td><td> 0.047</td><td> 0.0073</td><td> 0.157</td><td> 0.039</td>
<td> 9</td><td>Stora Enso</td><td> 275</td><td>Coated (WLC, C1S)</td><td> 0.033</td><td> 0.0049</td><td> 0.147</td><td> 0.029</td>
<td> 10</td><td>HadarTop</td><td> 170</td><td>Covered offset</td><td> 0.239</td><td> 0.0096</td><td> 0.040</td><td> 0.143</td>
It is evident that for all fibrous, coated (commodity) and uncoated substrates, the point structures of the invention have lower non-convexities (1-CX or DC<sub>do</sub>t) · The highest DCaot value, obtained for an uncoated substrate (Hadar Top), 0.010, is still less than 2/5 of the highest value.
111 Low of the roundness deviation of the reference ink points (RDR), obtained for a coated glossy substrate (Arjowiggins Gloss), 0.026.
On a per-substrate basis, the difference between DC<sub>dot</sub> and DRC is even more pronounced. The DC ratio<sub>d</sub>ot / RDC, also referred to as the K coefficient, ranges from about 0.04 to about 0.17, which corresponds to a factor of 6: 1 to 25: 1, on a per substrate basis.
Thus, according to some embodiments of the present invention, the coefficient of K can be at most 0.35, at most 0.32, at most 0.30, at most 0.27, at most 0.25, at most 0.22, at most 0.20, at most 0.19, or at most 0.18, for both coated (commodity) and uncoated substrates. The K coefficient can be at least 0.010, at least 0.02, at least 0.03, or at least approximately 0.04. In some cases, the K coefficient can be at least 0.05, at least 0.07, at least 0.10, at least 0.12, at least 0.15, at least 0.16, at least 0.17, at least 0.18 , at least 0.19, or at least about 0.20.
For uncoated substrates, the K coefficient can be at most 0.15, at most 0.12, at most 0.10, at most 0.09, at most 0.08, or at most 0.075, and
112 in some cases, at most 0.07 0, at most 0.065, at most 0.060, or at most 0.055, and in some cases, at most 0.050, at most 0.045, or at most 0.040.
The K coefficient can be at least 0.02 0, at least 0.03, at least 0.04, at least 0.06, at least 0.07, or at least approximately 0.08. In some cases, particularly for various commodity coated substrates, the K coefficient can be at least 0.10, at least about 0.12, at least about 0.14, at least about 0.16, at least about 0.18, or at least about 0.20.
Field of view
The ink dots in the ink dot structures of the present invention can consistently show good shape properties (eg, convexity, roundness, edge irregularity, and the like), whatever, to a large extent, of the topographic features. particular, local substrate, and regardless, to some degree, of the type of print substrate (coated or uncoated print substrates, plastic print substrates, etc.). The quality of ink dots in different technologies
113 Known printing, and in aqueous direct inkjet technologies, in particular, can vary appreciably with the type of printing substrate, and with the particular, local topographic characteristics of the substrate. It will be readily appreciated that, by way of example, when an ink drop is injected over a particularly flat local contour having a relatively homogeneous substrate surface (such as a wide fiber), the ink dot obtained can show significantly better properties. shape, with respect to the others, or the average of ink dots arranged elsewhere on the substrate.
The use of a more statistical approach, however, can better distinguish between the ink dot structures of the invention from the ink dot structures of the art. Therefore, in some embodiments of the present invention, the ink dot structures can be characterized as a plurality of ink dots arranged on the substrate, within a representative field of view. Assuming that the characterization of the point is obtained through image processing, a field of view contains a plurality of point images, of which at least 10 point images are suitable for image processing. Both the field of vision and
114 the dot images selected for analysis are preferably representative of the total ink dot population on the substrate (eg, in terms of dot shape).
As used herein in the description and in the claims section that follows, the term geometric projection refers to an imaginary geometric structure that is projected onto a printed side of a printing substrate.
As used herein in the description and in the claims section that follows, the term distinct ink dot refers to any image of ink or ink dots, at least partially arranged within the geometric projection, which is not neither a satellite point, nor an overlap point or dot image.
As used herein in the description and in the claims section that follows, the term mean deviation, with respect to roundness, convexity, and the like, of a plurality of different ink dots, refers to the sum of the individual distinct ink point deviations divided by the number of distinct individual ink points.
Process
115
A printed sample, preferably containing a high incidence of individual ink dots, is manually scanned under the LEXT microscope, using X20 magnification to obtain a field that includes at least 10 individual dots in a single frame. Care should be taken when selecting a field whose ink dot quality is fairly representative of the overall quality of the ink volume of the test print.
Each point within the selected frame is analyzed separately. Points that are split by the frame margins (which can be considered a square geometric projection) are considered part of the plot, and are analyzed. Any overlapping satellite points are excluded from the analysis. A satellite is defined as an ink dot whose area is less than 2 5% of the average dot area of the dots within the frame, for frames that have a generally homogeneous dot size, or as an ink dot whose area is less than 2 5% of the closest adjacent point, for non-homogeneous frames.
Each different ink dot is subsequently magnified with an X100 zoom, and image processing can be performed according to the procedure provided above with respect to the convex and roundness procedures.
116
Results
Figure 5F-1 provides an enlarged view of a small field of ink dots on a commodity-coated fibrous substrate (Arjowiggins Coated Recycled Gloss, 17.0g), the field produced using an available aqueous direct inkjet printer. commercially. Ink image A is a satellite, and was excluded from the analysis. Point B is split at the edge of the frame, and is included in the analysis (that is, the entire ink point is analyzed). The tail or projection C is considered to be part of the ink dot on its left. Thus, the field contains only 6 ink dots for image processing.
Figure 5F-2 provides an enlarged view of a field of an ink dot structure according to the present invention, in which the commodity coated substrate is identical to that of Figure 5F-1. The Ink image of D, by way of example, is a satellite, and is excluded from the analysis. Therefore, the field contains 12 ink dots for image processing.
It is apparent from a comparison of the figures that the ink dot field shown in Figure 5F-1 shows the shape of the upper dot and the
117 midpoint shape, relative to the ink dot field shown in Figure 5F-2.
Figure 5G-1 provides an enlarged view of a field of ink spots or smudges on an uncoated fibrous substrate (Hadar Top 170g-offset uncoated), the field is produced using an aqueous direct inkjet printer available from the market. At higher magnification, it became apparent that points E and F are distinct individual points. While several stains are fairly round and well formed, most stains show poor roundness and convexity, have poorly defined edges, and appear to contain multiple associating or weakly associated ink centers.
In contrast, Figure 5G-2 provides an enlarged view of a field of an ink dot structure according to the present invention, in which the uncoated substrate is identical to that of Figure 5G-1. Each ink dot shows good roundness and convexity, and has well defined edges. In addition, each ink dot is arranged on top of the thick, uncoated fibrous substrate.
The deviation of the roundness and non-convex data for each of the fields is provided in Tables 4A-4D.
The Ink Dot Structure Fields
118 according to the present invention (average) showed no convexities of 0.003 for the Arjowiggins coated substrate, and 0.013 for the Hadar Top uncoated substrate. These average values are very similar to the non-convexities shown by the individual ink dots of the present invention on these substrates (0.004 and 0.010, respectively). Similarly, the ink dot structure fields according to the present invention showed roundness deviations (average) of 0.059 for the Arjowiggins coated substrate, and 0.273 for the Hadar Top uncoated substrate. These mean values are higher than, but quite similar to, the roundness deviations shown by the individual ink dots of the present invention on these substrates (0.026 and 0.239, respectively). As expressed herein above, and as is evident from the view of Figures 5F-2 and 5G-2, the ink dots in the ink dot structures of the present invention tend to consistently show good shape properties (such as convexity). and roundness), largely independent of the particular local topographic characteristics of the substrate.
These exemplary results have been confirmed on several additional fibrous substrates, with base products as uncoated.
both coated
119
For all the fibrous substrates coated with basic products analyzed, the ink dot structure fields according to the present invention showed an average non-convexity of at most 0.05, at most 0.04, at most 0.03, at most 0.025 , at most 0.020, at most 0.015, at most 0.012, at most 0.010, at most 0.009, or at most 0.008.
For all the uncoated fibrous substrates tested, the ink dot structure fields according to the present invention showed a mean non-convexity of at most 0.085, at most 0.07, at most 0.06, at most 0.05, at at most 0.04, at most 0.03, at most 0.025, at most 0.020, at most 0.018, or at most 0.015.
120
TABLE 4A
TABLE 4B
COATED SUBSTRATE
Points Structure
Prior Art Ink (Fig. 5F-1)
Points Structure
Ink of the Invention (Fig. 5F-2)
<td>Point index</td><td>ER-l</td><td>l-CX</td>
<td> 1</td><td> 0.567</td><td> 0.038</td>
<td> 2</td><td> 0.946</td><td> 0.134</td>
<td> 3</td><td> 1.933</td><td> 0.132</td>
<td> 4</td><td> 0.675</td><td> 0.048</td>
<td> 5</td><td> 0.565</td><td> 0.030</td>
<td> 6</td><td> 0.972</td><td> 0.130</td>
<td>Average</td><td> 0.943</td><td> 0.085</td>
<td>Point Index</td><td>ER-l</td><td>l-CX</td>
<td> 1</td><td> 0.049</td><td> 0.003</td>
<td> 2</td><td> 0.070</td><td> 0.004</td>
<td> 3</td><td> 0.049</td><td> 0.003</td>
<td> 4</td><td> 0.060</td><td> 0.003</td>
<td> 5</td><td> 0.050</td><td> 0.003</td>
<td> 6</td><td> 0.054</td><td> 0.003</td>
<td> 7</td><td> 0.066</td><td> 0.003</td>
<td> 8</td><td> 0.079</td><td> 0.004</td>
<td> 9</td><td> 0.054</td><td> 0.004</td>
<td> 10</td><td> 0.057</td><td> 0.005</td>
<td> 11</td><td> 0.050</td><td> 0.002</td>
<td> 12</td><td> 0.068</td><td> 0.004</td>
<td>Average</td><td> 0.059</td><td> 0.003</td>
TABLE 4C
TABLE 4D
UNCOATED SUBSTRATE
Points Structure
Prior Art Ink (Fig. 5g-l)
Points Structure
Ink of the Invention (Fig. 5g-2)
<td>Point index</td><td>ER-l</td><td>l-CX</td>
<td> 1</td><td> 5.410</td><td> 0.225</td>
<td> 2</td><td> 3.878</td><td> 0.319</td>
<td> 3</td><td> 4.025</td><td> 0.311</td>
<td> 4</td><td> 1.415</td><td> 0.159</td>
<td> 5</td><td> 2.846</td><td> 0.297</td>
<td> 6</td><td> 3.566</td><td> 0.283</td>
<td> 7</td><td> 1.584</td><td> 0.145</td>
<td> 3</td><td> 4.051</td><td> 0.285</td>
<td>Average</td><td> 3.347</td><td> 0.253</td>
<td>Point index</td><td>ER-l</td><td>l-CX</td>
<td> 1</td><td> 0.277</td><td> 0.016</td>
<td> 2</td><td> 0.151</td><td> 0.007</td>
<td> 3</td><td> 0.212</td><td> 0.009</td>
<td> 4</td><td> 0.302</td><td> 0.017</td>
<td> 5</td><td> 0.323</td><td> 0.020</td>
<td> 6</td><td> 0.355</td><td> 0.015</td>
<td> 7</td><td> 0.316</td><td> 0.018</td>
<td> 3</td><td> 0.196</td><td> 0.007</td>
<td> 9</td><td> 0.274</td><td> 0.008</td>
<td> 10</td><td> 0.307</td><td> 0.021</td>
<td> 11</td><td> 0.247</td><td> 0.010</td>
<td> 12</td><td> 0.319</td><td> 0.011</td>
<td>Average</td><td> 0.273</td><td> 0,013</td>
121
In some modalities, the non-convex field is at least 0.0005, at least 0.001, at least 0.002, at least 0.003, or at least approximately 0.004. In some cases, and in particular for uncoated fibrous substrates, the field or mean of non-convexity can be at least 0.05, at least 0.07, at least 0.10, at least 0.12, at least 0.15, at least minus 0.16, at least 0.17, or at least 0.18.
For all the fibrous substrates covered with raw materials analyzed, the fields of the ink dot structure according to the present invention showed a
<td>mean roundness deviation of</td><td>to what</td><td>sumo</td><td> 0.60,</td><td>to what</td><td>sumo</td>
<td>0.50, at most 0.45, at most</td><td> 0.40,</td><td>to what</td><td>sumo</td><td> 0.35,</td><td>to what</td>
<td>at most 0.30, at most 0.25, at</td><td>sumo</td><td> 0.20,</td><td>to what</td><td>sumo</td><td> 0.17,</td>
<td>at most 0.15, at most 0.12,</td><td>or what</td><td>sumo</td><td> 0.10.</td><td></td><td></td>
For all the uncoated fibrous substrates tested, the ink dot structure fields according to the present invention showed a mean roundness deviation of at most 0.85, at most 0.7, at most 0.6, at most 0.5, at at most 0.4, at most 0.35, at most 0.3, at most 0.25, at most 0.22, or at most 0.20.
In some modalities, the mean roundness deviation is at least 0.010, at least 0.02, at least 0.03, or at least about 0.04. In some cases, the roundness deviation may be so
122
<td>less</td><td> 0.05,</td><td>by</td><td>the</td><td>less</td><td> 0.07,</td><td>by</td><td>least</td><td> 0.10,</td><td>by</td><td>the</td>
<td>less</td><td> 0.12,</td><td>by</td><td>the</td><td>less</td><td> 0.15,</td><td>by</td><td>least</td><td> 0.16,</td><td>by</td><td>the</td>
<td>less</td><td> 0.17,</td><td>or by</td><td>the</td><td>less</td><td> 0.18.</td><td></td><td></td><td></td><td></td><td></td>
While the non-convexity and deviation of the roundness values described above are for fields that have at least 10 points suitable for evaluation, they apply more to fields that have at least 20, at least 50, or at least minus 200 of those suitable points. Furthermore, the inventors have found that the distinction between the two non-convex values and the deviation of the roundness values of the ink dot structures of the invention from the ink dot structures of the prior art becomes even more statistically significant with increasing field size.
For all the tested plastic substrates described in greater detail below, the ink dot structure fields according to the present invention showed an average non-convexity of at most 0.075, at most 0.06, at most 0.05, at at most 0.04, at most 0.03, at most 0.025, at most 0.020, at most 0.015, at most 0.012, at most 0.010, at most 0.009, or at most 0.008; the fields of the ink dot structure according to the present invention showed a mean roundness deviation of at most 0.8, at most 0.7, at most 0.6, at
123 at most 0.5, at most 0.4, at most 0.35, at most 0.3, at most 0.25, at most 0.20, at most 0.18, or at most 0.15. Soft plastics, such as atactic polypropylene and various polyesters, showed a mean roundness deviation of at most 0.35, at most
0.3, at most 0.25, at most 0.20, at most 0.18, at most 0.15, at most 0.12, at most 0.10, at most 0.08, at most 0.06, at most 0.05, at at most 0.04, or at most
0.035.
Plastic substrates
Figures 5H-1 - 5H-3 provide enlarged top views of the ink dot structures in accordance with the present invention, wherein an ink dot is printed on each of several exemplary plastic printing substrates, including biaxially oriented polypropylene-BOPP (Figure 5H-1); anti-static polyester (Figure 5H-2); and atactic polypropylene (Figure 5H-3).
On all of the various plastic printing substrates used, and as exemplary shown in Figures 5H-1 - 5H-3, the ink dots of the present invention show superior shape and optical properties, including roundness, convexity,
124 edge irregularity, and surface roughness.
Figure 5H-4 provides an enlarged top view of an ink dot printed on a polyester substrate, in accordance with the present invention. Figure 5H-4 further provides a cross-sectional representation showing the roughness of the ink dot surface and the substrate. The ink dot has a height of approximately 600 nm. The height deviation is less than ± 50nm above the mean of 80% of the spot diameter, and less than ± 25nm above the mean of 60% of the spot diameter. Exemplary roundness and non-convex deviations are provided in Table 5.
TABLE 5
<td>Substrate Type</td><td>ER-1</td><td>1-CX</td>
<td>Unsightly BOPP</td><td> 0.1442</td><td> 0.0097</td>
<td>Atactic polyester</td><td> 0.0288</td><td> 0.0016</td>
<td>Polypropylene</td><td> 0.0299</td><td> 0.0020</td>
The non-convexity, or deviation from the convexity of the ink dots printed on a wide variety of plastic printing substrates, was at most 0.020, at most 0.018, at most 0.016, at most 0.014, at most at most 0.012, or at most 0.010. At least some of the ink dots, on all of these substrates, including BOPP,
125 showed no convexities of at most 0.008, at most 0.006, at most 0.005, at most 0.004, at most 0.0035,
0.0030 at most, at most 0.0025, or at most 0.0020. On polyester and atactic polypropylene substrates, typical ink dots showed non-convexities of at most 0.006, at most 0.004, at most 0.0035, and even more typically, at most 0.0030, at most 0.0025, or at most 0.0020.
On all the plastic substrates tested, the individual ink dots in the ink dot structures according to the present invention showed a roundness standard deviation of at most 0.8, at most 0.7, at most 0.6, at at most 0.5, at most 0.4, at most
0.35, at most 0.3, at most 0.25, at most 0.20, at most 0.18, or at most 0.15. In various soft plastics, such as atactic polypropylene and various polyesters, the individual ink dots showed a roundness standard deviation of at most 0.35, at most 0.3, at most 0.25, at most 0.20, at most 0.18, at most 0.15, at most 0.12, at most 0.10, at most 0.08, at most 0.06, at most 0.05, at most 0.04, or at most 0.035.
Figures 5H-5 - 5H-7 each provide an enlarged view of a field having an ink dot structure according to the present invention, each field containing the ink dots is printed on a
126 respective plastic substrate. In Figure 5H-5, the substrate is antistatic polyester; In Figure 5H-6, the substrate is polypropylene (BOPP WBI 35 microns (Dor, Israel)); In Figure 5H-7, the printing substrate is atactic polypropylene. In all these fields, each ink dot exhibits good roundness and convexity, has well-defined edges, and is arranged on top of the particular plastic substrate. The ink dots of the ink on plastic dot structures of the invention may closely resemble the ink dots on commodity coated substrates, particularly with respect to roundness, convexity, edge irregularity, and other optically shaped properties. . For a wide variety of plastic substrates, the ink-on-plastic dots of the invention show shape properties of optical structures (eg, roundness deviation, non-convexity) equal to, or exceeding, that of commodity coated substrates .
Optical Uniformity
The original ink film images provided in Figures 5A and 5B are not optically uniform. In general, ink film images
127 Arranged on uncoated paper are less optically uniform than the corresponding ink film images arranged on coated paper.
Furthermore, it can be seen that the ink dots of the invention have superior optical uniformity compared to the various forms of ink of the prior art. This appears to be for both printed and uncoated substrates. What is easily observed by the human eye can be quantified using image processing techniques. The ink volume uniformity measurement method is provided below.
Measurement of optical uniformity
Point images are loaded into ImageXpert software, preferably using the statistical rules provided above. Each image is loaded into each of the red, green, and blue channels. The channel selected for image processing is the channel that displays the highest visible detail, including the dot outline and color variation within the dot area, and the fibrous structure of the substrate surface. For example, the Red channel is typically more suitable for a cyan point, while the green channel is typically more suitable for a point.
128 magenta.
For each of the selected points, a line profile (preferably 3 line profiles for each of the at least 10 most representative points) is measured across the point area, crossing through the center of the point. Since the line profile is measured in a single channel, gray values (0-2 55, non-color values) are measured. Line profiles are taken through the center of the point and cover only the inner two-thirds of the point diameter, to avoid edge effects. The standard for the sampling rate is around 8 optical measurements along the line profile (8 uniformly-spaced measured gray values along each micrometer, or 125 nanometers +/- 25 nanometers per measurement at along the line profile), which was the automatic frequency of the ImageXpert Software, and which was found to be suitable and robust for the task in question.
The standard deviation (STD) of each of the line profiles is calculated, and multiple STDs of the line profile are averaged for each type of image printed at a single value.
Figures 6A-1 to 6J-2 provide images of ink spots or dots obtained using different printing technologies, and uniformity profiles
129 optics for it. More specifically, Figures 6A-1 through 6E-1 provide ink dot images arranged on uncoated paper, for the following printing technologies: HP Deskjet 9000 (Figure 6A-1); HP Indigo 7500 Digital Press (Figure 6A-2); Offset: Ryobi 755 (Figure 6A-3); Xerox DC8000 (Figure 6A-4); and for one embodiment of the printing technology of the invention (Figure 6A-5). Similarly, Figures 6F-1 to 6J-1 provide images of ink dots arranged on the coated paper of commodities, for fine printing technologies.
Figures 6A-2 through 6J-2 provide, respectively, a graphical representation (without color) of the relative value of gray as a function of the position on the line that passes through the center of the ink dot image, for each from the ink dot images provided by Figures 6A-1 to 6E-1 (on uncoated paper), and by Figures 6F-1 to 6J-1 (on coated paper). A relatively flat linear profile for a special ink image indicates high optical uniformity along the line.
The STD of each of the line profiles of each type of printed image is provided in Table 6, for coated and uncoated substrates. The results seem to confirm that the ink spots arranged on the fibrous printing substrates without coating
130 they have low uniformity with respect to the corresponding ink dots arranged on the coated fibrous print substrates.
On the other hand, for the uncoated substrates, the profile of the ink film line of the invention produced by the system of the invention and the process had an STD of 4.7, which compares favorably to the STD achieved using the various prior art technologies (13.7 to 19.1). For coated substrates, the inventive ink dot line profile produced by the inventive system and process had a STD of 2.5, which compares favorably, but less surprisingly, to STDs achieved using the various technologies of the prior art (from 4 to 11.6).
When comparing films or dots on coated papers, the average of each of the standard deviations (STD) of the dot profiles of the present invention was always below 3. More generally, the STD of the dot profiles of the present invention is less than 4.5, less than 4, less than 3.5, less than 3 or less than
2.7.
131
Table 6
<td rowspan="2"></td><td colspan="2">STANDARD DEVIATION</td>
<td>Covered</td><td>Uncoated</td>
<td>HP DeskJet 9000</td><td> 19.1</td><td> 4</td>
<td>HR Indigo 7500</td><td> 13.7</td><td> 11.6</td>
<td>Offset: Ryobi 755</td><td> 18.6</td><td> 5.75</td>
<td>Xerox DC8000</td><td> 15.4</td><td> 7</td>
<td>Invention System</td><td> 4.7</td><td> 2.5</td>
In contrast, the STD of the point uniformity profile was 5.75, and the STD of the LEP (Indigo) point uniformity profile was 11.6. Therefore, the STD values for the dots of the present invention differ markedly from the STD values of exemplary printed dots of the prior art, both on coated and uncoated papers.
When comparing films or dots on uncoated papers, the standard deviation (STD) of the dot profiles of the present invention was always less than 5. More generally, the STD of the dot profiles of the present invention is less than 10, less than 8, less than 7, or less than 6.
Because, as noted above, ink images can contain an extremely large plurality of individual or unique ink dots (at least 20, at least 100, at least 1,000, at least 10,000, or at least minus 100,000), you can
132 it is relevant to statistically define the ink dot structures of the invention in which at least 10%, at least 20%, or at least 30%, and in some cases, at least 50%, at least 70 %, or at least 90%, of the ink dots of the invention (or single-drop ink dots of the invention), arranged on any uncoated, coated (or coated commodity) fibrous substrate, show the standard deviations above for uncoated papers and for commodity coated papers.
Optical Density
Ink formulations containing a 1: 3 pigment to resin ratio (Clariant Hostajet Black O-PT nano dispersion) were prepared according to Example 6. The formulations were applied to a Condat Gloss® coated paper (135 gsm) using various coating rollers that produce wet layers having a characteristic thickness of 4-50 microns.
The above formulation contains approximately 9.6% ink solids, of which 2 5% is pigment, and about 7 5% is resin, by weight. In all tests, the resin to pigment ratio was maintained at 3: 1. The solids fraction of the
133 Ink in the ink formulations ranged from 0.05 to 0.12, by weight (5% to 12%). The detraction was done in a standard way, directly on the paper. The thickness of each ink film obtained was calculated.
Optical density is measured with an X-Rite 528 epectrodensitometer, using the absolute, T-state mode. The results are provided in Table 7. Figure 12 provides the obtained optical density points, along with a fitted curve (the lowest curve) of the obtained optical density as a function of film thickness. Although we do not know that the formulation is a prior art formulation, the fitted curve may represent the prior art optical density capabilities.
Table 7
<td>Main Cylinder Size (μπι)</td><td>Ink Solids Fraction</td><td>Ink Film Thickness (pm)</td><td>Density Optics</td>
<td> 50</td><td> 0.096</td><td> 4.80</td><td> 2.35</td>
<td> 24</td><td> 0.096</td><td> 2.30</td><td> 2.10</td>
<td> 12</td><td> 0.096</td><td> 1.15</td><td> 1.85</td>
<td> 6</td><td> 0.096</td><td> 0.58</td><td> 1.40</td>
<td> 4</td><td> 0.096</td><td> 0.38</td><td> 1.10</td>
<td> 12</td><td> 0.050</td><td> 0.60</td><td> 1.40</td>
<td> 12</td><td> 0.075</td><td> 0.90</td><td> 1.58</td>
<td> 12</td><td> 0.120</td><td> 1.44</td><td> 2.00</td>
134
The optical density of the ink film structures of the invention can be at least 5%, at least 7%, at least 10%, at least 12%, at least 15%, at least 18% , at least 20%, at least 22%, at least 2 5%, at least 2 8%, at least 3 0%, at least 35%, or at least 40% higher than any of the optical density points obtained and graphically represented in Figure 12, and / or higher than any point on the fitted curve represented by the function:
Οϋ ^ = 0.5321425673 + 1.87421537367 * H<sub>fl</sub>i<sub>m</sub> - 0.8410126431754 * (H<sub>fl</sub>i<sub>m</sub>)<sup>2</sup> +
0.1716685941273 * (II<sub>F</sub>i<sub>m</sub>)<sup>3</sup> - 0.0128364454332 * (H<sub>film</sub>)<sup>4</sup> where:
ODbaseiíne is the optical density provided by the fitted curve, and
Hfiim is the average thickness or average height of the ink film disposed on a printing substrate such as a fibrous printing substrate.
The specimen curves arranged on the fitted curve in Figure 12 are optical density curves of the structure of the ink film of the invention, in which the optical density is 7% greater or 15% greater, respectively, than OD<sub>base</sub>ii<sub>ne</sub>·
In absolute terms, the optical density of the ink film structures of the invention (OD<sub>inv</sub>ention)
135
<td>they can</td><td>to be</td><td>at least</td><td> 0.08,</td><td>by</td><td>the</td><td>less</td><td> 0.10,</td><td>by</td><td>the</td>
<td>less</td><td> 0.12,</td><td>at least</td><td> 0.15,</td><td>by</td><td>the</td><td>less</td><td> 0.18,</td><td>by</td><td>the</td>
<td>less</td><td> 0.20,</td><td>at least</td><td> 0.25,</td><td>by</td><td>the</td><td>less</td><td> 0.30,</td><td>by</td><td>the</td>
<td>less</td><td> 0.35,</td><td>or at least</td><td colspan="2">0.40 greater</td><td colspan="3">than anyone</td><td>of</td><td>the</td>
optical density points obtained and represented in Figure 12, and / or greater than any point on the fitted curve represented by the function provided above (OD<sub>basel</sub>i<sub>ne</sub>). Furthermore, for a film thickness of at least 1.5 microns, ODi<sub>nven</sub>tion can be at least 0.45, at least 0.50, at least 0.55, at least 0.60, at least 0.70, at least 0.80, at least 0.90, at least 1.00, at least 1.10, or at least 1.25 greater than any of the optical density points obtained and graphically represented in Figure 12, and / or greater than any point on the fitted curve represented by the function previously provided.
Figure 13 provides the optical density measurements of Figure 12, plotted as a function of pigment content or calculated average pigment thickness (T<sub>pig</sub>). The optical densities (Y axis) of Figure 13 are identical to those shown in Figure 12, but the X axis variable is the pigment content or calculated average pigment thickness, rather than the measured average ink film thickness or calculated. For the
136 so much,
ODbaseii ^ 0.5321425673 + 7.49686149468 * Tp¡<sub>g</sub> - 3.3640505727016 * (T<sub>pig</sub>)<sup>2</sup> + 0.6866743765092 * (Tp¡g)<sup>3</sup> - 0.0513457817328 * (Tpig)<sup>4</sup>
In the case of black pigments such as black pigments that include or consist of substantially carbon black, the calculated average pigment thickness may be more or less equal to the thickness of ink solids multiplied by the weight fraction of the pigment within the fraction of ink solids (by way of example, in the formulation referred to above, the weight fraction of the pigment is 0.25).
The optical density of the ink film structures of the invention can be at least 5%, at least 7%, at least 10%, at least 12%, at least 15%, at least 18 %, at least 20%, at least 22%, at least 25%, at least 28%, at least 30%, at least 35%, or at least 40% greater than any of the points of optical density obtained and graphically represented in Figure 13, and / or higher than any point on the fitted curve of 0D<sub>ba</sub>seiine as a function of the calculated average pigment thickness.
In absolute terms, the optical density of the ink film structures of the invention (OD<sub>in</sub>vention) can be at least 0.08, at least 0.10, so
137 minus 0.12, at least 0.15, at least 0.18, at least 0.20, at least 0.25, at least 0.30, at least 0.35, or at least 0.40 greater than any of the optical density points obtained and represented in Figure 13, and / or greater than any point on the fitted curve represented by the function provided above (OD<sub>base</sub>ii<sub>ne</sub>). Furthermore, for a film thickness of at least 1.5 microns, ODi<sub>nvent</sub>i<sub>on</sub> It can be at least 0.45, at least 0.50, at least 0.55, at least 0.60, at least 0.70, at least 0.80, at least 0.90, at least 1.00, at least 1.10, or by at least 1.2 5 greater than any of the optical density points obtained and represented in Figure 13, and / or greater than any point on the fitted curve of OD<sub>base</sub>ii<sub>ne</sub> as a function of the calculated average pigment thickness.
Color Range Volume
The color gamut of a particular printing technology can be defined as the sum total of all the colors that the printing technology can reproduce. While color ranges can be represented in different ways, a color range is generally represented in a color space.
138 three-dimensional.
ICC (International Color Consortium) profiles are often used by commercially available software to assess the volume of the color gamut.
The ISO 12647-2 (Modified Standard version), which is incorporated by reference for all purposes as set out in this document, refers to various printing parameters for offset lithographic processes, including CIELAB coordinates, gloss and ISO gloss. on five typical offset substrates.
The modified ISO 12647-2 standard defines the CIELAB color coordinates for the black-cyan-magenta-yellow print sequence, for each of the five typical offset substrates, and based on this, defines, for each of these substrates , a range of colors resulting from offset lithographic printing.
In practice, the volume capacity of the prior art color gamut can be at most about 400 kilograms (AE)<sup>3</sup> of coated wood-free paper (eg Type 1 and possibly Type 2 of ISO 12647-2 Modified Standard) used as a substrate in offset lithographic printing.
The volume capabilities of the color gamut
139 of the prior art may be somewhat lower for Type 3 substrates (at most about (380) kilo (AE)<sup>3</sup>) and for other types of offset lithographic printing substrates such as uncoated papers, for example various uncoated offset papers such as Type 4 and Type 5 of the modified ISO 12647-2 standard. The volume capacities of the prior art color gamut can be at most about 350 kilos (ΔΕ)<sup>3</sup> for such offset uncoated papers.
The thickness of the print image (dot or single film) associated with these color gamut volumes is assumed to be at least 0.9 to 1.1 microns.
In contrast, the volume of the color gamut of the ink film structures of the present invention, as determined, for example, by ICC profiles, may exceed or exceed the volumes of the previously provided color gamut. For each particular substrate type, the volume of the color gamut of the ink film structures of the invention may exceed the volume capacity of the respective existing color gamut by at least 7%, at least 10%, at least 12%, at least 15%, at least 18%, at least 20%, at least 25%, at least 30%, or at least 35%.
The volume of the color gamut of the
140 Ink film structures of the invention can exceed the volume of the aforementioned color gamut capabilities by at least 25 kilograms (AE)<sup>3</sup>, at least 40 kilo (AE)<sup>3</sup>, at least 60 kilo (AE)<sup>3</sup>, at least 80 kilo (AE)<sup>3</sup>, at least 100 kilo (AE)<sup>3</sup>, at least 120 kilo (AE)<sup>3</sup>, at least 140 kilo (AE)<sup>3</sup>, or at least 160 kilo kilo (AE)<sup>3</sup>.
In absolute terms, the color gamut volume of the ink film structures of the invention can be characterized by gamut volumes.
<td>of colors of at least 425 kilo (AE)<sup>3</sup></td><td>, by</td><td>the</td><td>less</td><td> 440</td>
<td>kilo (AE)<sup>3</sup>, at least 460 kilo (AE)<sup>3</sup>,</td><td>by</td><td>the</td><td>less</td><td> 480</td>
<td>kilo (AE)<sup>3</sup>, or at least 500 kilo (AE)<sup>3</sup>.</td><td>For</td><td>the</td><td colspan="2">substrates</td>
Type 1 and Type 2 and the like, the ink film structures of the invention can be further characterized by color gamut volumes of at least 52 0 kilo (AE)<sup>3</sup>, at least 540 kilo (AE)<sup>3</sup>, at least 560 kilo (AE)<sup>3</sup>, or at least 580 kilo (AE)<sup>3</sup>.
Without wishing to be limited in theory, the inventors believe that the increased volume of color gamut, as well as the improved optical density described above, may be at least partially, or largely, attributable to the lamination of the ink film. the invention on a top surface of the printing substrate. Because the shape of the film
141 can be largely determined before transfer to the substrate, the film can be integrally transferred from the ITM to the substrate. This continuous integral unit may be substantially solvent-free, so that there may be no penetration of any type of rubber carrier material into, or between, the substrate fibers. The integral film can form a laminated layer arranged entirely above the top surface of the fibrous printing substrate.
The ink film structures of the invention can achieve the various volumes of the established color gamut, not only within the range of 0.9 to 1.1 microns of film thickness, but surprisingly, at medium thicknesses or film heights that are more low or significantly less than the 0.9-1.1 micron range. The ink film structures of the invention can be characterized by these color gamut volumes for ink film thicknesses of less than 0.8 μπι, less than 0.7 μπι, less than 0.65 μπι, less than 0.6 μπι, less 0.55 μπι, less than 0.5 μπι, less than 0.45 μιη, or less than 0.4 μπι.
The ink film structures of the invention can also achieve the different volumes of the range of colors established in average thicknesses of
142 film that is at most 4 micrometers, at most 3.5 μιη, at most 3 μπι, at most 2.6 μιη, at most 2.3 μπι, at most 2 μιη, at most 1.7 μπι, at most 1.5 μιη, at most 1.3 μη, or at most 1.2 μη.
Furthermore, the ink film structures of the invention can also achieve full coverage of the color ranges defined by the ISO standard referenced above, within any of the film thickness ranges described above.
A new standard under development, ISO 15339 is provided in Table 8.
TABLE 8
<td>Condition of Print of Reference</td><td>Name</td><td>Typical use</td><td>ISO volume 15339 dE (CIELAS)<sup>3</sup></td>
<td> 1</td><td>Universal Coldset News</td><td>Newsprint, small range, Printing using cold offset, flexo, letterpress, etc.</td><td>100812.3 ¡23% pantones)</td>
<td> 2</td><td>Universal Heatset News</td><td>Improved newsprint, moderate gamut, printing using heatset and similar technologies</td><td>184483.3 (32% panties)</td>
<td> 3</td><td>Universal Prem Uncoated</td><td>Useful print on uncoated matte paper</td><td>176121.3 (31% panties)</td>
<td> 4</td><td>Universal Your perC 1</td><td>General printing on super calendered paper</td><td>262646.2 (39% panties)</td>
<td> 5</td><td>Universal Pub Coated</td><td>Magazine publication</td><td>345892 2 (47% pantones)</td>
<td> 6</td><td>Universal Prem Coated</td><td>Wide range, printing using rotary sheet offset, and gravure</td><td>398593.1 (52% panties)</td>
<td> 7</td><td>Universal Extra Big</td><td>Digital printing and potentially other high-end printing processes</td><td>515753.2 (62% panties)</td>
143
Color gamut prints were made using Dimatix SAMBA single pass inkjet print heads that have a nominal resolution of 1200dpi and provide an average droplet volume of 9PL.
The ink in the print head was kept at 22 ° C, the holder was kept at 70 ° C. Manual drying was performed at approximately 450 ° C in a volume flow of 16CFM. The transfer temperature was about 130 ° C. The ink formulations were prepared substantially as described above with respect to Examples 2, 5, 8, and 9.
For each run, 170 patches of different color combinations were printed and measured using a spectrophotometer, to create the color gamut. Each color separation was sequentially printed on a hot rubber holder and dried manually for approximately 2 seconds. The order of the separations was yellow, magenta, cyan and black. After all the separations were printed, the image was transferred to the paper by applying pressure using a cylindrical weight.
Each individual color separation had a thickness of up to 600, up to 650, or up to 700 nm. The total thickness was at most 2,000 nm, and on average around
144 1,700 nm, l, 800nm or 1900nm. In some runs, each individual color separation had a thickness of up to 450, up to 500, or up to 550 nm, and the corresponding average total thickness was approximately 1,300 nm, 1,400 nm, or 1,500 nm.
All comparisons were made with standard white, as if printed on the same medium.
The software used to create a color profile of the prints was ilProfiler version 1.4.2 (XRite Inc., Grand Rapids, MI). Measurements were made using an ilPro2 spectrophotometer (X-Rite Inc.), and standard techniques (similar to those of ilProfiler) were used to plot the graphs and to calculate the volume of the color gamut.
Abrasion resistance
An important feature of printed ink films is abrasion resistance. Abrasion resistance is a property of printed ink that describes the degree to which the printed image can maintain its surface and structural integrity under prolonged rubbing, scratching and rubbing. During transportation and handling, the exposed surface of printed ink films can be noticeably worn, breaking the
145 Print quality. Consequently, a wide variety of printed products (eg, magazines and brochures) may require ink film structures that have superior abrasion resistance.
Abrasion resistance can typically be improved by using suitable formulations comprising resins that have good abrasion resistance properties. Alternatively or additionally, special components such as waxes and / or hard drying oils can be introduced into the formulation.
The introduction of waxes or oils into the ink formulation can affect the overall attributes of the ink and can also lead to other printing related or printing related process problems. Therefore, providing the only necessary abrasion resistance by means of abrasion of resistant resins can be advantageous at least in this regard.
The inventors have discovered that in the ink formulations and ink film structures of the present invention, various resins, having relatively low volumetric or mechanical abrasion resistance properties, can advantageously contribute to the thermo-rheological behavior of ink formulations, whereby at least one
146 From: the development of the ink film, the transfer from the intermediate transfer member or rubber holder, and the adhesion to the printing substrate, can be appreciably improved. The low mechanical properties of the resins can include a low hardness value.
The inventors have found that the abrasion resistance of print images printed with ink formulations of the invention containing such resins is surprisingly high with respect to the volumetric abrasion resistance properties of those resins.
Abrasion resistance was measured by sweeping an abrasive block on top of each sample a number of times, and measuring the optical density of the samples compared to the reference values established for the samples prior to abrasive test. The samples were placed in a TMI (Testing Machine incorporated) ink rub tester (model # 10-18-01) and a dry ink rub test was performed using a 1.8 kg test block having a piece of paper Condat Gloss® (135 gsm) arranged on it. The optical densities of the samples were measured before the test and after 100 cycles of abrasion. This measurement procedure
147 Abrasion resistance is recommended by the TMI Instruction Manual, and is based on the procedure of ASTM D5264.
By way of example: the high molecular weight polymer of the Joncryl® 2178 film-forming emulsion was tested for abrasion resistance, and was found to have excellent abrasion resistance properties. An ink formulation containing Joncryl® 2178 was prepared, and applied to Condat Gloss® paper (135 gsm) with a 12 micron coating stick. With this ink formulation, a wet thickness of 12 μπι roughly corresponds to a dry film that has a film thickness of 1.2 μπι. The detraction was carried out in the usual way. Next, the dry ink film sample was tested for abrasion resistance. The optical density loss was only 18% after 100 abrasion cycles, which is considered an excellent result for various printing applications.
The Joncryl® 2178 film-forming emulsion was further tested for thermoreological compatibility with the process of the invention, and was found to have low transfer properties.
A second lower molecular weight resin (Neocryl® BT-26) was tested for resistance to
148 abrasion proof film, and found to have relatively low abrasion resistance properties. As with the first resin, an ink formulation was prepared containing the aforementioned second resin, and applied to the Condat Gloss® paper (135 gsm) using the 12 pm coating stick. The obtained dry film, having a thickness of about 1.2 pm, was subjected to the abrasion resistance described above. The optical density loss was 53% after 100 abrasion cycles, almost three times the loss supported by sample 1.
The ink formulation of the invention was further tested for thermo-rheological compatibility with the method of the invention, and was found to have adequate transfer properties.
The inventors then tested this second resin-containing ink formulation having relatively low abrasion resistance properties in a printing system and processing method of the present invention. Again, Condat Gloss® paper (135 gsm) was used as the printing substrate. Some of the ink film structures produced were evaluated to determine various printing properties of the ink film and structure, including the
149 abrasion resistance.
The printed substrate obtained using the second ink formulation was subjected to an abrasion resistance test identical to that performed for the reduction samples. Surprisingly, the optical density loss was 16.6%, which is comparable to the abrasion resistance of the first highly abrasion-resistant dry ink film sample, and is a good enough result for a wide range of applications. Print.
In another exemplary abrasion resistance test, an ink formulation was prepared, according to the composition provided in Example 8. The ink was applied to Condat Gloss® paper (135 gsm) using the 12 µπι coating rod. Next, the ink was dried by hot air and the abrasion resistance was tested, as described above. The optical density loss was 30% after 100 abrasion cycles.
In another exemplary abrasion resistance test, the ink formulation described above was used to produce a dry film by the method of the invention. The dry film, having a thickness of approximately 1 micrometer, was obtained by applying the wet ink (12 μπι, as mentioned
150 above) in a hot silicone tub holder (130 ° C) [silanol-terminated polydimethylsiloxane], the
<td colspan="3">film drying, and transfer</td><td>of</td><td colspan="2">the movie</td>
<td>dry from</td><td>Condat Gloss® paper</td><td>(135 gsm).</td><td>The</td><td>lost</td><td>of</td>
<td>density</td><td>optics was 19%</td><td>after</td><td> 100</td><td>cycles</td><td>of</td>
abrasion.
Adhesive failure
The adhesive properties of the ink film structures of the invention (inter alia, Example 4) were evaluated and compared with the adhesive properties of ink dot or ink film structures of the prior art. A standard test procedure used: the adhesion of quantitative test ink FTM 21 from FINAT (Fédération Internationale des
Fabricants et Transformateurs d'Adhesifs et Thermocollants sur Papiers et Autres Soporta), provided below.
FINAT FTM 21
Ink Adhesion - Basic
Area of application. This method allows a quick evaluation of the degree of adhesion of a
151 print or lacquer to a self-adhesive material.
Definition. The printing ink or lacquer is applied to the substrate and cured in the printing press or using a standard method appropriate for the type of ink. Ink adhesion is then calculated by the amount of ink that can be removed when the adhesive tape is applied and removed. The resistance of the ink to mechanical removal is also measured by scratching the ink and by deformation under pressure.
Test equipment. A means of applying and curing ink. High release adhesion tape ('aggressive'), eg Tesa 7475 (acrylic based), Tesa 7476 (rubber based), or 3M Scotch 810 rollers. FINAT roller to smooth the tape over the specimen. Metal spatula. Gloves
Test pieces. If the required ink has not been applied to the substrate as part of the printing process, samples are prepared for proofing by coating the ink to a uniform thickness (for example, with a Meyer bar for low-viscosity inks) and for curing the coating as recommended by the supplier. Sheets A-4 are a conveniently sized sample for this
<td>proof.</td><td>The condition of</td><td>23 ° C ± test</td><td>2 ° C</td><td>and a humidity</td>
<td>relative</td><td>50% (RH)</td><td>± 5% RH. Yes</td><td>is</td><td>possible, the</td>
<td>test tubes</td><td colspan="2">will be conditioned for</td><td>the</td><td>minus four</td>
152 hours before rehearsal.
Tape test. Place the sample on a smooth, flat, hard surface and apply the adhesive tape, leaving a small part of the tape unattached to the test piece, making sure that no air bubbles are trapped under the tape. Using the FINAT roller, press down on the tape passing the roller twice in each direction on the sample, and then fold the unattached part of the tape on itself at a 180 ° angle. Within 20 minutes after rolling the tape, mounting the sample to a frame, or using one hand to hold the specimen firmly, pull the free piece of the tape toward you with the other hand: slowly at first at constant speed, then very quickly and accelerate. (The fastest speed is the most aggressive test.) FINAT Technical Handbook, 6th. Edition, 2001 53.
Sample performance is recorded by comparison with control samples that have been previously measured, or by reference to the following classification:
Grade 1 No ink removal
Grade 2 Low ink removal (<10%)
Grade 3 Moderate ink removal (10 - 30%)
Grade 4 Severe ink removal (30 - 60%)
Grade 5 Almost total ink removal (>
60%)
153
Exemplary results are provided in
Table 9.
Direct inkjet (drop-on-demand) technologies show low ink adhesion to various plastic substrates. Solid ink technology exemplified by XEROX Phaser 8560 and latex printing technology exemplified by HP Designjet Z6200 also showed low ink adhesion to various plastic substrates. Offset lithography, gravure printing, and some LEP and DEP technologies display strong adhesive properties on tested plastic substrates.
With respect to various plastic substrates, including polypropylene sheets (eg, biaxially oriented, polypropylene-BOPP), polyethylene sheets, and polyethylene terephthalate sheets, the ink film structures of the present invention show strong adhesive properties .
In some embodiments of the invention, the plastic dot ink structures showed an adhesive failure of at most 10%, and more typically, at most 5%, when subjected to a standard tape test (FINAT FTM 21 , basic ink adhesion test). In most cases, the dot-on-plastic ink structures were free or
154 substantially free of adhesive failure when subjected to this tape test.
I know
TABLE 9
<td colspan="2">Print</td><td rowspan="2">Substrate Type</td><td colspan="2">MIDDLE GRADE</td>
<td colspan="2">Technology | Device</td><td>without cutting</td><td>with cut</td>
<td colspan="2">Variable Rotary Offset Printing</td><td>Polyethylene (red)</td><td> 1</td><td> 1</td>
<td colspan="2">Rotogravure</td><td>Cellulose</td><td> 1</td><td> 1</td>
<td>Flexography</td><td>COMEXI</td><td>Polyethylene</td><td> 1.66</td><td> 2</td>
<td>Flexography</td><td></td><td>PP</td><td> 1</td><td> 1</td>
<td>LEP</td><td>INDIGO</td><td>Shrunken Rotary Inventory</td><td> 1</td><td> 1</td>
<td>Inkjet (Industrial)</td><td>EFI Jetrion</td><td>PP</td><td> 1</td><td> 1</td>
<td>DEP (LED base)</td><td>XEIKON</td><td>PP</td><td> 1</td><td> 2</td>
<td>Rotogravure</td><td></td><td>Polyethylene</td><td> 1</td><td> 1</td>
<td>LEP</td><td>INDIGO WS 6600</td><td>Polyethylene</td><td> 1</td><td> 1.66</td>
<td>Solid ink</td><td>XEROX Phaser 8560</td><td>PP</td><td> 5</td><td> 5</td>
<td>Solid ink</td><td>XEROX Phaser 8560</td><td>Jolybar Synt paper. 60</td><td> 5</td><td> 5</td>
<td>Solid ink</td><td>XEROX Phaser 8560</td><td>100 PP90M</td><td> 5</td><td> 5</td>
<td>Solid ink</td><td>XEROX Phaser 8560</td><td>PPXLABEL110M</td><td> 5</td><td> 5</td>
<td>Latex</td><td>HP DesignjetZ62OO</td><td>PP (HP Everyday Matte)</td><td> 4.33</td><td> 4.33</td>
<td>Ink injection</td><td>Epxon Stylus SX-125</td><td>PP</td><td> 5</td><td> 5</td>
<td>Ink injection</td><td>Epxon Stylus SX-125</td><td>PETF-Slim</td><td> 5</td><td> 5</td>
<td>Ink injection</td><td>Epxon Stylus SX-125</td><td>Polyethylene</td><td> 5</td><td> 5</td>
<td>Ink injection</td><td>Epxon Stylus SX-125</td><td>PETF-Coarse</td><td> 5</td><td> 5</td>
<td>Ink injection</td><td>HP DeskJet 9803</td><td>PP</td><td> 5</td><td> 5</td>
<td>Ink injection</td><td>HP DeskJet 9803</td><td>PETF-Slim</td><td> 5</td><td> 5</td>
<td>Ink injection</td><td>HP DeskJet 9803</td><td>Polyethylene</td><td> 5</td><td> 5</td>
<td>Ink injection</td><td>HP DeskJet 9803</td><td>PETF-Coarse</td><td> 5</td><td> 5</td>
<td></td><td></td><td></td><td></td><td></td>
<td>Present Invention</td><td>Landa Press</td><td>PP (synthetic paper)</td><td> 1</td><td> 1</td>
<td>Present Invention</td><td>Landa Press</td><td>PP</td><td> 1</td><td> 1</td>
<td>Present Invention</td><td>Landa Press</td><td>PETF-Slim</td><td> 1</td><td> 1</td>
<td>Present Invention</td><td>Landa Press</td><td>Polyethylene</td><td> 1</td><td> 1</td>
<td>Present Invention</td><td>Landa Press</td><td>PETF-Coarse</td><td> 1</td><td> 1.33</td>
Glass transition temperature of the resin
The inventors have found that in selecting resins for use within formulations that
155 Supported by the ink film structures of the present invention, the softening temperature (or glass transition temperature of at least partially amorphous resins) can be a useful indicator of resin suitability. Specifically, the resins used in the ink formulations (and arranged in the ink films of the present invention) can have a T<sub>g</sub> below 47 ° C or below 45 ° C, and more typically below 43 ° C, below 40 ° C, below 35 ° C, below 30 ° C, below 25 ° C, or below 20 ° C. More generally, from a process standpoint, the ink formulations disposed of in the ITM, after becoming pH adjusting agents or devoid of substantially no water, any co-solvent, and any other vaporizable material to be vaporized under process conditions, for example, (producing ink solids, ink residue, or the like), and / or the resins thereof, may have a T<sub>g</sub> below 47 ° C or below 45 ° C, and more typically below 43 ° C, below 40 ° C, below 35 ° C, below 30 ° C, below 25 ° C, or below 20 ° C.
Thermo-rheological properties
The process of the invention may include heating the film or ink image, during
156 transport on the surface of the image transfer member, to evaporate the aqueous vehicle from the ink image. Heating can also facilitate the reduction of the viscosity of the ink to allow the transfer conditions from the ITM to the substrate. The ink image may be heated to a temperature at which the residue of organic polymeric resin film and dye remaining after evaporation of the aqueous vehicle becomes tacky (eg, by softening of the resin).
The film residue on the surface of the image transfer member can be dry or substantially dry. The film includes the resin and colorant of the ink formulation. The film residue may further include small amounts of one or more surfactants or dispersants, which are typically soluble in water at the pH of the ink (ie, prior to injection). The film residue may further include one or more plasticizers.
The ink film residue may become tacky before it reaches the print cylinder. In this case, the film can be cooled at the printing station, due to its contact with the substrate and exposure to the environment. The already tacky ink film can immediately adhere to the substrate on which it is
157 printed under pressure, and the cooling of the film may be sufficient to reduce the adhesion of the film to the image transfer surface to the point that the film is carefully detached from the intermediate transfer member, without compromising adhesion to the substrate.
Sticky (or stickiness) can be defined as the property of a material that allows it to bond with a surface in immediate contact under light pressure. The tack behavior can be highly related to various viscoelastic properties of the material (polymer resin, or ink solids). Both viscosity and elastic properties appear to be of importance: Viscous properties at least partially characterize the ability of a material to spread over a surface and form intimate contact, while elastic properties at least partially characterize the bond strength. of the material. These and other thermo-rheological properties are dependent on speed and temperature.
By proper selection of the thermo-rheological characteristics of the film residue, the cooling effect can increase the cohesion of the film residue, whereby its cohesion exceeds its adhesion to the transfer member so that the
158 all or substantially all of the film residue is separated from the image transfer member and printed as a film on the substrate. In this way, it is possible to ensure that the film residue is printed on the substrate without significant modification to the area covered by the film or its thickness.
Viscosity temperature scans - up and down - were performed using a Thermo Scientific HAAKE RheoStress® rheometer
6000 It has a TM-PE-P Peltier plate temperature module and a measurement geometry (spindle) P20 Ti L.
Dry ink residue samples having a depth of 1 mm in a module of diameter 2 cm were tested. The samples were dried overnight in an oven at an operating temperature of 100 ° C. A sample (compressed) volume was inserted into the 2 cm diameter module and softened by slight heating. The sample volume was then reduced to the desired size by reducing the spindle to reduce the sample volume to the desired depth of 1mm.
In the temperature ramp mode, the sample temperature was allowed to stabilize at a low temperature (typically 25 ° C to 40 ° C) before being raised to a high temperature (typically 160 ° C at
159
190 ° C) at a rate of approximately O.33 ° C per second. Viscosity measurements were taken at intervals of approximately 10 seconds. The sample temperature was then allowed to stabilize at high temperature for 120 seconds before being slowed down at low temperature, at a rate of approximately 0.33 ° C per second. Once again, the viscosity measurements were taken at intervals of approximately 10 seconds. Oscillation temperature sweeps were performed in a range of 0.001 and with a frequency of 0.1 Hz.
In the description and in the claims section that follows, the values for dynamic viscosity were determined quantitatively only by the acceleration and deceleration temperature of the method described above.
Figure 7 shows decelerated temperature sweep traces of dynamic viscosity as a function of temperature, by various dry ink formulations suitable for the ink film structure of the present invention. After reaching a maximum temperature of approximately 160 ° C, and 120 seconds of waiting, the temperature was reduced to as described.
The lowest viscosity curve is that of a dry residue from a yellow ink formulation of the
160 invention, containing approximately 2% pigment solids, and produced according to the procedure described above. At approximately 160 ° C, the rheometer measured a viscosity of approximately 6.7-10® cP. As the temperature decelerated, the viscosity steadily and monotonously increased to approximately 6.7 · 10<sup>7</sup> cP at 95 ° C, and at about 48 · 10<sup>7</sup> cP at 58 ° C.
The intermediate viscosity curve is that of a dry residue of a cyan ink formulation of the invention, containing approximately 2% pigment solids, and produced according to the procedure described above. At approximately 157 ° C, the rheometer measures a viscosity of approximately 86 · 10<sup>6</sup> cP. As the temperature decelerated, the viscosity increased to approximately 187 · 10<sup>6</sup> cP at 94 ° C, and up to about 8 · 10θ cP at 57 ° C.
The highest viscosity curve is that of a dry residue of a black ink formulation of the invention, containing approximately 2% pigment solids, and produced according to the procedure described above. At approximately 160 ° C, the rheometer measured a viscosity of approximately 196-10® cP. As the temperature decelerated, the viscosity steadily and monotonously increased to approximately 763-10® cP at 95 ° C, and to approximately 302 · 10<sup>7</sup> cP at 59 ° C.
161
Figure 8 is a plot of decelerated temperature sweep of dynamic viscosity as a function of temperature, by various dry ink formulations of the present invention, versus various ink residues of prior art ink formulations. The viscosity curves of the prior art formulations are labeled 1 to 5, and are represented by dotted lines; The viscosity curves of the formulations of the invention are labeled A through E, and are represented by solid lines. The ink formulations of the present invention include the three described above in relation to Figure 7 (A = black; C = cyan, and E = yellow), and two ink formulations (B, D) containing approximately 2% in solids weight of an aqueous magenta pigment preparation [Hostajet Magenta E5B-PT (Clariant)], along with about 6% of various styrene-acrylic emulsions. The residues of the prior art inks are prepared from various commercially available inkjet inks of different colors.
An enlarged view of the graph in Figure 8, for viscosities less than 36-10<sup>8</sup>, is provided in Figure 9. Only the viscosity curves of the formulations of the invention A to E, and of formulation 5
162 of the prior art, can be seen in Figure 9.
<td></td><td>Is</td><td>evident from</td><td>the strokes,</td><td>and of the</td>
<td>magnitude</td><td>of</td><td>the viscosities, which</td><td>waste</td><td>from ink</td>
<td>dry from</td><td>the</td><td>various formulations</td><td>ink of</td><td>The technique</td>
<td>previous</td><td>not</td><td colspan="2">present nothing or substantially</td><td>nothing of</td>
Flow behavior over the entire temperature measurement range, up to at least 160 ° C. The peaks observed at extremely high viscosities in some traces of the prior art formulations appear to have no physical significance. The lowest viscosity measured for each of the prior art residue films was within a range of at least 135-10<sup>7</sup> cP at least 33 · 10<sup>8</sup> CP. The lowest value within this range, 135-10<sup>7</sup> cP, is more than 6 times the value of the highest viscosity of any of the residues of the ink formulations of the invention, at approximately 160 ° C.
Furthermore, during the deceleration phase of the experiment, samples 1 to 5 of the prior art displayed viscosity values exceeded the measured viscosity at approximately 160 ° C, and / or appeared high enough to prevent film transfer. . In practice, the inventors of the present invention successfully transferred the five ink films of the invention to a substrate of
163 printing, but they failed to transfer any of the five prior art ink films to a printing substrate, even after heating to over 160 ° C.
The inventors have calculated the ratio of a cold dynamic viscosity, at least at a temperature within a range of 50 ° C to 85 ° C, to a hot dynamic viscosity, at least at a temperature within a range of 125 ° C at 160 ° C. The inventors believe that this relationship may be important in distinguishing between ink formulations that meet the multiple needs of the process of the invention, and ink formulations that do not meet the multiple requirements of the process of the invention.
Analysis of Ink Film on Printed Substrates
Basic Procedure:
Three sheets of Condat Gloss® paper (135 g / cm<sup>2</sup>, B2, 750x530 mm) were printed on a digital press in accordance with PCT Application N<sup>to</sup> PCT / IB2013 / 051716 (Lawyer's reference LIP 5/001 PCT), using ink formulations of the present invention (magenta, yellow, cyan and black). After 1 week, the leaves were cut into 3x3 cm pieces and inserted into 3 00
164 grams of a gue solution contains 1% of 2-amino-2-methyl1-propanol dissolved in water capable of sufficiently dissolving images of printed ink using various water soluble inks. In this deinking procedure, the solution was stirred for 10 minutes at room temperature (eg, around 23 ° C), after which the mixture was filtered through a 10 micron filter. The filtrate, which mainly contains the dissolved ink and the pigment particles, was dried using a rotary evaporator. The filtered residue was then dissolved in 5 grams of dimethyl sulfoxide (DMSO) and then dried in an oven at 110 ° C for 12 hours to produce the recovered residue.
The thermo-rheological behavior of the recovered residue obtained from the deinking process is characterized by the viscosity measurements in an acceleration and deceleration sweep of the temperature (as described earlier in this document). The results obtained are represented in Figure 10.
<td>Of the</td><td colspan="2">figure 10 appears from</td><td>gue manifesto</td><td>the</td>
<td>behavior</td><td>thermo-rheological</td><td>of the</td><td colspan="2">ink solids</td>
<td>drawn from</td><td>the images</td><td>printed</td><td>It's similar</td><td>to the</td>
<td>behavior</td><td>thermo-rheological</td><td colspan="2">characteristic of</td><td>the</td>
Dry ink residues produced directly by drying ink formulations of the present invention. Result
165 furthermore evident that the thermo-rheological behavior of the recovered residue is markedly different from the thermo-rheological behavior of the dry residues of various water-based inkjet ink formulations such as samples 1 to 5 (as shown in
Figure 8).
In another test, black HP inkjet ink (as supplied for use in HP DeskJet: 9803) from the cartridge was dried to form a residue. The residue was dissolved in 5 grams of dimethyl sulfoxide (DMSO) and then dried in an oven at 110 ° C for 12 hours. 100 mg of the dry sample was dissolved / dispersed in 0.5 ml of distilled water (or a suitable solvent such as DMSO). After stirring, the liquid material was placed in a silicon rubber mold. The mold was then placed on a plate (heated to 250 ° C) for 10 minutes. The obtained dry tablet was allowed to cool to room temperature, and then subjected to a dynamic viscosity measurement at high temperature (~ 190 ° C). The viscosity, in cP, is graphically represented in Figure
11.
Identical black inkjet ink was also printed on multiple sheets of Condat: Gloss® paper using the aforementioned HP inkjet printer. After 1 week, the sheets were cut into pieces
166 small and were introduced into a 1% solution of 2-amino-2-methyl-1-propanol in distilled water, as described substantially earlier in this document.
The flask was shaken for 10 minutes at room temperature, after which the mixture was filtered through a 10 micron filter. The filtrate was dried using a rotary evaporator. The residue was dissolved in 5 grams of dimethyl sulfoxide (DMSO) and then dried in an oven at 110 ° C for 12 hours. 100 mg of the dry sample was dissolved in 0.5 ml of distilled water (or a suitable solvent such as DMSO). After stirring, the liquid material was introduced into the silicon rubber mold. The mold was then placed on a plate (heated to 250 ° C) for 10 minutes. The dry tablet obtained from the deinking of the HP printed inkjet samples was allowed to cool to room temperature, and then subjected to a dynamic high temperature (~ 190 ° C) viscosity measurement. The viscosity, in cP, is plotted in Figure 11.
The inkjet ink residue obtained by deinking the HP samples showed a dynamic viscosity that was similar to the dynamic viscosity shown by the dry residue of the identical HP inkjet ink.
A similar test was performed for a black ink formulation of the present
167 invention. Dynamic viscosity measurements were carried out at high temperature (~ 190 ° C), both for the dry ink residue and for the recovered ink residue according to the procedure described above. The viscosity of each sample, in cP, is graphically represented in Figure 11.
Once again, the recovered inkjet ink residue, obtained by deinking the ink film structures of the invention, shows a dynamic viscosity that was similar to the dynamic viscosity shown by the dry inkjet ink residue of identical the invention.
In a more advanced procedure, 3 sheets of Condat paper (135 g / cm2, B2, 750x530 mm) were printed on a printing system as described in Applicant's PCT copending application, No. PCT / IB2013 / 051716, using inks such as described in this document, and more detailed in PCT application N<sup>2</sup> PCT / IB2013 / 051755 (lawyer reference LIP 11/001 PCT), using Landa inks, and they were subjected to the following procedure: after 1 week, the sheets were cut into 3x3 cm pieces and introduced in 300 grams of a solution Containing 1% of 2-amino-2-methyl-L-propanol dissolved in water, which is capable of sufficiently dissolving printed ink images using various water soluble inks. Yes,
168 however, the solution remains colorless, the water separates, and an identical weight of a less polar solvent, ethanol, is introduced. Again, if the solution remains colorless, the solvent is removed, and an identical weight of a less polar solvent, methyl ethyl ketone, is introduced. The procedure continues successfully with less polar solvents: ethyl acetate, toluene, and Isopar ™ (synthetic mixture of isoparaffins). After 5 hours of stirring at room temperature with the most appropriate solvent, the mixture is filtered through a 5 micron filter. The filtrate or filtrates containing the dissolved ink are dried using a rotary evaporator. The residues are then dissolved in 5 grams of DMSO (or one of the solvents mentioned above) and dried in an oven at 110 ° C for 12 hours to produce the recovered residue. The thermo-rheological behavior of the recovered residue is characterized and compared to a dry sample of the original ink, when available.
The inventors attribute the improvement in the thermo-rheological results of this procedure (that is, significantly closer to the results obtained by direct drying of the ink for injection) to the greater dissolution of the printed ink, both due to the increase in the time of residence as by the use of additional solvents. Therefore, this advanced procedure is
169 You can use it advantageously to determine the thermo-rheological properties of dry ink from the ink residue recovered from printed matter, such as magazines and brochures.
The absolute dynamic viscosity values of the prior art inkjet ink residues exceed the dynamic viscosity values of the inkjet ink residues of the invention by a factor of more than 30-40.
It is apparent that the prior art absolute dynamic viscosity values and the inkjet residues of the invention can be reproduced substantially by measuring the absolute dynamic viscosity values of the corresponding inkjet ink residues recovered from the printed images. . Furthermore, it is evident that this method can be used to characterize an inkjet ink residue by reconstituting the ink from printed substrates. One of ordinary skill in the art will readily appreciate that other, potentially superior procedures can be used to deink a printed substrate and produce the recovered ink residue for rheological, thermo-rheological, and / or chemical analysis.
Ink Formulations and Ink Film Compositions
170
Among other things, the present inkjet inks are aqueous inks, as they contain water, typically at least 30% by weight and more commonly about 50% by weight or more; optionally, one or more water miscible co-solvents; at least one colorant dispersed or at least partially dissolved in water and an optional co-solvent; and an organic polymeric resin binder, dispersed or at least partially dissolved in water and an optional co-solvent.
It will be appreciated that acrylic based polymers can be negatively charged at alkaline pH. Accordingly, in some embodiments, the resin binder has a negative charge at pH 8 or higher; In some embodiments, the resin binder has a negative charge at pH 9 or higher. Furthermore, the solubility or dispersibility of the binder resin in water can be affected by pH. Thus, in some embodiments, the formulation includes a pH-raising compound, non-limiting examples of which include diethylamine, monoethanolamine, and 2-amino-2-methyl propanol. Such compounds, when included in the ink, are generally included in small amounts, for example, about 1% by weight of the formulation and generally not more than about 2% by weight of the formulation.
171 formulation.
It will also be appreciated that acrylic based polymers having free carboxylic acid groups can be characterized in terms of their charge density or, equivalently, the number of acid, i.e. the number of milligrams of KOH required to neutralize one gram of dry polymer . Therefore, in some embodiments, the acrylic-based polymer has an acid number in the range of 70 to 144.
The ink film of the ink film structure of the invention contains at least one colorant. The concentration of the at least one colorant within the ink film can be at least 2%, at least 3%, at least 4%, at least 6%, at least 8%, at least 10%, at least 15%, at least 20% less, or at least 22%, by weight of the complete ink formulation. Typically, the concentration of the at least one colorant within the ink film is at most 40%, at most 35%, at most 30%, or at most 25%.
More typically, the ink film can contain 2-30%, 3-25%, or 4-25% of at least one colorant.
The colorant can be a pigment or a colorant. The particle size of the pigments can
172 depend on the type of pigment and the size reduction methods used in the preparation of the pigments. Generally the D<sub>50</sub> of the pigment particles can be within a range of 10 nm to 3 00 nm. Pigments of various particle sizes, used to give different colors, can be used for the same impression.
The ink film contains at least one resin or resin binder, typically an organic polymeric resin. The concentration of the at least one resin within the ink film can be at least 10%, at least 15%, at least 20%, at least 25%, at least 35%, so minus 40%, at least 50%, at least 60%, at least 70%, or at least 80% by weight. The total concentration of the colorant and resin within the ink film can be at least 10%, at least 15%, at least 20%, at least 30%, or at least 40% by weight. More typically, however, the total concentration of the colorant and resin within
<td>the movie</td><td>of</td><td>ink can be</td><td>of</td><td>by</td><td>at least 50%,</td><td>by</td><td>the</td>
<td>minus 60%,</td><td>by</td><td>at least 70%,</td><td>by</td><td>the</td><td>minus 80%, or</td><td>by</td><td>the</td>
<td>minus 85%.</td><td>In</td><td>many cases,</td><td>the</td><td colspan="3">total concentration</td><td>of the</td>
colorant and resin within the ink film can be at least 90%, at least 95%, or at least 97% by weight of the ink film.
173
Within the ink film, the weight to resin ratio of the colorant can be at least 1: 1, at least 2: 1, at least 2.5: 1, at least 3: 1, by at least 4: 1, at least 5: 1, or at least 7:
1.
The weight ratio of the resin to the colorant within the ink film structures of the invention can be at most 15: 1, at most 12: 1, or at most 10: 1. In some applications, particularly when it is desirable to have an ultra-thin ink film laminated on the printing substrate, the weight ratio of the resin to the dye can be at most 7: 1, at most 5: 1, at most at most 3: 1, at most 2.5: 1, at most 2: 1, at most 1.7: 1, at most 1.5: 1 at most
1.2: 1, at most 1: 1, at most 0.75: 1, or at most 0.5: 1.
Specific resins that may be suitable for use in the ink formulation of the invention, the system and method of the present invention include water soluble acrylic styrene copolymers within a particular range of molecular weights and a low glass transition temperature (T<sub>g</sub>). Commercial examples of such copolymers can include Joncryl® HPD 296, Joncryl® 142E, Joncryl® 637, Joncryl® 638, and Joncryl® 8004; Neocryl® BT-100, BT-26 Neocryl®, Neocryl®
BT-9, and Neocryl® BT-102. Nominally, the solution or
174 Resin dispersion can be, or include, a solution or dispersion of styrene acrylic copolymer (or co- (ethyl methacrylic acid acrylate). The styrene acrylic copolymer from the ink formulation ultimately remains in the ink film adhered to the printing substrate.
The average molecular weight of the styrene acrylic co-polymer (or co- (ethyl methacrylic acid acrylate) may be less than 100,000, less than 80,000, less than
70,000, less than 60,000, less than 40,000, or less than 20,000 g / mol.
The average molecular weight of the styrene acrylic co-polymer can be at least 10,000, at least 12,000, at least 13,000, or at least 14,000, and in some cases, at least 16,000, or at least 18,000. g / mol.
In one embodiment, the ink film in the ink film structures according to the present invention is devoid of, or substantially devoid of, wax. Typically, the ink film according to the present invention contains less than 30% wax, less than 20% wax, less than 15% wax, less than 10% wax, less than 7% wax, less than 5% wax, less than 3% wax, less than 2% wax, or less than 1% wax.
In one embodiment, the ink film according
175 with the present invention it is devoid of, or substantially devoid of, oils such as mineral oils and vegetable oils (eg, linseed oil and soybean oil), or various oils used in offset ink formulations. Typically, the ink film according to the present invention contains at most 20%, at most 12%, at most 8%, at most 5%, at most 3%, at most 1%, at at most 0.5%, or at most 0.1% by weight, of one or more oils, cross-linked fatty acids, or derivatives of fatty acids produced after air drying.
In one embodiment, the ink film in accordance with the present invention is devoid, or substantially devoid, of one or more salts, including salts used to coagulate or precipitate the ink on a transfer member or on a substrate (eg, chloride calcium). Typically, the ink film according to the present invention contains at most 8%, at most 5%, at most 4%, at most 3%, at most 1%, at most 0.5%, at at most 0.3%, or at most 0.1% of one or more salts.
In one embodiment, the ink film in accordance with the present invention is devoid of, or substantially devoid of, one or more photoinitiators. Typically, the ink film according to the
176 The present invention contains at most 2%, at most 1%, at most 0.5%, at most 0.3%, at most 0.2%, or at most
0.1% of one or more photoinitiators.
In one embodiment, the printing substrate of the ink film structure of the invention is devoid of, or substantially devoid of, one or more soluble salts, including salts used for, or suitable for ink coagulation or precipitation, or components of the itself, on the substrate (for example, calcium chloride). In one embodiment, the ink film structure printing substrate of the invention contains, per 1 m 2 of paper, at most 100 mg of soluble salts, at most 50 mg of soluble salts, or at most 3 0 mg of soluble salts, and more typically, at most 20 mg of soluble salts, at most 10 mg of soluble salts, at most 5 mg of soluble salts, or at most 2 mg of soluble salts.
In one embodiment, the ink film in the ink film structures according to the present invention contains at most 5%, at most 3%, at most 2%, at most 1%, or at most 0.5 %, by weight, of inorganic filler particles such as silica.
In one embodiment, the dried resins present in the ink film of the invention can have a solubility of at least 3%, at least 5%, or at least
177 minus 10% in water, at least at a particular temperature within a temperature range of 20 ° C to 60 ° C, at a pH within a range of 8 to 10 or within a range of 8 to 11.
In one embodiment, the recovered ink film of the invention can have a solubility of at least 3%, at least 5%, or at least 10% in water, at least at a particular temperature within a range of temperature from 20 ° C to 60 ° C, at a pH within a range of 8 to 10 or within a range of 8 to 11.
Water resistance of printed images
ASTM F2292 - 03 (2008), Standard Practice for Determining the Water Resistance of Images Produced by Inkjet Printers Using Four Different Drip, Spray, Immersion, and Rub Test Methods, can be used to evaluate the water resistance of ink dots and printed films on various substrates. The inventors used three of these test methods: drip, spray, and dip, to evaluate water resistance.
In all three tests, the inventive ink film structures showed full water resistance; I know
178 ink was not observed to run, disperse, or transfer.
Identification of Nitrogen-Based Conditioners on a Printed Image on a Substrate
When, prior to printing, the outer surface of the ITM is pre-treated or conditioned with a chemical agent that is, or contains, at least one nitrogen-based conditioning agent such as a polyethylene imine (PEI), transferring the printed image to a substrate typically can result in at least some of the nitrogen-based conditioner also being transferred. This conditioner can be detected using X-ray photoelectron spectroscopy (XPS) or by other means that will be known to those of ordinary skill in the art of polymer analysis or chemical analysis of polymers or species containing organic nitrogen.
In an exemplary demonstration, two printed paper substrates were prepared under substantially identical conditions (including: injection of aqueous ink having nanopigment particles onto a transfer member; drying of the ink on the transfer member, and transfer of the ink film
179 produced to the particular substrate, except that the first substrate is printed without preconditioning of the transfer member, while for the second substrate the ITM is conditioned with a polyethylene imine. XPS analysis of the printed images was performed with a VG Scientific Sigma Probe and monochromatic Al Ka X-rays at 1486.6eV having a beam size of 400 μπι. The spectral data was recorded with a step energy of 150eV. To identify the chemical state of nitrogen, they performed high-energy resolution measurements of Nls with a step energy of 50EV. The base level bonding energies of the different peaks were normalized by setting the bonding energy of the Cls to 285.OeV. Deconvolution of the observed peaks revealed that the PEI-treated sample contained a single peak at approximately 402 eV, corresponding to a
<td>group</td><td>c-nh<sub>2</sub><sup>+</sup>-c.</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>By</td><td>therefore</td><td>in</td><td>some</td><td colspan="2">modalities of</td><td>the</td>
<td colspan="2">invention, it</td><td>provides</td><td>a</td><td>image</td><td>from ink</td><td>printed</td><td>than</td>
<td>has</td><td>a peak</td><td colspan="2">unique from XPS to</td><td> 402.0 ±</td><td>0.4 eV,</td><td> 402.0 ±</td><td> 0.3</td>
<td>eV, or</td><td> 402.0 ±</td><td>0.2 eV.</td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>THE</td><td>inventors</td><td colspan="3">They have found</td><td>what in</td><td>the</td>
top surface or top of film, distal to top surface of substrate, surface nitrogen concentration may exceed
180 appreciably the nitrogen concentration within the film mass. The nitrogen concentration within the film mass can be measured at a depth of at least 30 nanometers, at least 50 nanometers, at least 100 nanometers, at least 200 nanometers, or at least 300 nanometers per below the surface of the top film.
In some embodiments, the ratio of surface nitrogen concentration to nitrogen concentration within the film mass is at least 1.1: 1, at least 1.2: 1, at least 1 , 3: 1, at least 1.5: 1, at least 1.75: 1, at least 2: 1, at least 3: 1, or at least 5: 1.
In some embodiments, the ratio of nitrogen to carbon (N / C) at the surface of the film greater than a ratio of nitrogen to carbon (N / C) within the mass of the film is at least 1.1: 1, at least 1.2: 1, at least 1.3: 1, at least 1.5: 1, at least 1.75: 1, or at least 2: 1.
In some embodiments, the concentration of a secondary amine group on the surface of the top film exceeds a concentration of a secondary amine group within the mass of the film.
In some embodiments, the concentration of a tertiary amine group on the film surface
181 higher exceeds a concentration of a tertiary amine group within the film mass.
In some embodiments, the concentration of secondary and tertiary amino groups on the surface of the top film exceeds a concentration of secondary and tertiary amino groups within the mass of the film.
In some embodiments, the top film surface contains at least one PEI.
In some embodiments, the surface of the top film contains at least one guar poly cationic quaternium, such as guar hydroxypropyltrimonium chloride, and one guar hydroxypropyl hydroxypropyltrimonium chloride.
In some embodiments, the top film surface contains a polymer that has quaternary amino groups, such as an HCI salt of various primary amines.
As used herein in the description and in the remaining claims section, the term "dye" refers to a substance that is considered, or is considered to be, a dye in the printing art.
As used herein in the description and in the claims section that follows, the term
182 Pigment refers to a finely divided solid dye having an average particle size (D50) of at most 300 nm. Typically, the average particle size is within a range of lOnm at 300nm. The pigment can have an organic and / or inorganic composition. Typically, pigments are insoluble in, and essentially physically and chemically unaffected by, the vehicle or the medium in which they are incorporated. Pigments can be colored, fluorescent, metallic, magnetic, transparent or opaque.
Pigments can alter appearance by selective absorption, interference, and / or light scattering. They are generally dispersedly incorporated into a variety of systems and can retain their crystalline or particulate nature throughout the pigmentation process.
As used herein in the description and in the claims section that follows, the term dye refers to at least one colored substance that is soluble or enters solution during the application process and gives color by selective absorption of the light.
As used herein in the description and in the claims section that follows, the term average particle size, od<sub>50</sub>, with reference to the particle size of the pigments, refers to a
183 mean particle size, by weight, as determined by a laser diffraction particle size analyzer (eg Mastersizer ™ 2000 from Malvern Instruments, England), using standard practice.
With respect to fibrous printing substrates, those skilled in the printing art will appreciate that the coated papers used for printing can be broadly, functionally and / or chemically classified into two groups, coated paper designed for use with methods. non-inkjet printing (eg, printing) and coated papers specifically designed for use with inkjet printing methods that employ aqueous offset inks. As is known in the art, the first type of coated papers uses mineral fillers not only to replace some of the paper fibers in order to reduce costs, but to impart specific properties to the paper, such as improved printability, gloss , opacity and smoothness. In coated paper, minerals such as white pigments are used to hide the fiber, thereby improving gloss, whiteness, opacity and softness. Commonly used minerals for this purpose are kaolin, calcined clay, ground calcium carbonate, precipitated calcium carbonate, talc, gypsum, alumina, satin white, white
184 fixed, zinc sulfide, zinc oxide, and plastic pigment (polystyrene).
Coated papers designed for use in inkjet printing methods have hitherto not been unsuitable for use with aqueous inkjet inks, or to produce print spots or smudges that may be manifestly different from printing structures. printed ink film of the present invention.
In contrast, specialty coated papers designed for use with inkjet inks, which in some cases may have the filler pigment layer as with other types of coated papers, may also include a highly porous mineral layer, usually of silica, in combination with a water-soluble polymer such as polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP), which acts as a binder, on which the ink is printed. Such coated inkjet papers are designed to quickly remove water from the printed ink, facilitating ink drop printing with good uniformity and edge roughness. The present invention encompasses ink drops printed on uncoated paper, as well as coated paper that is not designed for the use of inkjet ink, but some embodiments of the present
185 The invention is not intended to encompass ink drops printed on special inkjet coated paper.
Therefore, in some embodiments, the substrate is an uncoated paper. In other embodiments, the substrate is a coated paper that does not contain a water-soluble binder polymer in a layer on which the ink is printed.
As used herein in the description and in the claims section that follows, the term commodity coated fibrous printing substrate is intended to exclude high-end and specialty coated papers, including inkjet coated paper and photo papers.
In a typical paper coating of a commodity-coated fibrous printing substrate, the coating formulation can be prepared by dispersing pigments, such as kaolin clay and calcium carbonate, water, then adding a binder, such as copolymer of polystyrene butadiene and / or an aqueous solution of cooked starch. Other paper coating ingredients, such as rheology modifiers, biocides, lubricants, antifoam compounds, crosslinkers, and pH adjusting additives may also be present in small amounts in the coating.
186
Examples of pigments that can be used in coating formulations are kaolin, calcium carbonate (chalk), china clay, amorphous silica, silicates, barium sulfate, satin white, aluminum trihydrate, talc, titanium dioxide, and mixtures of the themselves. Examples of binders are starch, casein, soy protein, polyvinyl acetate, styrene-butadiene latex, acrylate latex, vinyl acrylic latex, and mixtures thereof. Other ingredients that may be present in the paper coating are, for example, dispersants such as polyacrylates, lubricants such as stearic acid salts, preservatives, antifoaming agents that can be either oil-based, such as silica dispersed in oil of hydrocarbon, or water based such as hexalenglycol, pH adjusting agents such as sodium hydroxide, rheology modifiers such as sodium alginates, carboxymethylcellulose, starch, proteins, high viscosity hydroxyethyl cellulose, and alkali soluble latices.
As used herein in the description and in the claims section that follows, the term fibrous printing substrate of the present invention is understood to include specifically:
newsprint including newsprint
187 standard, phone book paper, smooth paper and super calendered paper;
• coated mechanical papers including light coated paper, medium weight coated paper, heavy weight coated paper, smooth coated papers, and coated offset film;
• Wood-free uncoated papers, including offset papers, lightweight papers;
• wood-free coated papers including standard thin coated papers, light weight coated papers, art papers;
• special thin papers, including copy papers, digital printing papers, continuous paper;
• cardboard and cardboard; and • cardboard packaging.
As used herein in the description and in the claims section that follows, the term fibrous printing substrate of the present invention is specifically intended to include all five types of fibrous offset substrates described in the standard
ISO 12647-2.
The patent or patent application contains at least one drawing executed in color. Copies of this
188 Patent or patent application publication with color drawing (s) will be provided by the Office upon request and payment of the necessary fee.
It will be appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Although the invention has been described in conjunction with specific embodiments thereof, it is apparent that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, it is intended to encompass all of these alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims. All publications, patents and patent applications mentioned in this description, including the appendices, are incorporated in their entirety by reference in the description, to the same extent as if each individual publication, patent application or patent were specifically and individually indicated as incorporated in the present description by reference. In addition, the citation or identification of
189 any reference to this application shall not be construed as an admission that such reference is available as a prior art to the present invention.
190
Contents20
27 sheets
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338 members in 15 offices
Priority claims79
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| 2013000822 | International Bureau of the World Intellectual Property Organization (WIPO) | W | |
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| 61641653 | – | – | – |
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| 61645076 | – | – | – |
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| 61645085 | – | – | – |
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Members338
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| CA2866209A1 | Canada | A1 | |
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1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Correction or change in generalHH | HH |
Numbers
- Publication
- 2014010682
- Publication, DOCDB
- 2014010682
- Publication, EPODOC
- MX2014010682
- Application
- 2014010682
- Application, DOCDB
- 2014010682
- Application, EPODOC
- MX20140010682
Titles
- Spanish
- ESTRUCTURAS DE PELÍCULA DE TINTA
Classification
- IPC, 2
- C09D11 02
- B41J2 01