Heat transfer sheets

(54) Title: Transfer method and heat release transfer device for marking or decorating a textile material or other absorbent surface with a pattern

The numbers in brackets indicate the international identification code. INID code. Letters in clamps indicate international document code

7708451-5 i

The present invention relates to a method of printing fabrics and other materials using a transfer sheet or web which carries a printed pattern or design in advance.

Great efforts have been made for many years to develop a transfer printing system for the decoration of textiles, since a satisfactory system of this kind has many advantages. An obvious advantage for the textile manufacturer is that he does not have to invest in expensive printing equipment or use the professionals in the field. An almost equally important advantage is that the system enables the textile manufacturer to keep layers of unprinted fabric and transfer webs, which means a greatly reduced investment in stocks and greater flexibility.

Despite these advantages, only one type of transfer printing system has received widespread use for textile decoration, namely the vapor phase transfer system. In the vapor phase transfer systems, a molding is printed on a carrier web using an ink containing dyes which sublimates at temperatures of 180-250 ° C. The carrier web is placed in contact with the fabric to be decorated, and the design is transferred by heating the carrier web, which is usually paper, to a temperature where a large proportion of the dyes in the form

The coating sublimates and condenses on the fabric. A typical steam transfer method of this type is described in British Patent Specification 1,443,763 (Sublistatic SA). Fabrics stained by steam phase transfer have good grip, and in the case of polyester fibers, the method results in fairly rapid staining. However, the main limitation of the vapor phase staining is that it is not suitable for dyeing cellulosic fibers, such as cotton, since sublimable dyes do not securely adhere to such fibers, and the method is relatively slow and requires a residence time of up to 30 s for complete dye transfer.

German Patent 2,505,940 discloses a method of decorating fabrics by means of a transfer web, wherein a thermoplastic film comprising the decoration is physically transferred from a carrier web and attached to the textile system and the thermoplastic film is formulated as a thermoplastic adhesive so that it is soft and sticky under the influence of heat. By selecting a carrier sheet with a release surface (e.g., a silicon-coated paper), the hot, tacky film comprising the design can be attached to the fabrics, and upon cooling, the film can be separated from the carrier. In this way, the foil is bound to the textile surface. Several problems soon became apparent when the method of German patent 2,505,940 was tested in practice. Basic problems were that the dyes or pigments forming the pattern in the transferred foil had to be transferred from the foil into the fibers of the fabric and that the polymer matrix which formed the foil had to be removed or dissolved, since the fabric would otherwise have the appearance and grip of a plastic coated material. The German patent does not provide a satisfactory solution to this problem, since subsequent heating of the fabric with the transferred foil in contact with metal plates or rolls is likely to contaminate the plates and rolls with the sticky mass formed upon heating the foil. A further difficulty in the method according to the German patent application is that high quality printing on surfaces with release properties is not possible, since the low wettability of such surfaces leads to repulsion and other printing defects. Finally, the need to cool the foil prior to tearing introduces an unwanted restriction on the maximum possible speed of the method.

Attempts have also been made to provide a transfer system in which a liquid ink is reconstituted upon application to the fabric. Theoretically, such a system would appear to be the most satisfactory solution, as it seems to be

7708451-5 best mimics conventional printing from colored plates or rollers. The practical implementation of a liquid phase transfer system has been undone by the problem of providing a printing ink which melts into a printable liquid at a sufficiently low temperature so as not to damage the fabric and which is at the same time solid and non-sticky at room temperature so that the transfer web or sheet can be stacked or is rolled without blocking or marking. Previous systems of this kind therefore essentially involve tolerating any blocking of the transfer sheet and comparatively high temperatures and transfer pressures used to ensure transfer of the pattern to the fabric. Unwanted operating temperatures and pressures are unsuitable as they can distort or damage the fabric. Earlier systems of this latter type are described in U.S. Pat. Nos. 2,883,286 and 2,911,280.

The present invention is based on the discovery that a printing ink which is solid and non-blocking at room temperature but which readily melts into a printable ink at relatively low temperatures can be obtained by dispersing in the ink a substance which is solid and forms a color separate from the carrier. phase at room temperature but which melts at the operating temperature into a liquid, which at least does not increase the viscosity of the other constituents of the paint or which can be removed at the operating temperature by sublimation.

According to the present invention, there is provided a method of labeling or decorating a textile material or other absorbent surface with a pattern, and heat release transferable means for decorating or labeling textiles and other absorbent surfaces. The method and the transfer device have the features of claims 1 and 6 respectively.

The transfer device according to the present invention is used for decorating textiles or other counterfeit materials by arranging the transfer layer and the recipient in contact with each other and heating sufficiently to melt the transfer layer while keeping the transfer layer and recipient in intimate contact with one another, for example in a press. It has been found that the transfer mechanism involves converting the transfer layer into a relatively low viscous liquid film which is transferred to the liquid phase receiver. The transfer efficiency is good, although the portion of the polymer layer being transferred depends on the relative absorbency of the receiver and the carrier sheet. When transferring patterns to textiles!

and receivers of the same high degree of absorbency, the transfer efficiency is excellent and the transfer layer flows into the receiver to an extent that depends on several factors, including the film thickness and contact pressure of the transfer layer.

The purpose of preparing the transfer layer should be to achieve a composition having a 'melt viscosity in the transfer | device operating temperature within that range;¹ which is normally selected for conventional printing of liquid ink receivers. Optimum;

melt viscosities depend on the nature of recipients used and transfer conditions, including transfer contact pressure, but should generally be less than 100 P, normally lower than 30 P. At low contact pressures, e.g., 0.07-0.35 kp / cm, the melt viscosity is preferred. | show less than 15 P, eg 1-10 P or below.

Of course, the particulate solid should be a non-sticky solid at normal room temperature and melt or sublime at the used transfer temperature so as not to disturb it!

melt flow of ink into the material to be printed.}

Liquid phase transfer which provides flow into an absorbent substrate has many advantages because, for example, in a textile substrate such important physical properties of the substrate as porosity, surface texture and grip are substantially retained after the transfer and at the same time the transferred pattern has excellent properties such as abrasion resistance, washability, dryness and heat resistance, which are important in textile substrates for use in clothing.

All types of absorbent substrates can be decorated in the manner of the present invention, and include woven and knitted fabrics for clothing, furniture and packaging, nonwoven fabrics, fiberglass, leather, paper and other fibrous materials such as mats and foam plastics. The substrates are absorbent due to their fiber or cellular structure or surface roughness and the absorbency is indicated by their oil absorption value.

Transmission at melt viscosities over conventional liquid inks can be accomplished by applying higher pressures or vacuum to facilitate flow into the substrate. Therefore, the liquid phase transfer according to the invention precludes solid state transfer, in which the transfer layer is retained as a coherent film during transfer and forms a decorated substrate where the transfer layer

7708451-5 exists as a film or skin on the surface of the substrate. Such solid phase transfer involves retaining a coherent film layer after transfer and varies the physical properties of the substrate, such as porosity and surface structure, and produces a label-like effect.

The purpose of the particulate solid is to allow the heat-activatable transfer sheets to be stacked and transported under normal ambient conditions without blocking the sheets or marking the transfer layer on adjacent layers. To achieve this, the particulate solid should be present in at least the surface of the transfer layer as individual particles in the base layer formed by the polymer layer. It is important to avoid formation of solid solutions of the particulate solid in the polymer, since the desired antiblocking properties are generally achieved only when a heterogeneous transfer layer comprising individual solid particles of the antiblocking component of the polymer exists.

In selecting suitable particulate solids, materials which dissolve readily in solvents for the polymer are preferably avoided, since with such materials it is difficult to prepare the heat activatable transfer device of the invention without forming a solution of the particulate solid in the polymer.

While some incompatibility between the particulate solid and the polymer components is suitable at low temperature, it is advantageous to choose a particulate solid which dissolves in the polymer (or vice versa) at their melting temperature. An important advantage of these latter materials is that the particulate solid is removed from the surface film of the transfer layer and therefore cannot interfere with the transfer of liquid polymer layers to the receiver. Dissolution of the particulate solid in the polymeric layer of the transfer layer at or near the melting temperature also has the advantage of lowering the melting point of the polymeric components, while further forming a solution normally reduces the melting viscosity of the transfer layer.

Particulate solids containing ester, amide or ketone groups are often soluble in a wide range of polymers and represent a preferred class of particulate solids.

In general, the particulate solids used in the transfer device of the present invention should have a melting point of at least about 60 ° C. If the melting point is considerably lower, the product has insufficient storage stability at high ambient temperatures, which sometimes occur in hot climates. The upper melting point limit (sublimation temperature) of the particulate solid is determined

7708451-5 of the maximum working temperature of the receiver to which the pattern is to be applied, and also of the carrier sheet. For textiles, the maximum permissible temperature for most fabrics is about 200 ° C. Since the polymers forming the transfer layer are melted over a temperature range (which expands if the particulate solid forms a solution with the polymer components at the elevated temperature), it is often possible to prepare a transfer layer which, after heating to its melting temperature, remains melted and sufficiently liquid. it has cooled considerably below its first melting temperature. As previously pointed out, solid esters, amides and ketones of aromatic, cyclic or short chain hydrocarbon groups (especially 10 carbon atoms or less) are a preferred group of particulate solids which often form solutions with the polymer components in the molten state. Within this group of particulate solids are included substances which are sometimes referred to as solid plasticizers, for example, aliphatic, aromatic and cycloaliphatic phthalates. Examples of specific materials that can be used as particulate solids in the heat-activatable transfer device of the invention are given by their melting points below:

Mp, ° C

<td>octadecanamide</td><td> 102-104</td>

<td>dimethyl</td><td> 140-142</td>

<td>Sorbitorhexaacetat</td><td> 100-4</td>

<td>dicyclohexyl</td><td> 65</td>

<td>p-toluenesulfonamide</td><td> 136-7</td>

<td>N cyklohexylsulfonamid</td><td> 86</td>

<td>diphenyl</td><td> 69</td>

<td>Camphor</td><td> 176-178</td>

<td>Heptaklornaftalen</td><td> 115</td>

Examples of particulate solids which, from a phase melt, separate from the polymer are octadecanamide and low molecular weight polymers such as linear polyesters, polyamides and polyethylene.

Some of the above substances sublimate at the elevated temperatures at which the transfer device is used, such as dimethyl terephthalate and, to a lesser extent, camphor, and are thus completely or partially removed from the transfer layer during the heat-activated transfer to the receiver.

The present invention includes a method of labeling a surface,

7708451-5, such as a textile, which comprises providing on said surface a heat-activatable transfer device comprising a polymer coating on a carrier sheet, the coating having individual particles of a non-sticking solid in at least the exposed surface layer of the coating, such that the exposed surface is substantially non-blocking at normal room temperature, and exposing the polymer to a heat source whereby the polymer melts and transmits to that surface; to be labeled, and the non-sticking solid sublimates or melts to form a liquid mixture with the polymer, which mixture is no more viscous than the molten polymer as such.

The decoration of liquid phase textiles in the manner of the present invention yields valuable results in close agreement with the conventional decoration of textiles by direct printing with liquid ink, in particular the maintenance of the important physical properties of the substrate. However, the print quality of the decorated fabrics obtained by the invention is significantly superior to that obtainable by direct printing, especially in reproduction of fine details and color tones as well as color registers in multicolor printing. the transfer layer of the present invention has a predetermined thickness which also provides accurate color density control.

In one embodiment of the invention, the transfer layer is transparent or translucent and is arranged as a continuous coating or as discrete coating portions on the carrier sheet, the pattern or marking being printed or otherwise provided on the exposed surface of the transfer layer, and when transferring the printed layer, the printed pattern is transported. in the substrate.

In an alternative embodiment, the transfer layer as such constitutes the pattern to be transferred to the substrate.

Since the layer is transferred in liquid phase, a coherent coherent layer is not transferred onto the substrate surface, so that the physical properties of the substrate are significantly altered, such as porosity or surface texture. The flow of transfer material into the substrate itself contributes to the good hardening properties obtained in the transferred pattern.

The polymer backing or components of the transfer layer may include one or more polymers, prepolymers or the like in admixture. A prepolymer is a very low molecular weight monomer or polymer. In one embodiment of the invention, it may be over

The hardening properties of the layered sheet are increased by using a polymer system which further polymerizes in situ in the substrate during or after the heat-activatable transfer. In a particular embodiment of the invention, a soft crosslinking polymer or two mutually reactive polymers or a polymer and a crosslinking agent or a prepolymer and a polymer can be used in admixture to obtain in situ polymerization. In particular, the heat-activatable transfer can be accomplished at a temperature to initiate the cross-linking reaction, which can proceed to completion, if necessary, with additional heating. In situ polymerization can be accomplished by photopolymerization, whereby the transferred layer is subjected to UV or electron radiation after deduction from the carrier sheet.

The degree of flow characteristics required in the transfer layer on specific substrates depends on the substrate type and the end use of the substrate. For example, with a textile fabric that requires unilateral decoration, flow to a depth of penetration is sufficiently limited to provide hardness properties, such as rubbability, and preserve physical properties such as surface texture, grip and porosity. Decoration of a textile fabric, which requires uniform coloring throughout the thickness of. fabric, requires significantly higher flow properties in the heated transfer layer. With a given substrate, the flow properties are shown to depend on the composition of the polymer substrate, the thickness of the transfer layer, the temperature, the residence time and the transfer pressure, and the type and concentration of solid fusible material. All of these decorating effects can be obtained in the manner of the present invention.

Most preferably, the solid particulate material is incorporated as a dispersion of fine particles into the polymeric layer of the transfer layer. This can be accomplished by mechanically dispersing the solid meltable or sublimable materials as a powder in the polymer substrate prior to forming the transfer layer on the support sheet. Volatile organic solvents and water can be used to lower the viscosity of the polymeric substrate to produce the transfer layer by coating or printing, and these are evaporated to form the dry transfer sheet. When such solvents are used, they are preferably selected such that they do not dissolve the particulate solids to any significant extent.

The solid particulate material may also be incorporated into the transfer layer by applying the same in the form of a fine

7708451-5 distributed powder, jet or liquid on the surface of the transfer layer, while the latter is sticky, for example before complete drying. This incorporation makes it possible to use such solid particulate materials which are otherwise too soluble in the solvents of the polymer components. Excess powder can be removed by brushing and / or vacuum such as on a bronzing machine. It may also be appropriate to incorporate the solid fusible material into the polymer backing in cold or hot solution or dispersion in volatile organic solvents or water so that upon cooling or drying the material is present as solid particles in the layer.

It has been found that with certain combinations of polymer substrate and solid meltable material, the flow properties are maintained for a period of time after cooling of the transfer layer prior to contact with the substrate. It is believed that such delayed flow is maintained until solidification of the solid occurs, which can be a slow crystallization process. Accordingly, heat-activatable transfer can be achieved at a lower temperature than that achieved during the heating step, which is useful for heat-sensitive substrates and also allows the transfer layer to be heated as a separate step prior to arranging the transfer layer in contact with the substrate.

Many heat softening polymeric substrates, which are particularly suitable for use in the invention, are sticky or at least block or become damaged during handling and storage of the transfer sheets. Part of the solid particles in the layer really exist in the exposed surface of the transfer layer, where they eliminate tack and provide non-blocking and excellent handling properties, and this is one of the important functions of the solid material.

Thus, a polymer support which is soft and sticky at room temperature and has extremely good heat flowability can be used, and the heat transfer layer is solidified by a suitable concentration of particles of the solid material. Another function of the particulate solid is that the printability, stretching and typing properties of the transfer layer are also significantly improved by the inclusion of finely divided solid particles in the transfer layer. A fine mat for the application of the ideal surface pattern is formed.

A coherent transfer layer may be applied to the carrier sheet by coating, such as rolling, reverse rolling or curtain coating. Coherent or discrete portions of transfer layers can be applied by printing or panel coating. One

7708451-5 coating layers may be colorless or colored to provide a background color in the latter case. Thereafter, the pattern layer is printed on or otherwise formed on the exposed surface of the transfer layer to form a composite transfer layer, so that the pattern during transfer is transported with the liquefied transfer layer into the substrate. In all these cases, the pattern layer need not contain a solid meltable: component, although flow is facilitated if some meltable material is incorporated. All common printing methods of lithography, letterpress, gravure, flexography, screen printing and jet printing can be used to print the pattern using single or multicolor printing presses, and excellent printing quality and fast curing of the ink and fast drying are obtained.

Likewise, pencil drawing, including felt tip pen, brush and spray painting, tape and carbon paper printing, and electrostatic printing can be used, and in the latter, the particulate material must have a melting point (sublimation temperature) above the temperature reached in the electrostatic printing machine. . A pattern can be formed on the surface of the transfer layer by a dry transfer process, in which, for example, a pattern of dry ink is transferred to the layer from a dry transfer sheet of the kind described in British Patent 959,670.

A clear, transparent or colored transfer layer may also be applied to the carrier sheet after application of the pattern layer, or alternatively the pattern layer may be arranged in a stack relationship between the two transfer layers.

The pattern layer may also comprise the transfer layer as such and in these cases consists of heat-softenable polymer substrate and solid, particulate material as well as coloring or latent coloring material. The colored pattern layer, printed by a thin film method such as gravure or flexography, can be printed by a multi-station press with one or more works of colorless pattern layer of similar composition to increase the thickness of the transfer layer to obtain sufficient flow into comparatively thick substrates, such as textile substrates. Alternatively, one or more works of colorless layer may first be applied to the carrier sheet in discrete areas slightly larger than the final color pattern layer (s) to avoid the following registration problems with the printed pattern.

When a coherent transfer layer is applied to the carrier sheet, various other functional properties can be readily imparted to it, which are

7708451-5 valuable when decorating particularly absorbent substrates, such as textiles for clothing. These functional properties include fold resistance, flame resistance, swelling properties and heat sealing properties, which are later useful for fusible inserts and applications.

A sufficient concentration of solid particulate material should be incorporated into the transfer layer to provide this non-blocking and good handling properties during storage and to exhibit liquid phase transfer upon heating. Generally, when the transfer sheet is formed by applying the transfer layer, the concentration of solid particulate material required for printability is such that a matte or semi-matte finish is obtained on the transfer layer. A concentration of 30-80% is generally required, but it should be noted that the concentration depends on the particular polymer substrate and other factors already described.

Heat-softenable polymers which can be used in the polymer backing include acrylic, methacrylic, amino formaldehyde, epoxy, vinyl, linear polyesters, alkyds, hydrocarbon resin, polyamide, polyurethane and chlorinated rubbers. Suitable monomers and prepolymers include mono- and multifunctional acrylates, acrylated polyurethane and acrylic epoxy. Water-soluble polymers include polyethylene oxide and polyvinylpyrrolidone.

Polymers which alone cannot be readily melted by heating, but which together with particulate solids of the type described above form low viscous liquids upon heating, are an important class of polymers which can be used in the invention. Specific examples of such polymers are nitrocellulose, ethyl cellulose, ethyl hydroxyethyl cellulose and cellulose acetate butyrate.

Heat-softenable polymers also include cross-linked types which can be softened by depolymerization upon heating. For example, when heated to 330 ° C or higher, polyester polyurethane is rapidly depolymerized into products with flow properties, which are believed to consist of low molecular weight polyesters and polyisocyanates. These components are then copolymerized at room temperature for about 24 hours.

The carrier sheet should preferably have comparatively low absorbency for the heated transfer layer to ensure transfer of a significant portion of the transfer layer. The absorbent capacity of the carrier sheet should be less than that of the substrate, and the carrier sheet should not soften at the transfer temperature. Absorption performance may be measured with. the oil absorption value and very low values ​​are obtained with paper carriers by parchment, coating, impregnating or laminating the paper or using highly ground pulp and regenerated cellulose.

Specific examples of suitable carrier sheets are vegetable parchment paper, parchment paper, machine-coated paper, and regenerated cellulose film,

Plastic foil backing sheets can also be used, such as polyester and even polypropylene, at suitable transfer temperatures, and these foils can also be used laminated on a paper support. It is also possible to use carrier sheets with excellent release properties, such as paper coated or impregnated with silicon or Quilon, and in such cases the very poor printability of these support sheets is overcome by applying a coherent transfer layer to the carrier sheet and arranging the pattern on the transfer layer.

Suitable equipment for heat-activatable transfer of individual transfer sheets, manufactured in accordance with the invention, includes a heated crucible with means for applying pressure to the transfer sheet and the substrate assembly. A heated drum is used for transfer when the transfer sheet is a continuous web, the transfer calender used for vapor phase transfer is suitable and usually a much higher operating speed can be used with transfer sheets according to the invention because the residence time is shorter than during the vapor phase transfer. Vacuum can be utilized to increase flow into the substrate by lowering the air pressure below the substrate, the transfer layer does not need to be heated at the same time as pressure is applied, and the fastest heat-activatable transfer is obtained by direct action of a flame on the transfer layer using a gas burner which is directed toward a continuous web of transfer sheets as this is passed around a water-cooled cylinder. Immediately after the burner, the transfer web meets the support web, which may be preheated, and both are guided by the pressure of a pair of nip rollers. The temperature at which the transfer layer is heated and the temperature of the nip can be easily controlled and very high speeds are achieved. When the dye material consists of water-soluble dyes or latent dyes, steam or superheated steam can be used for heating.

The entire transfer sheet is normally heated uniformly so that the entire pattern is transferred. Heat can also be localized using conduction heating with a heated mold to provide a

7708451-5 transmission that reproduces the contour of the mold. At present, it is believed that the transfer of the molten transfer layer to the substrate takes place in a similar manner to the transfer of a liquid ink layer in conventional printing, i.e., the ink layer is cut transversely and the portion of the ink film transferred to the substrate depends on various known factors such as the viscosity of the ink. and the absorbent capacity of the substrate.

Pigments are dispersed in the transfer or pattern layer to produce colored effects. Dyes, which are soluble in the polymer backing or pattern layer constituents, are also suitable. Latent dyes consisting of textile dyes, such as fiber reactive dyes, dispersion dyes, direct dyes, acid dyes and leuco dyes, can also be incorporated into the transfer or pattern layer, and the color and hardness of these dyes on textile substrate develops by using steam over heat, using heat or steam. the transfer or later. Dyeing agents may also be incorporated to facilitate color development on the fabric, such as finely dispersed sodium carbonate solids for fiber-reactive dyes and finely dispersed acid and wool and nylon acid dyes. Covering dyes require the incorporation of both alkali and a reducing agent, such as sodium formaldehyde sulfoxylate.

EXAMPLE 1

A clear, transparent transfer layer is provided on a carrier sheet of vegetable parchment paper by applying the following liquid composition.

parts by weight

1st Epoxy polymer as a solution with 60% solids in ethoxy ethanol (solution weight) 19.8

2nd Aminopolymer as a solution with 20% solids in ethoxyethanol6,6

3rd Phenoxy polymer as a solution with 32% solids in ethoxy ethanol acetate22.0

4th Finely ground, solid, fusible material dicyclohexyl phthalate46.3

5th Etoxietanol5,3

100.0 Non-volatile constituents 68.3%

Solid digestible material as% of total non-volatile constituents%

7708451-5

The heat softening epoxy polymer is a low molecular weight polymer containing reactive epoxy end groups, and the amino resin is a crosslinking agent prepared by reacting ethylene diamine with a low molecular weight epoxy resin to form blocked amino groups which do not react with additional epoxy resins at room temperature. The phenoxy polymer is a heat softening linear polyether obtained from bisphenol A and epichlorohydrin without epoxy end groups and has a relatively high molecular weight (15000-30000). The dicyclohexyl phthalate is a solid plasticizer for polymer components 1, 2 and 3 and melts at 69 ° C. The resulting composition was applied to one surface of the carrier sheet by coating or screen printing to obtain a dry coating weight of 5-30 g / m, depending on the substrate to be decorated and the required decorating effect. The dry layer thickness variation obtained by screen printing is obtained by printing with monofilament polyester mesh varying from 200 mesh / cm to 32 mesh / cm. The wet support layer was dried by evaporation on a hot air dryer at a maximum of 40 ° C. This clear transfer layer has a fine matte finish in the dry state, is non-blocking during storage and is not damaged during handling. It has excellent liquid flow properties when heated to 150-180 ° C and is transferred to textile substrates such as thin woven cotton fabric, charm tie cotton jersey, knitted polyester and woven denim when applied under a pressure of 0.07-035 kP / cm for a residence time of 5- 15 s.

EXAMPLE 2 transfer sheets prepared in Example 1 having a coating weight 2 of 20 g / m were printed with 4-color offset lithography using the following ink:

1st Trichromatic yellow pigment (color index pigment yellow 13) 14.0

2nd Polymerlösning40,0

3rd Microfine polyethylene wax2.0

4th Metyletylketoxim1,0

5th Polymerlösning30,0

6th Aliphatic hydrocarbon; boiling point 260-290 ° C9.0

100,0

7th Polymer Solution:

Phenol modified resin ester 50.0

Non-yellowing vegetable oil10.0

Distillate; boiling point 260-290 ° C40.0

100,0

7708451-5

The yellow pigment was dispersed in a three-roll mill in 2, 3 and 4, then 5 and 6 were added to obtain the required color viscosity and tack value.

Purple, cyan and black inks of the four-color set were similarly prepared by exchanging the yellow pigment with:

Trichromatic purple pigment (color index pigment Red 57) 18 Trichromatic cyan pigment (color index pigment Blue 15) 16 Trichromatic black pigment (carbon black 18 plus color index pigment Blue) 1

Printing was performed on a single-color or multi-color wear printing press using the color sequence yellow, purple, cyan and black. Excellent print quality was obtained and the inks cured very quickly due to the matte carrier layer surface. The printing was allowed to dry overnight.

The obtained printed transfer sheet was tested by applying to knitted cotton jersey T-shirts using a crucible press. The upper crucible was heated to 180 ° C and the transfer sheet placed in line on the T-shirt, which was placed on the lower crucible coated with a 1 cm thick layer of silicone rubber. The crucible was closed to provide a pressure of 0.11 kP / cm for 5 seconds, after which the press was opened and the support sheet removed while still warm. The printed pattern was essentially transferred to the T-shirt fabric, leaving only a small remnant of the backing sheet. The fabric's handling, scraping properties and air permeability were essentially unchanged and the pattern transmitted showed significant penetration into the fabric and did not exist as a shell on the surface. The pattern had high resistance to ironing, washing, dry cleaning as well as wet and dry abrasion resistance.

EXAMPLE 3

A clear transparent transfer layer was coated onto a vegetable parchment carrier sheet using a liquid coating composition having the composition set forth below. The application is accomplished by reverse rolling to obtain a coherent layer. The layer was dried by evaporation with hot air at 40 ° C and had a dry coating weight of 5-50 g / cm, with the specific value being selected to fit the substrate being decorated.

7708451-5

1, Polyvinylbutyral as a solution with 30% solids in ethoxyethanol7.5

2nd Isobutylated melamine-formaldehyde polymer as 55% solids in isobutanol16.5

3rd Dicyklohexylftalat42,5

4th Etoxietanol33,5

100,0

Non-volatile constituents 53.8%

Solid digestible material as% of total non-volatile constituents 79.0%

The polymer solutions and solvent (1, 2 and 4) were mixed and the finely ground solid plasticizer powder (3) was added with high speed stirring at room temperature just before coating or printing. The dry transfer sheet was non-blocking and could be stacked or rolled and had a fine matte finish with excellent printability and stretching properties. The polymer (1) was heat softenable and crosslinked upon heating with the polymer (2), which is a very soft, low molecular weight material.

EXAMPLE 4

A gravure ink of the following composition was printed directly on a parchment paper carrier to form a pigmented transfer layer:

1st Akrylsampolymer25,0

2nd Hexahydroximetylmalamin8,0

3rd p toluensulfonamid42,0

4th Toluen25,0

100,0

5th Organic pigment5.0

The particulate solid (3) was mixed by high speed stirring into a cold solution of the polymers (1 and 2) dissolved in the solvent (4). The pigment (5) was ground into the liquid ink carrier and additional solvent (5) was added to adjust the viscosity to fit the gravure printing press.

The polymer substrate (1 and 2) of this color, heated to 180 ° C, is a highly viscous mass with insufficient flow properties for printing fabrics. The dry color carrier containing the solid (3), heated to 180 ° C, gives a low viscosity liquid (about 1 Ps) with excellent flow properties, due to the softening effect of the solid (3).

7708451-5

EXAMPLE 5

Decorative or identification marks are provided on the transfer layer of the sheets made in Example 1 by stretching using a felt tip pen containing a ink of solvent-soluble dyes in solution in hydrocarbon solvent. The labeling dried quickly by evaporation and absorption of solvents into the transfer layer, and after transfer in heat to cotton fabric, silk fabric, wool fabric or polyester fabric, a sharp printing with excellent hardening properties was obtained. Similar marking can also be achieved on the transfer layer since it has already been decorated by printing, so that composite printed and drawn characters can be obtained.

EXAMPLE 6

A clear transparent transfer layer of the following composition was applied as a uniform coating on vegetable parchment 2 having a surface weight of 72 g / m by reverse rolling to obtain a dry 2 weight of 16 g / m.

1st Hydroxyl-functional polyacrylate as% solids in butanolxylol solvent 40.0

2nd Melamine-formaldehyde polymer as 50% solids in butanol xylol solvent 40.0

3rd Stearamid20,0

100,0

Non-volatile constituents 60%

Solid digestible material as% of total non-volatile constituents 33%

The polymer (1) was a low molecular weight heat softening material, and the solid meltable material (3) was added to the hot polymer solution to melt. The mixture was cooled to room temperature with gentle stirring to form a fine dispersion of the solid digestible particles in the polymer solution.

EXAMPLE 7

Example 1 was repeated except that dicyclohexyl phthalate was exchanged for the same concentration of heptachlorophthalene.

The resulting transfer worked in the same manner as in Example 1, but gave cotton, wool, polyester and nylon a considerable degree of flame resistance.

EXAMPLE 8

Example 1 was repeated except for a swelling agent

7708451-5 (4: 4'-dinitrosulfanilide in an amount of 20% 1 was also incorporated into the lacquer. The swelling agent swells or expands and forms a charred foam mass upon exposure to very high temperatures, such as a low. 4: 4'-dinitrosulfanilide has a swelling temperature of 220 ° C, so that heat-activatable transfer can be achieved at a significantly lower temperature, for example 150 ° C.

EXAMPLE 9

A transfer layer prepared entirely by offset litho printing was prepared as follows, incorporating a solid, non-stickable fusible material into the transfer layer by application as a dry powder to the wet printing ink.

1st 50% w / w solution of rosin ester in petroleum distillate 260-290 ° C73.00

2nd Linseed oil, 30 Ps9.00

3rd Copper phthalocyanine, β-form18.00

100,00

Component 1

The heat softening polymer consisted of dimerized rosin esterified with pentraerythritol having a softening point of about 180 ° C. The polymer was dissolved in low KB aliphatic hydrocarbon solvent, 260-290 ° C, to form a 50% w / w solution.

Component 2

Flaxseed oil was added to the polymer solution to improve the printability of the litho ink.

Component 3

This component is a trichromatic blue pigment which was dispersed in the mixture of 1 and 2 in a three-roll mill to a grain according to Hegman of 6.

The color was printed by offset lithography on machine-coated paper, and a dry powder jet of p-toluenesulfanamide was applied to the printed sheet to cover and attach to all web color portions prior to stacking. Alternatively, the web printing may be conducted through a bronzing machine in which the bronze powder has been replaced by p-toluenesulfonamide, which is the non-stickable digestible material. The dry powder makes the printing non-sticky, so sheets can be stacked on top of one another.

transfer to thin woven fabric was carried out for 5 seconds at 180 ° C and 0.14 kP / cm. The powder melted into a low viscous liquid which had a solvent effect on the polymer substrate and formed a liquid.

7708451-5 that floated into the fabric.

About 7Q% of the transfer layer was transferred to the fabric with good penetration, and. 30% remained in the machine-coated paper. By exchanging the paper with vegetable parchment paper, about 8Q% was transferred due to the lower absorbency of this later paper.

EXAMPLE · 10

A colorless lithographic ink was prepared using the composition of Example 9 in which the colored pigment was replaced with p-toluenesulfonamide at a concentration of 35%. This ink was first printed as a colorless transfer layer on the paper and imprinted with the 4-color halo litho colors of Example 9, and p-toluenesulfonamide was applied to the colored ink as a dry powder prior to stacking. The entire printing operation was carried out on a multicolor press, so that only a single dry powder application was performed prior to printing stacking.

The colorless layer and the color layer formed a composite transfer layer. transfer in the same manner as in Example 9 achieved a color transfer efficiency of over 90% with excellent fabric penetration.

EXAMPLE 11

A photopolymerizable colorless transfer layer was prepared on vegetable parchment carrier sheets by coating or screen printing the following liquid composition and drying by evaporation of the solvent at below 50 ° C.

<td> 1.</td><td>Acrylic polyurethane</td><td> 17,1</td>

<td> 2.</td><td>2-phenoxyethyl</td><td> 7,3</td>

<td> 3 .</td><td>benzophenone</td><td> 1,7</td>

<td> 4.</td><td>benzyldimethylketal</td><td> 0,7</td>

<td> 5.</td><td>Michler's ketone</td><td> 0,07</td>

<td> 6.</td><td>butoxyethanol</td><td> 24,4</td>

<td> 7.</td><td>p-toluenesulfonamide</td><td> 48,73</td>

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Component 1 is a difunctional ethylenically unsaturated photopolymerizable prepolymer.

Component 2 is a photopolymerizable monomer.

Components 3, 4 and 5 are photoinitiators.

Component 6 is a volatile solvent.

Component 7 is a solid meltable at low temperature.

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The liquid composition was prepared by admixing the toluene sulfonamide in the solution obtained by mixing other components.

The formed dry transfer layer had a matte non-blocking surface which was then applied with the colored inks of Examples 2, 4 or 5.

Alternatively, the liquid composition may be colored by dispersing pigments on a three-roll mill and applied as a single transfer layer by screen printing on the carrier sheet.

transfer to textile fabric was carried out at 160 ° C and 0.1 kp / cm 2 for 4 s, and after heat removal for the carrier sheet disposal, the transferred pattern was photopolymerized and cross-banded by UV radiation using a 3 cm diameter quartz mercury vapor lamp which was operated at 80 W / cm tube length. The fabric was moved under the lamp at a distance of 2 cm at a speed of 100 m / min. Cross-linking makes the transfer non-softenable by heat and increases wash resistance and dry-wash resistance.

EXAMPLE 12

A clear, colorless varnish was prepared by mixing the following materials:

1st Melamine-formaldehyde epoxy copolymer as 60% w / w concentration in 1: 1 62.5

2nd Dimethyl terephthalate 37.5

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The dimethyl terephthalate was present at a concentration of 50%, based on the total amount of non-volatile constituents.

This composition was applied as a colorless transfer layer as in Example 1, except that the composition could be dried at 100 ° C without melting component 2.

The non-blocking transfer sheet was printed by offset lithography using the inks of Example 9 to provide excellent print quality.

transfer was carried out at 170 ° C for 10 s at about 0.1 kP / cm, and the heat activatable transfer and extraction was carried out in an air flow which disposed of the dimethyl terephthalate in the form of a steam which condensed as crystals as the exhaust gas was cooled. The sublimable material is therefore mainly disposed of during transfer and recycled for reuse.

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