Self-dispersed pigments and methods for making and using the same

<u style="single">Field of use</u> The present invention relates to a method for producing a self-dispersing pigment. More specifically, the present invention relates to surface modification of pigments. Pigments whose surface is modified by covalent bonds are well known in the industry as self-dispersing pigments. This surface modification can be performed in an aqueous environment and can be said to be environmentally friendly. Furthermore, the present invention relates to end applications including, but not limited to, surface modified pigments, such as, but not limited to, coatings, paints, papers, adhesives, latexes, toners, fabrics, fibers, plastics and inks. Specific examples of end applications include, but are not limited to, printing inks for paper, fabrics, textiles, metal modifications and plastics, wood stains, writing tools and color filters. The present invention also relates to inks such as inkjet inks.

<u style="single">background</u> Pigments have some advantages over water-soluble dyes when it comes to inks, coatings, paints, papers, adhesives, latexes, toners, fabrics, fibers, wood stains, color filters and plastics. There is. Pigments can exhibit at least one of superior light resistance, water resistance, optical density and edge clarity compared to water-soluble dyes. Unfortunately, however, pigments also tend to precipitate during storage, which initially limits their use in harsh applications such as inkjet inks. With the advent of medium mills that grind pigment particles to the submicron level in combination with colloid-stabilizing chemical additives, the use of pigment dispersions in inkjet ink formulations has advanced. However, chemical additives increase the viscosity of the dispersion, which can make it difficult to eject ink through a small opening in the inkjet printhead. In addition, chemical additives can significantly increase the costs associated with the preparation of the above substances and are therefore economically unfavorable. Further, since the chemical additive (that is, the dispersant) does not have to be bound to the surface of the pigment, it may hinder the stabilization. Therefore, there is still a need to solve at least some of the problems primarily associated with existing dye-based and dye-based systems that use chemical additives, especially to improve the ink composition for use in inkjet printers. In addition, there is still a need for improvements in pigment-based materials that eliminate at least some of the problems primarily associated with existing dye-based and dye-based systems that use chemical additives.

<u style="single">Overview</u> In one aspect, the invention may comprise reacting cyanuric chloride with about 3 equivalents of a second compound or a mixture of second compounds to replace total reactive chlorine to form substituted triazines. A reforming method can be provided. Alternatively, the substituted triazine can be reacted with the surface of the pigment to form a surface-modified pigment.

In another aspect, the invention is X- [Y]._nA reactive compound having a reactive group is reacted with the second compound NS-ZM to substitute a reactive intermediate [Y]._a-X- (NS-ZM)_bIt is possible to provide a method for modifying a pigment, which may include forming a pigment. In addition, the method replaces the pigment with a reactive intermediate [Y]._a-X- (NS-ZM)_bIt is also possible to form a surface-modified pigment by binding a substitution-reactive intermediate to the surface of the pigment. X may be a sulfonyl, phosphoryl or 1,3,5-triazinyl group. Y may be a halogen leaving group, N may be a nucleophilic group, S may be an organic group, and ZM may be an ionizable terminal group. Further, n may be an integer of 1 to 3, b may be an integer of 1 to 3, and a = nb. NS-ZMs may be the same or different, respectively, if n is the same as or greater than b, and if b is 2 or 3, respectively.

In yet another aspect, the invention can provide a method of modifying a pigment, which may include attaching a reactive group to the surface of the pigment. The reactive group can then be replaced with an organic substrate having an ionizable end group. Pigments are Pigment Red 122, Pigment Violet 19, Pigment Violet 23, Pigment Red 202, Pigment Red 188, Pigment Yellow 155, Pigment Yellow 97, Pigment Green 7, Pigment Blue 15: 3, Pigment Blue 15: 4, and Pigment Yellow. You can choose from a group of 74.

In a further aspect, the invention can provide a method of modifying the pigment, which may include binding the reactive group XY to the surface of the pigment. Y can then be replaced with the organic substrate NS-ZM to form a surface-modified pigment to which XNS-ZM is attached. X may be a sulfonyl, phosphoryl or 1,3,5-triazine group. Y may be fluorine, chlorine, bromine or iodine. N may be an amine group, an imine group, a pyridine group or a thiol group. S may be a substituted or unsubstituted alkyl, aryl, or polymer chain having a molecular weight range of about 300 to about 8000. Z may be a carboxyl group, a sulfonyl group, a phenol group, a phosphoryl group, an ammonium group, a trimethylammonium group or a tributylammonium group. M may be a halide, a loaded electroion, a proton in the salt form, or a cation in the salt form.

Another aspect of the invention will become apparent by examining the detailed description and accompanying drawings.

<figref num="1">It is a figure which shows the low-resolution X-ray photoelectron spectroscopy (XPS) spectrum about the untreated carbon black sample and the carbon black sample obtained in Examples 1, 20, 31 and 41.</figref><figref num="2">It is a figure which shows the high-resolution N1s XPS spectrum about the untreated carbon black sample and the carbon black sample obtained in Examples 1, 20, 31 and 41.</figref><figref num="3">It is a figure which shows the high-resolution O1s XPS spectrum about the untreated carbon black sample and the carbon black sample obtained in Examples 1, 20, 31 and 41.</figref><figref num="4">It is a figure which shows the high-resolution S2p XPS spectrum about the untreated carbon black sample and the carbon black sample obtained in Examples 1, 20, 31 and 41.</figref><figref num="5">FIG. 5 shows low resolution XPS spectra for Pigment Blue 15 samples obtained in untreated Pigment Blue 15 and Pigment Blue 15 obtained in Examples 7, 9, 11, 16 and 42.</figref><figref num="6">FIG. 5 shows high resolution O1s XPS spectra for 15 untreated Pigment Blue samples and 15 Pigment Blue samples obtained in Examples 7, 9, 11, 16 and 42.</figref><figref num="7">FIG. 5 shows high resolution Na1s XPS spectra for 15 untreated Pigment Blue samples and 15 Pigment Blue samples obtained in Examples 7, 9, 11, 16 and 42.</figref><figref num="8">It is a figure which shows the low resolution XPS spectrum about the untreated Pigment Red 122 sample and the Pigment Red 122 sample obtained in Examples 14, 21, 37 and 45.</figref><figref num="9">FIG. 5 shows high resolution O1s XPS spectra for untreated Pigment Red 122 samples and Pigment Red 122 samples obtained in Examples 14, 21, 37 and 45.</figref><figref num="10">FIG. 5 shows high resolution Na1s XPS spectra for Pigment Red 122 samples obtained in Examples 14, 21, 37 and 45.</figref><figref num="11">FIG. 5 shows high resolution S2p XPS spectra for Pigment Red 122 samples obtained in Examples 14, 21, 37 and 45.</figref><figref num="12">It is a figure which shows the low resolution XPS spectrum about the untreated Pigment Yellow 74 sample and the Pigment Yellow 74 sample obtained in Examples 15, 29 and 46.</figref><figref num="13">It is a figure which shows the high-resolution C1s XPS spectrum about the untreated Pigment Yellow 74 sample and the Pigment Yellow 74 sample obtained in Examples 15, 29 and 46.</figref><figref num="14">It is a figure which shows the high-resolution O1s XPS spectrum about the untreated Pigment Yellow 74 sample and the Pigment Yellow 74 sample obtained in Examples 15, 29 and 46.</figref>

<u style="single">Detailed explanation</u> Before discussing all embodiments of the invention in detail, it should be understood that the invention is not limited in its application to the structural details and component arrangements described in the following description. The present invention can take other embodiments and can be implemented and implemented in a variety of ways. It should also be understood that the expressions and terms used herein are for illustration purposes only and should not be considered limiting. "Including," "including," or "having," and the use of these heterogeneous expressions is meant to include, as used herein, the items listed below and their equivalents, as well as additional items.

Further, it should be understood that all the numerical ranges shown in the present specification include all values from the minimum value to the maximum value. For example, if the concentration range is stated as 1% to 50%, values such as 2% to 40%, 10% to 30%, or 1% to 3% are explicitly listed herein. It is assumed that it is. There are only a few examples of specific objects, and the numbers between the minimum and maximum values listed and all possible combinations of numbers that include these values are expressly described herein. Please understand that it is.

In one embodiment, the present invention provides a method for modifying a pigment. This method may involve binding organic groups to charged end groups (loaded or positively charged) with the intervention of reactive molecules to obtain surface-stabilized modified pigments. Although not limited to the theory, this stabilization is also achieved by the uniform distribution of similarly charged groups covalently bonded on submicron-sized pigment particles by repulsive force. Conceivable.

In another embodiment, the present invention provides a method for modifying pigments. This method involves a chlorosulfonation step to form a reactive sulfonyl chloride intermediate, which can then be reacted with the appropriate organic molecule described above. In one aspect, the degree of chlorosulfonate can be increased to obtain a liquid gel or micelle-like composition. These form a stable dispersion when pulverized with an untreated pigment.

In yet another embodiment, the present invention provides a dispersion containing a self-dispersing pigment formed by the reaction of a pigment with a reactive intermediate bound to a suitable organic molecule as described above. The selection of reactive intermediates that are stable in an aqueous environment is another aspect of the invention.

In another embodiment, the invention provides a method of modifying a pigment, which may comprise attaching a reactive group to the surface of the pigment and then substituting the reactive group with an organic substrate having an ionizable end group. do.

In a further embodiment, the present invention provides a dispersion containing water and a self-dispersing pigment containing from about 0.01 to about 1.0 mmol S and about 0.01 to about 2.0 mmol of active hydrogen per gram of pigment. In another embodiment, the present invention provides a dispersion containing water and a self-dispersing pigment containing from about 0.06 to about 0.7 mmol S and about 0.07 to about 1.6 mmol of active hydrogen per gram of pigment.

<u style="single">Manufacturing method of self-dispersing pigment</u> One aspect of the present invention relates to a method for producing a stable self-dispersing pigment.

As used herein, the term "pigment" means an insoluble substance in a solvent used to add color to substrates such as plain paper or coated paper, films and other types of receiving media. The pigment may be black as well as other colors.

As used herein, the term "self-dispersing" pigment is a pigment that has a covalently bonded stabilizing group on its surface to form a stable aqueous dispersion in the absence of additional dispersants. means.

As used herein, the term "stable" refers to the changes that a dispersion undergoes over time when the dispersion is stored at ambient temperature for at least about 3 months to about 6 months to about 2 years. However, it means that the change shown in the important properties to be measured (eg, at least one of average particle size, viscosity, surface tension or pH) is the smallest change showing less than 10%. Accelerated test methods include a thermal stability test performed at about 70 ° C for at least about 1 week, or a thermal stability test performed at about 70 ° C for at least about 4 weeks.

In the first embodiment, the method for producing a self-dispersing pigment is as follows: (1) The pigment (P) is reacted with a reactive compound having an XY reactive group and a halogen-containing reagent, and the reactive group XY is formed on the surface of the pigment (P). And (2) react the pigment-reactive intermediate (P) XY with the second compound NS-ZM to form a self-dispersing pigment (P) XY. P)-Generally includes the step of forming XS-ZM (replacement step). An example of this embodiment is, but is not limited to, the step of attaching the reactive group XY to the surface of the pigment; and then substituting Y with the organic substrate NS-ZM and binding XNS-ZM. It may include a method of modifying a pigment, which may include the step of forming a surface modifying pigment.

In the second embodiment, the method for producing the self-dispersing pigment (P) -XS-ZM is as follows: (1) A reactive compound having an XY reactive group is reacted with the second compound NS-ZM to carry out a substitution reactive intermediate. The step of forming the compound XS-ZM (substitution step); and (2) reacting the pigment (P) with the substitution-reactive intermediate XS-ZM and using a second substitution reaction, the substitution-reactive intermediate. It may include the step of binding XS-ZM to the surface of the pigment to form the self-dispersing pigment (P) -XS-ZM. Examples of this embodiment are not limited to these, but X- [Y]._nA reactive compound having a reactive group is reacted with the second compound NS-ZM to substitute a reactive intermediate [Y]._a-X- (NS-ZM)_bSteps to form; pigment and substitution reactive intermediate [Y]_a-X- (NS-ZM)_bTo form a surface-modified pigment by binding a substitution-reactive intermediate to the surface of the pigment (in this case, n is an integer of 1 to 3; b is an integer of 1 to 3; and a = nb; where n is the same as or greater than b, and b is 2 or 3, then NS-ZMs are the same but different, respectively. It may include a method of modifying a pigment which may contain (may). In one embodiment, NS-ZMs may be different if b is 2 or 3.

In the third embodiment, the method for producing the self-dispersing pigment (P) -XS-ZM is as follows: (1) The reactive compound having an XY reactive group is reacted with the second compound NS-ZM, and the first substitution is performed. The step of forming the reactive intermediate XS-ZM (substitution step) and (2) reacting the reactive compound with the XY reactive group with a second compound N2-S2-Z2M2 different from step (1). , The step of forming the second substitution-reactive intermediate X-S2-Z2M2 (substitution step); (3) Reaction of the pigment (P) with the substitution-reactive intermediates XS-ZM and X-S2-Z2M2. , May include the step of binding the substitutional reactive intermediates to form the self-dispersing pigment Z2M2-S2-X- (P) -XS-ZM. In some cases, S-ZM and S2-Z2M2 may be the same and all reactive groups may be substituted. The final bond to the pigment surface may be one of the radically mediated disproportionation reactions.

In the fourth embodiment, the method for producing the self-dispersing pigment (P) -XS-ZM is (1) a step of using a pulverizing aid to pulverize and disperse the pigment to form an aqueous pigment dispersion; 2) A step of reacting a reactive compound having an XY reactive group with a second compound NS-ZM to form a first substitutionally reactive intermediate XS-ZM (substitution step); (3) XY reactive group. (Substitution step); (4) The pigment (P) pre-crushed with a pulverization aid is reacted with the substitution-reactive intermediates XS-ZM and X-S2-Z2M2, and the substitution-reactive intermediate XS- Steps of binding ZM and X-S2-Z2M2 to the surface of the pigment to form the self-dispersing pigment Z2M2-S2-X- (P) (R) -XS-ZM; and (5) Purifying the self-dispersing pigment However, it may include a step of removing impurities such as a grinding aid. In some cases, S-ZM and S2-Z2M2 may be the same.

In each of these embodiments, the reactive compound may have an XY reactive group, where X is, but is not limited to, carbonyl, sulfonyl, phosphoryl, cyanuryl and NH. Examples of Y include, but are not limited to, acid halide leaving groups such as fluorides, chlorides, bromides and iodides. can. In one suitable embodiment, X may be a sulfonyl, phosphoryl or cyanuryl (1,3,5-triazinyl). The acid halide-forming reagent contains a halogen. Examples of such reagents include, but are not limited to, chlorosulfonic acid, thionyl chloride, phosphoryl chloride and combinations thereof. Chlorine can be replaced with other halogens in these compounds. The reactive compound is stable in an aqueous medium for a short period of time at low temperatures.

During the substitution step, at least one leaving group Y of the XY reactive group is substituted with the second compound NS-ZM, where N is a nucleophilic group such as amine, imine, pyridine or thiol. Yes, S has, but is not limited to, organic groups such as substituted or unsubstituted alkyls, aryls, and more than about 1-100 carbons, or about 300-about 8000. Examples include polymer chains having a molecular weight in the range, and in the case of stabilization by negative charge, ZM is an acidic end group, in which case Z is not limited to these. , Carboxyl, sulfonyl, phenol, and phosphoryl, and M may be either a proton or a cation if it is present in salt form. This substitution can add charge and bulk to the surface of the pigment. This replacement step can be performed in an aqueous medium. The choice of acidic terminal functional group depends on the end application, but the basic advanced functional group must have sufficient nucleophilicity to replace the leaving group Y. The second compound may include polymers, amines, amino acids, alcohols, thiols, and combinations thereof. Examples of the second compound and N2-S2-Z2M2 NS-ZM are, but are not limited to, aminobenzoic acid, aminobenzene sulfonic acid, aminophenol, amino sulfonic acid, polyethoxylated amino acid, sulfanic acid. Sodium, sulfanic acid, sodium p-aminobenzoate, p-aminophenol, ethyl 4-aminobenzoate, taurine, oleic acid (amino), sodium aminooleate, tetramethylammonium 4-aminobenzoate, and sodium 4- Aminophenolates can be mentioned. Further, as the second compound, an organic polymer substrate can be mentioned. Examples of organic polymeric substrates include, but are not limited to, linear alkyl and branched chain ethoxy and propoxy chain polymers with known molecular weight ranges of 300 to 3000 MW, Huntsman.

In the case of positive charge stabilization, ZM may be a positively charged quaternary ammonium type terminal group, where Z is, but not limited to, ammonium, trimethyl. It may be ammonium and tributylammonium, where M may be a halide or any charged ion. Examples of the second compounds NS-ZM and N2-S2-Z2M2 are, but are not limited to, diamino monocyclic aromatic compounds or cations consisting of polyethyleneimine, polyguanidine, quaternary ammonium compounds and the like. Sex polymers can be mentioned.

The final self-dispersing pigment can be represented by the formula (P) -XS-ZM for the first and second embodiments. In some cases, there may be a plurality of -S-ZMs bound to pigments containing different second compounds. For the third embodiment, the final self-dispersing pigment can be represented by the formula Z2M2-S2-X- (P) -XS-ZM. Finally, the meaning of the use of "2" to modify N, Z, M and S indicates that N2, Z2, M2 and S2 are the same as or different from N, Z, M and S. N2, Z2, M2 and S2 can be selected from the same options described above for N, Z, M and S.

In order to explain the present invention, specific examples of the first embodiment are shown below (in the formula, P represents a pigment). <chemistry num="1"><img file="JP6946397B2_D0001.tif" /></chemistry>

In order to explain the present invention, specific examples of the second embodiment are shown below (in the formula, P represents a pigment). <chemistry num="2"><img file="JP6946397B2_D0002.tif" /></chemistry>

In order to explain the present invention, specific examples of the third embodiment are shown below (in the formula, P represents a pigment). <chemistry num="3"><img file="JP6946397B2_D0003.tif" /></chemistry>

Embodiments of the present invention will be described in more detail below. In general, a method for producing an autocovariant pigment begins with selecting a raw material for the pigment.

<u style="single">Pigment</u> Examples of pigments that can be surface-modified according to the present invention include azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, thioindigo pigments, triphenylmethane lake pigments, and oxazine lake pigments. It is not limited. Specifically, examples of those having a yellow color tone include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 16, 17, 65, 74, 83, 97. , 138, 150, 151 and 155. Examples of those having a red tone include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38, 41, 48, 49, 50, 51, 52, 57, 58, 60, 64, 83, 88, 89, 90, 112, 114, 122, 123, 166, 188, 202, CI Pigment Violet 19 and 23. Examples of those having a blue hue include CI Pigment Blue 1, 2, 15, 15: 3, 15: 4, 16, 25 and 75. Those having a green hue include, for example, CI Pigment Greens 7 and 36. Examples of those having a black tone include CI Pigment Blacks 1 and 7. Commercially available color pigments include, for example, Pigment Red 122 and Pigment Violet 19 (Lansco Colors, Montvale, NJ, or BASF Color, Charlotte, NC, or Clariant Colors, Charlotte, NC, or Sun Chemical, Cincinnati, OH. Pigment Blue 15: 1 (sold by Fanwood Chemical, Fanwood, NJ), Pigment Blue 15: 3, Pigment 15:

Moreover, carbon black is also mentioned as a suitable pigment. Carbon black is a general term for carbon particles derived from thermal decomposition or incomplete combustion of natural gas and hydrocarbons such as coal tar-derived aromatic oils, mineral oils, coal tar distillations and acetylene. There are now over 100 individual grades of carbon black available on the market, each with its own unique set of characteristics and properties. Any acidic carbon black, neutral carbon black and alkaline carbon black can be effectively applied to the treatments disclosed in the present invention. These include channel black, gas black, lamp black, thermal black, acetylene black and furnace black. More specifically, suitable carbon blacks include channel blacks. The quality of the carbon black used affects important properties of the dispersion such as average particle size, opacity, tint and stability. Examples of commercially available carbon blacks are those sold by Cabot (Elftex 8, Black Pearls® 490, Black Pearls). (Registered Trademarks) 120, Monarch® 120, Monarch® 700, Monarch® 880, Monarch® 1000, Monarch® 1100, Monarch® 1300, Monarch ( Registered Trademarks) 1400, Mogul® L, Regal® 99R, Regal® 250R, Regal® 300R, Regal® 330R, Regal® 400R, Regal® Trademarks) 500R, Regal® 660R), sold by Degussa (NIPex® 150IQ, NIPex® 150, Printex® 55, Printex® 80, Printex (Trademarks) Registered Trademarks) 90, Printex® A, Printex® G, Printex® U, Printex® V, Printex® 140U, Printex® 140V, Purex® LS35, Corax® HP160, Thermal Black N990, NIPex® 160IQ, NIPex® 90, Special black 4, Special black 4A, Special black 5, Special black 6, Special black 100, Special black 250, Color black FW1, Color black FW2, Color black FW2V, Color black FW18, Color black FW200, Color black S150, Color black S160, and Color black S170), sold by Columbia ( Raven® 780, Raven® 5000UII, Raven® 1255, Raven® 2500U, Raven® 3600U, Raven® 3500, Raven® 7000, Raven (Registered trademark) 1220, and Raven® 1225), and those sold by Mitsubishi Kagaku KK (MA8, MA11, MA77, MA100, MA220, MA230, MA600, MCF88, # 10B, # 20B, # 30, # 33, # 40, # 44, # 45, # 45L, # 50, # 55, # 95, # 260, # 900, 970 #, # 1000, # 2200B, # 2300, # 2350, # 2400B, # 2650, # 2700 , # 4000B, and CF9), but are not limited to these.

Pigments are available in a variety of particle sizes. In general, smaller particle sizes can result in higher surface areas, and higher surface areas can result in higher concentrations of hydrophilic surface groups. This ultimately enhances the dispersibility of carbon black in the aqueous medium. Therefore, the particle size may affect the dispersibility of the surface-modified pigment. For example, the average primary particle size of carbon black in the present invention may be less than about 50 nm, especially less than about 30 nm, especially less than 20 nm, especially less than about 10 nm. Aggregates of carbon black particles may be less than about 200 nm, especially less than about 150 nm, especially less than about 100 nm. The surface area of carbon black particles is about 100 m²Greater than / g, especially about 150m²Greater than / g, especially about 200m²It may be larger than / g. Carbon black particles with larger dimensions can be ground to the desired dimensions before or during surface modification using any number of techniques known to those of skill in the art. Such techniques include ball mills, grinders, flow jet mixers, impeller mills, colloidal mills, and sand mills (eg, "Super Mill", "Agitator Mill", "Dyno-mill", or "Beads Mill" trade names. (Commercially available in), but is not limited to these. Examples of the mill medium include, but are not limited to, glass beads, zirconia beads, and stainless steel beads. The mill medium may contain particles in a dimensional range of about 0.1 mm to about 3 mm, more specifically about 0.01 mm to about 5 mm. If the carbon black is easily milled, a rotary homogenizer or ultrasonic homogenizer can be used to reduce the particle size. In one embodiment, the surface-modified black pigment is composed of primary particles with a diameter of less than about 30 nm and aggregates with a diameter of about 200 nm or less, and has a diameter of about 100 m.²Manufactured from commercially available grade carbon black pigments with a surface area greater than / g.

Prior to producing the self-dispersing pigment, the pigment may or may be oxidized with an oxidizing agent such as nitric acid, ozone, hydrogen peroxide, persulfate, hypohalite or a combination thereof. It does not have to be. Aqueous oxidation of carbon black using sodium hypochlorite is described in US Pat. No. 2,439,442, issued April 13, 1948, and US Pat. No. 3,347,632, issued October 17, 1967 (see each). To be incorporated herein by After oxidizing the pigment, the method of the invention is then used to bond the compound of formula XS-ZM to the pigment surface to complete the newly introduced surface charge groups.

In some cases, prior to producing the self-dispersing pigment, the pigment can be moistened and ground and dispersed to nano-sized particles using a milling aid. The pigment may be in powder form or wet cake form before being milled with a milling aid. Grinding can be performed before, during, or after the reaction with the substitution intermediate. After completion of the binding reaction, the milling aid is removed using a purification method known to those skilled in the art to form a dispersion primarily containing the modified pigment and water. Examples of crushing aids are, but are not limited to, Triton X-100 (sold by Ashland Inc., Dublin, OH), Igepal CA-630 (sold by Rhodia, Cranbury, NJ). ), As well as Surfynol CT 121, 131 and 141 (sold by Air Products, Allentown, PA).

In one example of the first embodiment, the reactive compound containing sulfonyl chloride is bound to a pigment such as carbon black by chlorosulfonated with chlorosulfonic acid. The combination of acid strength, reaction temperature and time determines how many sulfonyl groups are attached to the pigment surface. In one embodiment, chlorosulfonic acid is carried out with an amount of chlorosulfonic acid that is five times the weight of carbon black.

In addition, chlorosulfonate can be carried out using a mixture of chlorosulfonic acid and thionyl chloride to prevent in situ hydrolysis. The amount of thionyl chloride can be extensively varied to control the degree of hydrolysis or to prevent hydrolysis altogether. In one embodiment, chlorosulfonate is carried out with 348 g of chlorosulfonic acid and 30 g of thionyl chloride.

The ratio of pigment to acid (weight basis) is determined primarily by operational efficiency such as mixing, ease of transfer, and cost. Chlorosulfurication of pigments can be carried out in the absence of additional solvents by using an excess of chlorosulfonic acid. A minimum ratio of acid to pigment of about 5 is very suitable for providing a good mixture throughout the reaction. Large excesses (eg, ratios of about 20) not only have no significant effect, but also increase the cost of both material and handling. In one embodiment, chlorosulfonic acid is used in an approximately 5-fold excess (w / w). In another embodiment, the ratio of pigment to chlorosulfonater is at least about 4: 1 (w / w). In yet another embodiment, the ratio of pigment to chlorosulfonater is from about 1:20 to about 1: 1 (w / w). In a further embodiment, the chlorosulfonic acid agent may be a mixture of chlorosulfonic acid and thionyl chloride in a ratio of about 3: 1 to about 6: 1 (w / w).

The chlorosulfonate of the pigment is carried out at a temperature rising temperature for a period of about 2 days or less. The reaction temperature during chlorosulfonate may be at least about 140 ° C, especially at least about 130 ° C, especially at least about 120 ° C. Further, the reaction temperature during chlorosulfonate may be about 60 ° C. or lower, particularly about 90 ° C. or lower, especially about 120 ° C. or lower. This includes embodiments in which the reaction temperature during chlorosulfonate is from about 120 ° C to about 130 ° C, and more specifically to about 140 ° C or less. In another embodiment, the reaction temperature during chlorosulfonate is from about 25 ° C to about 160 ° C. Generally, the higher the temperature, the shorter the reaction time required to achieve the desired concentration of sulfonyl groups on the pigment surface. For example, the desired chlorosulfonate at a reaction temperature of 140 ° C can take about 6 hours, whereas comparable chlorosulfonate at 80 ° C is considered to take more than 72 hours. .. In some embodiments, the reaction time may be at least about 2 hours, in other cases at least about 6 hours, and in other cases at least about 24 hours. In other embodiments, the reaction time may be about 48 hours or less, in other cases about 24 hours or less, and in other cases about 6 hours or less. This includes embodiments where the reaction time is from about 1 hour to about 48 hours. During chlorosulfonate, the contents of the reaction vessel are agitated to ensure proper mixing.

After chlorosulfonation, the reaction mixture can be quenched in water. In some embodiments, the reaction mixture is cooled to less than about 20 ° C before quenching, in other cases to less than about 60 ° C before quenching, and in other cases before quenching. Can be cooled to temperatures below about 90 ° C. This includes embodiments in which the reaction mixture is cooled to a temperature of about 20 ° C to about 90 ° C before quenching. The water to which the reaction mixture is added can be at or below a temperature of about 10 ° C, using, for example, ice, a chiller or a combination thereof. In one embodiment, the quench temperature can be maintained at about 0 ° C to about 5 ° C to maintain the reactive sulfonyl chloride intermediate. Chlorosulfonated products, called wet cakes, can be isolated from water by filtering and washing to remove excess reactants and water soluble products. It can be washed with water below 5 ° C.

The pigment-reactive intermediate is then replaced with at least one second compound containing an organic group that prevents hydrolysis to return to the acid. In one embodiment, the pigment-reactive intermediate can be used immediately for reaction with the second compound. For example, carbon black with a reactive sulfonyl chloride group can be immediately reacted with an organic compound containing amino-terminated and acidic-terminated groups. The second compound containing an organic group can be selected depending on the desired end use of the pigment.

The pigment-reactive intermediate can react with the second compound in the region of acidic pH (about 2 to about 5). The acidic pH range enhances the stability of the reactive compound and reduces the degree of unwanted reactions such as hydrolysis and self-condensation. This reactive compound preferentially reacts with a base such as a primary amine even when aminophenol is used as an organic group. This reaction can be directed primarily to the amino terminus by appropriate selection of reaction conditions well known to those of skill in the art (eg, pH, temperature and dilution). For example, the pH may be from about 2 to about 5, and the temperature may be from about 0 ° C to about 5 ° C. In another embodiment, the particle size of the pigment can be reduced by carrying out the reaction in a bead mill while the pigment-reactive intermediate is being reacted with the second compound. Due to the corrosiveness of the second compound, suitable constituent materials that are resistant to strong acids and strong bases can be selected to prevent metal leaching into the product.

The reaction of the pigment-reactive intermediate with the second compound can be carried out with mixing for about 2 hours to about 4 hours. In one embodiment, the reaction can be forcibly completed by heating the mixture to a high temperature of about 60 ° C to about 90 ° C.

Another example of the first embodiment is, but is not limited to, the step of attaching the reactive group XY to the surface of the pigment; and then substituting Y with the organic substrate NS-ZM and XNS- ZM (in the formula, X is a sulfonyl, phosphoryl or 1,3,5-triazinyl group; Y is a halogen leaving group; N is a basic leaving group; S is an organic group; ZM is an organic group It may include a method of modifying a surface-bearing pigment, which may include the step of forming a surface-modified pigment to which an ionizable end group) is attached. Most of the pigment surface can be modified to form a liquid gel. The liquid gel can then be ground with an excess of untreated pigment and water to form a stable aqueous pigment dispersion. Examples of modifying the surface of most pigments are, but are not limited to, chlorosulfonating the pigment at a temperature of at least about 90 ° C for at least about 1 hour and chlorosulfonated pigments (ie, pigments). Includes forming (sulfonyl chloride).

In one example of the second embodiment, the reactive compound containing a cyanuryl group is replaced with a second compound containing an organic group. The Substitution Reactive Intermediate-XS-ZM is then attached to a pigment such as carbon black using cyanuric chloride. The combination of pH, reaction temperature and time determines how many groups are attached to the surface of the pigment. In one embodiment, the reaction is carried out with 52 g cyanuric chloride per 120 g of carbon. In another embodiment, the reaction is carried out with 15 g cyanuric chloride per 40 g of carbon.

In some embodiments, a slurry of a second compound containing an organic group, cyanuric chloride, water, ice and a base is made. A second compound containing an organic group may be selected by the desired end use of the pigment Ru.

In one example of the third embodiment, the reactive compound containing a cyanuryl group is replaced with a second compound containing two organic groups, which may be the same or different. The two substitution-reactive intermediates XS-ZM and X-S2-Z2M2 are then bound to pigments such as carbon black by using cyanuric chloride. The combination of pH, reaction temperature and time determines how many groups are attached to the surface of the pigment. This method can be carried out sequentially by first reacting with a slurry of a second compound containing an organic group, cyanuric chloride, water, ice and a base. The system is completed with a second slurry of different second compounds, including organic groups, cyanuric chloride, water, ice, acids and bases.

The ratio of cyanuric chloride to the second compound is generally determined by the stoichiometric ratio, the concentration of which is adjusted to mix well. The reaction of cyanuric chloride with the second compound can be carried out with mixing for about 2 hours to about 4 hours.

In the example of the fourth embodiment, the stoichiometric ratio (replaces all three chlorines) with a second compound or a mixture of the second compounds before reacting the total reactive chlorine in cyanul chloride with the pigment. To replace by manipulating 3 equivalents) and temperature (higher than about 90 ° C). Substituted triazine is formed by this reaction, and this substituted triazine can be bound to the surface of the pigment. The mixture of the second compound may contain one, two or three different second compounds. In these examples, reaction initiators such as persulfate components are used to influence or accelerate the binding process. In some embodiments, the reaction can be carried out at a temperature of about 25 ° C to about 90 ° C. In another embodiment, the pigment may be ground to less than about 100 nm before, during, or after reacting the pigment with the substituted triazine.

The pigment is mixed with this "reagent" to produce a dispersion. In the embodiment where there are two slurries containing different second compounds, the pigment is continuously mixed with the slurry. The temperature of the dispersion can be maintained at about 0 ° C to about 15 ° C for about 1 hour to about 2 hours. The mixture of the reactive compound (eg, substituted triazine) dispersion and the pigment is then heated to a temperature within about 2 days. A free radical initiator such as potassium persulfate can be added to accelerate the reaction. The reaction temperature may be at least about 40 ° C, especially at least about 50 ° C, especially at least about 60 ° C. Moreover, the reaction temperature may be below about 90 ° C, especially below about 80 ° C, especially below about 60 ° C. This includes embodiments where the reaction temperature is from about 50 ° C to about 60 ° C, especially below 90 ° C. In general, temperatures above 50 ° C are required for free radical initiators to be effective. This includes embodiments where the reaction time is about 16 to 24 hours. The contents of the reaction vessel are agitated during the reaction to ensure proper mixing. The modified pigment can be filtered to remove excess reactants and impurities.

In one embodiment, the reactive compound (eg cyanuric chloride) reacts with the second compound in the acidic pH range (about 2 to about 5). The acidic pH range enhances the stability of the reactive compound and reduces the degree of unwanted reactions such as hydrolysis and self-condensation. This reactive compound preferentially reacts with a base such as a primary amine even when aminophenol is used as an organic group. This reaction can be directed primarily to the amino terminus by appropriate selection of reaction conditions (eg, pH, temperature and dilution) well known to those of skill in the art. For example, the pH may be from about 2 to about 5, and the temperature may be from about 0 ° C to about 5 ° C.

In some cases, the particle size of the pigment can be reduced by performing the reaction in a bead mill while the pigment is being reacted with the base-XS-ZM. Due to the corrosiveness of the second compound, suitable constituent materials that are resistant to strong acids and strong bases can be selected to prevent metal leaching into the product.

Reacting a reactive compound or second group containing an acid derivative with a pigment can produce acidic surface groups, which can reduce the pH of the reaction mixture. Lower pH can lead to destabilization of the modified pigment dispersion or slurry of reactive compound and second compound during substitution and can also increase viscosity. Therefore, if necessary, the pH may be adjusted with a basic reagent before or during the substitution. The pH of the reaction mixture during the substitution may be about 7 or higher, especially about 8 or higher, especially about 9 or higher. The pH can be adjusted by any method known in the art, for example by adding a base. Suitable bases include, but are not limited to, alkaline hydroxides and calcium-free alkaline hydroxides (eg, NaOH, KOH, LiOH, NH).₄OH), alkaline carbonates and bicarbonates (eg, LVDS)₃, KHCO₃), And organic bases (eg, dimethylethanolamine and triethanolamine). In particular, suitable pH regulators include calcium-free sodium hydroxide.

<u style="single">Surface modification pigment</u> After completion of the reaction, the self-dispersing pigment can be isolated from the reaction mixture as a dry powder. The resulting modified pigment can be purified using various techniques known to those skilled in the art to remove unreacted raw materials, by-products salts, and other reactive impurities. The purification method may include, but is not limited to, a filtration method, a centrifugation method, or a combination of the two. The modified pigment can also be isolated, for example by evaporation, or recovered by filtration and drying using techniques known to those of skill in the art.

Alternatively, the self-dispersing pigment can be provided as a concentrated aqueous pigment dispersion. The self-dispersing pigment dispersions of the present invention are purified to remove organic and inorganic impurities and other unwanted free species that may coexist in the dispersion as a result of the manufacturing process. Can be done. Purification methods include, but are not limited to, water washing, reverse osmosis and ultrafiltration. In some embodiments, the dissolved impurities are ultrafiltered until the chloride and sulfate content of the feed sample adjusted to 10% solids is less than about 150 ppm, especially less than about 100 ppm, especially less than about 25 ppm. Can be removed by If necessary, the pH of the dispersion can be adjusted prior to purification. A sufficient amount of acid or base can be added to adjust the pH of the dispersion to at least about 7, especially at least about 8, especially at least about 9. This includes embodiments where the pH of the dispersion is from about 7 to about 9. The dispersion can be concentrated, if desired, by removing some of the water. In some embodiments, the dispersion is concentrated to at least about 8% solids, in other cases at least about 14% solids, and in other cases at least about 20% solids. This includes embodiments where the dispersion is concentrated to a solid content of about 8% to about 16%. In other embodiments, the dispersion is concentrated to at least about 10% solids, in other cases at least about 18% solids, and in other cases at least about 20% solids. This includes embodiments where the dispersion is concentrated to about 14% to about 8% solids.

It is also possible to add a bactericidal agent to the dispersion to suppress the growth of microorganisms. Examples of suitable bactericides are sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazolin-3- On, methylisothiazolinone, and chloromethylisothiazolinone include, but are not limited to. Commercially available disinfectants include Proxel® CRL, Proxel® BDN, Proxel® GXL, Proxel® XL-2, and Proxel® TN (Arch Chemicals,). (Sold by Smyrna, GA), as well as XBINX® (PMC Specialties Group, Inc., Cincinnati, (Sold by Ohio). Generally, a small amount, eg 0.05-5%, especially 0.1-1%, especially 0.2-0.4% by weight of disinfectant is used in the dispersant. It contains 0.3% by weight of fungicide.

Agents for imparting fluidity and stability can also be added to the dispersant. Examples of such agents are US Pat. No. 5,059,248 (filed October 22, 1991), US Pat. No. 5,591,455 (filed January 7, 1997), and US Pat. No. 5,595,592 (filed January 21, 1997). ) (Each of these is incorporated herein by reference). Specific examples include, but are not limited to, linear aliphatic substituted glycine compounds and salts thereof. As used herein, the term "linear aliphatic substituted glycine" means a glycine compound in which the amino group of glycine is substituted with a linear aliphatic group. Examples of agents of this type that can be used in the practice of the present invention are ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, iminodiacetic acid and ethanoldiglycine, and their alkali metals. (Eg sodium) salts, alkaline earth metal (eg calcium) salts, and ammonium salts. Other similar linear aliphatic substituted glycine compounds known to those of skill in the art and salts thereof can also be used. In some embodiments, the salts of ethylenediaminetetraacetic acid described above are used because of their effectiveness, cost effectiveness and non-toxicity. In some embodiments, these agents may make up about 0.5-3.5% by weight, preferably about 1.5-2.5% by weight, of the pigment in the dispersant composition.

The dispersion can be filtered through a filter cartridge, depending on the needs of the dispersion for a given end use. In some embodiments, the nominal pore size of the filter cartridge is about 5 microns or less, especially about 1 micron or less, especially about 0.5 micron or less, especially about 0.2 micron or less.

In addition to powders and dispersions, self-dispersing pigments can also be isolated as water wet press cakes. In the press cake form, the self-dispersing pigment is not as agglomerated as in the dry form, so the self-dispersing pigment is subject to large amounts of deagglomeration, for example when used in ink production. do not need.

If desired, the charge equilibrium counterion associated with the surface modifying group as a result of the binding / substitution process may be at least partially substituted or altered by the use of appropriate base or salt forms, or It can be exchanged or replaced with other suitable cations using known ion exchange methods such as ultrafiltration, reverse osmosis, conversion to acid form as an intermediate. Examples of counterions are, but are not limited to, alkali metal ions (eg, Na).⁺, K⁺And Li⁺), NR₁R₂R₃H⁺, And their combinations (in the formula, R₁, R₂And R₃Independently, H or C₁-C₅ Alkyl groups (which may be unsubstituted or substituted) include, for example, tetraethylammonium ion (TEA), tetramethylammonium ion (TMA), ethanolammonium ion, triethanol. Ammonium ion, tetrabutylammonium ion, etc.

<u style="single">Properties of modified pigments</u> The self-dispersing pigment exhibits at least one of long-term high temperature stability, water resistance and highlighter fastness than expected for pigment particles with sulfonic acid or carboxylic acid groups attached. Also, it may have a particle size distribution suitable for use in high speed injection applications.

The self-dispersing pigment can have the following properties. The solid content% in the modified pigment may be about 8 to 16.

The pH of the modified pigment dispersion may be about 5 to about 10.

The viscosity of the modified pigment dispersion may be from about 1 to about 10 cps, particularly from about 1.3 to about 7.6 cps.

The surface tension of the modified pigment dispersion may be about 39 to about 72 dynes / cm.

The amount of Na and K in the modified pigment dispersion can be an indicator of the newly bound anionic substrate (sulfanilic acid or 4-aminophenolic acid or 4-aminobenzoic acid in Na / K form). The amount of Na may be about 100 to about 6500 ppm, and the amount of K may be about 30 to about 1200 ppm.

The increase in S content in the modified pigment dispersion may be due to the introduction of sulfonyl groups and / or the binding of sulfonated substrates such as, but not limited to, sulfanilic acid. The S content in the modified pigment may be about 50 ppm to about 2600 ppm. In one embodiment, the content of S in the modified pigment may be about 50 ppm with respect to the binding of 4-aminobenzoic acid and 4-aminophenol. In another embodiment, the content of S in the modified pigment may be about 1700 ppm if sulfanilic acid is attached to the pigment by a sulfone bond.

<u style="single">Uses of modified pigments</u> The self-dispersing pigment according to the present invention can be used in many end-use applications. These uses include, but are not limited to, coatings, paints, papers, adhesives, latexes, toners, fabrics, fibers, plastics, and inks. Specific examples include, but are not limited to, printing inks for paper, fabrics, textiles, metal modifications and plastics, wood stains, writing tools and color filters. The self-dispersing pigment produced by the method of the present invention is particularly suitable for use in printing applications and wood stains. In one embodiment, the pigmented inkjet inks of the invention can be useful in high quality printing on inkjet photo printers.

One aspect of the present invention relates to an inkjet ink preparation using the above self-dispersing pigment. Inkjet formulations containing such pigments can do at least one of the following: 1) provide high resolution and high density uniform, bleed-free images on print media; 2) ink at the tip of the nozzle. Does not cause typical nozzle clogging caused by drying; 3) Quickly dries on paper; 4) Good light and water resistance; 5) Good long-term storage stability; 6 ) Shows print characteristics that are not related to paper quality.

The ink composition of the present invention can be produced by combining the above-mentioned modified pigment with an aqueous vehicle and any suitable additive. The amount of modified pigment (based on weight) in the ink composition is at least about 0.1%, especially at least about 10%, especially at least about 20%. Further, the amount (weight basis) of the modified pigment in the ink composition is about 12% or less, particularly about 8% or less, especially about 5% or less. This includes embodiments in which the amount of modified pigment (based on weight) in the ink composition is present in an amount in the range of about 2% to about 12%.

The aqueous vehicle may contain water, or water in combination with one or more water-soluble organic solvents. The water-soluble organic solvent can be combined with water to form an aqueous vehicle. Examples of the water-soluble organic solvent include alcohols, polyhydric alcohols such as ethylene glycol, ketones and ketone alcohols, such as acetone and diacetone alcohols, ethers such as tetrahydrofuran and dioxane, and lower alkyl ethers of polyhydric alcohols. For example, ethylene glycol monomethyl (or monoethyl) ether, nitrogen-containing solvents such as pyrrolidone, N-methyl-2-pyrrolidone, sulfur-containing solvents such as thiodiethanol, saccharides and derivatives thereof, such as glucose, oxyethylene adducts of glycerin; and di. Examples include oxyethylene adducts of glycerin. The water-soluble organic solvent can be used alone or in combination. When a mixture of water and a water-soluble organic solvent is used, the amount (weight basis) of the water-soluble organic solvent in the ink composition is at least about 5%, especially at least about 15%, especially at least about 25%. Further, the amount (weight basis) of the water-soluble organic solvent in the ink composition is about 50% or less, particularly about 30% or less, particularly about 15% or less. This includes embodiments where the amount (weight basis) of the water-soluble organic solvent in the ink composition is from about 5% to about 30%. The amount of water in the ink composition is at least about 40%, especially at least about 50%, especially at least about 60%. Further, the amount of water in the ink composition is about 90% or less, especially about 80% or less, especially about 70% or less. This includes embodiments where the amount of water in the ink composition is from about 40% to about 80%.

Additives may be included in an aqueous vehicle to impart various desired properties, such as those required to adapt an ink to the requirements of a particular inkjet printer, or light stability, smear resistance. A balance of properties, viscosity, surface tension, coating permeability, optical density, adhesive strength, highlighter resistance, or crust resistance can be provided. For example, penetrants can be added to reduce bleeding, improve wetting of the print medium, or improve the overall performance of the printed image. Examples of penetrants include, but are not limited to, alkyl alcohols having 1 to 4 carbon atoms, such as ethanol, glycol ethers, such as ethylene glycol monomethyl ether, diols, such as 1,2. -Alkyldiol, formamide, acetamide, dimethyl sulfoxide, sorbitol and sulfolane. The penetrant can be used alone or in combination. The amount of penetrant (based on weight) in the ink composition ranges from 0% to about 60%, especially from about 2% to about 40%, especially from about 5% to about 20%. This includes embodiments in which the amount of penetrant (based on weight) in the ink composition is present in an amount in the range of about 10% to about 15%.

Surfactants can be added to the aqueous medium to reduce the surface tension of the ink composition. The surfactant may be an anionic surfactant, a nonionic surfactant, and / or a cationic surfactant. Suitable surfactants include those described below, as well as US Pat. No. 5,116,409 (filed May 26, 1992), US Pat. No. 5,861,447 (filed January 19, 1999), and US Pat. Listed in Nos. 6,849,111 (filed February 1, 2005), each of which is incorporated herein by reference.

Surfactants are commercially available under a variety of well-known trade names, for example, the PLURONIC® series (BASF Corporation, Parsippany, NJ), the TETRONIC® series (BASF Corporation), to a small extent. , Parsippany, NJ), ARQUAD® Series (Akzo Chemical Inc., Chicago, Ill.), TRITON® Series (Union Carbide Corp., Danbury, Conn.), SURFONIC® Series (Texaco) Chemical Company, Houston, Tex.), ETHOQUAD® Series (Akzo Chemical Inc., Chicago, Ill.), ARMEEN® Series (Akzo Chemical Inc., Chicago, Ill.), ICONOL® Series (BASF Corporation, Parsippany, There are NJ), SURFYNOL® series (Air Products and Chemicals, Inc. Allentown, Pa.), And ETHOMEEN® series (Akzo Chemical Inc., Chicago, Ill.).

Surfactants can be used alone or in combination. The amount of surfactant in the ink composition (based on weight) may range from 0% to about 10%, in particular from about 0.1% to about 10%, in particular from about 0.3 to about 5%. This includes embodiments in which the amount of surfactant in the ink composition (based on weight) may range from about 0.1% to about 8%.

One or more wetting agents can be added to the aqueous vehicle to prevent clogging of the inkjet nozzles due to drying during the waiting time. The wetting agent can be selected from substances having high hygroscopicity and high water solubility. Examples of wetting agents include, but are not limited to, polyols such as glycerol, lactams such as 2-pyrrolidone, urea compounds such as urea, 1,3-dimethylimidazolidinone, sugars such as sorbitol. , 1,4-Cyclohexanedimethanol, 1-methyl-2-piperidone, N-ethylacetamide, 3-amino-1,2-propanediol, ethylene carbonate; butyrol acetone and Liponic EG-1. The amount of the wetting agent used is not particularly limited, but in general, the amount of the wetting agent (based on weight) in the ink composition is 0% to about 30%, particularly about 1% to about 15%, and particularly about 5%. It may be in the range of ~ about 10%.

The polymer can be added to the ink composition to improve the water resistance, abrasion resistance, and highlighter resistance of the image on the print medium. Suitable polymers include polyvinyl alcohol, polyester, polyester melamine, styrene-acrylic acid copolymer, styrene-maleic acid copolymer, styrene-maleic acid-alkyl acrylate copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-alkyl acrylate copolymer, Examples include, but are not limited to, styrene-maleic acid semi-ester copolymers, vinyl-naphthalene-acrylic acid copolymers, vinyl naphthalene-maleic acid copolymers and salts thereof. The amount of polymer (based on weight) in the ink composition may range from 0% to about 5%, in particular from about 0.1% to about 3%, in particular from about 0.2% to about 2.5%. This includes embodiments in which the amount of polymer (weight basis) in the ink composition may range from about 0.1% to about 3.0%.

The ink composition of the present invention can be buffered to a desired pH using a number of pH regulators. Suitable pH regulators include alkaline hydroxides, alkaline carbonates and bicarbonates, triethylamine, dimethylethanolamine, triethanolamine, mineral acids, hydrochloric acid, and sulfuric acid. The pH regulator can be used alone or in combination. The amount (weight basis) of the pH regulator in the ink composition may range from 0% to about 3.0%, in particular from about 0.1% to about 2.0%, in particular from about 0.5% to about 1.5%. This includes embodiments in which the amount (weight basis) of the pH regulator in the ink composition ranges from about 0.2% to about 2.5%.

Preservatives such as fungicides and fungicides can also be added to the ink composition. Examples of suitable preservatives are sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazolin-3- On, methylisothiazolinone, and chloromethylisothiazolinone are mentioned. Commercially available disinfectants include UCARCIDE® 250 (sold by Union Carbide Company), Proxel® CRL, Proxel® BDN, Proxel® GXL, Proxel®. ) XL-2, Proxel® TN (sold by Arch Chemicals, Smyrna, GA), Dowicides® (Dow Chemical, Midland, Mich), Nuosept® (Huls America, Inc.) ., Piscataway, NJ), Omidines® (Olin Corp., Cheshire, Conn), Nopcocides® (Henkel Corp., Ambler, Pa), Troysans® (Troy Chemical Corp., Newark, NJ), and XBINX® (PMC Specialties Group, Inc., Cincinnati, Ohio). Preservatives can be used alone or in combination. The amount of preservative (based on weight) in the ink composition may range from 0% to about 1.5%, particularly from about 0.05% to about 1.0%, especially from about 0.1% to about 0.3%. This includes embodiments in which the amount of preservative (weight basis) in the ink composition may range from about 0.05% to about 0.5%.

The ink composition may contain one or more viscosity modifiers. Examples of the viscosity modifier include rosin compounds, alginic acid compounds, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, salts of polyacrylic acid, polyvinylpyrrolidone, gum arabic, and starch. The amount (weight basis) of the viscosity modifier in the ink composition may range from 0% to about 10%, in particular from about 0.5% to about 8%, in particular from about 1% to about 5%. This includes embodiments in which the amount (weight basis) of the viscosity modifier in the ink composition may range from about 1% to about 7%.

In addition, other additives that can be contained in the aqueous vehicle include antioxidants, ultraviolet absorbers, chelating agents, conductivity regulators, viscosity regulators, oxygen absorbers, anticorrosion agents, and curling inhibitors. , Anti-bleeding agents, antifoaming agents, and buffers. The ink composition of the present invention may contain one or more colorants in addition to the pigment dispersion liquid of the present invention.

The ink composition of the present invention is particularly suitable for use as an ink composition for inkjet printing in which droplets of the ink composition are ejected from a printing apparatus and deposited on a substrate to form an image. Suitable printing devices include continuous inkjet (CIJ), drop-on-demand valve (DoD Valve), and piezoelectric drop-on-demand (Drop-on-Demand Piezo-Electric). (DoD Piezo)), and thermal inkjet (Thermal Ink Jet (TIJ)), but are not limited to these. Similarly, any suitable substrate can be used, including plain paper, bond paper, coated paper, transparent materials, textile materials, plastics, polymer films, and inorganic substrates. However, those skilled in the art will appreciate that the ink compositions described above may also have applications in other areas, such as, but not limited to, general writing tool applications and stamp applications. It should be obvious.

The ink composition of the present invention can be used alone or in combination with a base color to form a black image, or in combination with other ink compositions to form a colored image. In some embodiments, the ink compositions of the present invention are used in combination with one or more other ink compositions such as cyan ink, magenta ink, and / or yellow ink. In another embodiment, cyan ink, magenta ink, and yellow ink are overprinted to form a black image, and this printing is used in combination with the printing of the black ink of the present invention.

<u style="single">Wood stain</u> Another aspect of the present invention relates to an aqueous preparation using the above self-dispersing pigment as a wood stain and a coating agent. Wood stains containing such pigments can exhibit at least one of the following properties: 1) good wood absorption and adhesion; 2) good transparency; 3) excellent water resistance and light resistance.

Water resistance is measured by the difference in DE * measurements of wood stain between the immersion area and the control. A lower DE * value can indicate higher water resistance. A small DE * can indicate that there is no or minimal color change due to decomposition or loss. For example, a low DE * value can exhibit high water resistance as seen in carboxy-modified pigment dispersions. The DE * value of the modified pigment dispersion can be about 0 to about 3. A specific example is a pigment modified with 4-aminobenzoic acid. In another example, the carboxy-modified Pigment Blue 15 and Pigment Yellow No. 74 dispersions had low DE * values of about 0.19 and 0.43, respectively. Delta E is the difference between the two tones. The L, a and b values are measured based on the spherical color. + L = white, -L = black, + a = red, -a = green, + b = yellow, -b = blue. C is chromaticity (saturation) and H = Hue. Recordings are measured using a spectrophotometer. Delta E = (L)₁-L₂)² + (a₁-a₂)² + (b₁-b₂)²。

<u style="single">Dressing</u> Coating agents containing such pigments may exhibit at least one of the following properties: 1) Good adhesion to substrates such as metals, paper, glass, plastics and wood; 2) Ease of application and drying; 3 ) Good weather resistance, water resistance and light resistance; 4) Good gloss retention; 5) Good chemical resistance and cohesion resistance.

Similar to water resistance, the resistance of the dressing to strong acids and bases is measured as the difference between the spot portion and the control DE * value. The DE * value of the modified pigment dispersion may be about 0 to about 3. In one example, the coating agent containing modified carbon black had a low DE * value for acid resistance of about 0.08. In another example, the coating agent containing Modified Pigment Blue No. 15 had a low DE * value for strong base resistance of about 1.56.

<u style="single">Color filter</u> Another aspect of the present invention relates to an aqueous preparation using the self-dispersing pigment in a color filter. Color filters have applications in the field of display images, such as, but not limited to, desktop monitors / laptop screens, LCD TV screens, mobile phone display panels, digital camera screens, and GPS panels. Color filter formulations containing the pigments of the present invention may exhibit at least one of the following properties: 1) Good adhesion to glass and plastic film substrates; 2) Good transparency; 3) Easy to apply and dry Properties; 4) Good heat resistance and light resistance.

The transmittance of a particular color filter is measured to determine its usefulness. Color filters have maximum transmittance in a narrow band and can provide the highest utility.

In one embodiment, the carbon black may not have a transmission band, the magenta pigment dispersion may have a minimum transmittance in the range of about 520 to about 560 nm, and the yellow pigment dispersion may have a minimum transmittance. The cyan pigment dispersion may have a minimum transmittance in the range of about 400 to about 480 nm, and the cyan pigment dispersion may have a minimum transmittance in the range of about 600 to about 680 nm.

<u style="single">Printing</u> Another aspect of the present invention relates to an aqueous preparation using the self-dispersing pigment in a printing application. The print formulation containing the pigment of the present invention may exhibit at least one of the following properties: 1) Good adhesion to textiles (eg cotton, nylon, polyester, wool, polyacrylic acid, or blends thereof). 2) Ease of application and drying; 3) Good water resistance and light resistance; 4) Good wash fastness.

The wash resistance and water resistance of the dyed fabric can be measured by the difference in DE * values between the control fabric and the washed fabric.

The DE * value of the modified pigment dispersion can be about 0 to about 3. In one example, the modified carbon black can have a low DE * value of about 0.23. In another example, Modified Pigment Yellow No. 74 may have a high DE * value of about 6.72.

<p> Specific embodiments of the present invention are provided in the following examples. The following examples are provided to illustrate the invention and assist those skilled in the art of manufacturing and using the invention. These examples are by no means intended to limit the scope of the invention.</p><p><u style="single">Example 1</u><u style="single">Pigment dispersion (Example showing chlorosulfonate in chlorosulfonic acid and thionyl chloride followed by binding of small molecules)</u> Primary particle size is 20nm and BET surface area is 160m²Commercially available gas carbon black (65 g) manufactured by Degussa (Burr Ridge, IL), which is / g, was chlorosulfonated with 332 g of experimental grade chlorosulfonic acid at 120 to 4 ° C for 20 hours. The reaction mixture was cooled to 56 ° C. and 68.5 g of thionyl chloride was added dropwise. After adding total thionyl chloride, the reaction product was reheated to 103-5 ° C and maintained at that temperature for 4 hours. The reaction mixture was then cooled to room temperature and quenched in water and ice, adjusting the quenching temperature below -5 ° C. The precipitate product was isolated by filtration and washed with ice-cold water (&lt;5 ° C) to remove lysates. Then, at 2-5 ° C, a solution of ethyl 4-aminobenzoate (Aldrich, experimental grade, 21.7 g) in 140 g DI water containing 15.5 g of concentrated hydrochloric acid (37%) and a product cake (253 g). ) And reacted. After mixing at 2000 rpm for 30 minutes, then Hockmeyer media mill (Hockmeyer Equipment Corp., Elizabeth City, 20% of which (sold by North Carolina), ground it at 5000 rpm using a 0.4 mm YTZ medium (sold by Quackenbush Co., Inc., Crystal Lake, Illinois). The temperature was raised to 10 ° C and the pH was adjusted to 4.7 by the addition of the sodium acetate solution. Grinding was continued for another 5 hours. One hour after the start of pulverization, the pH was raised to 12.6 by adding calcium-free sodium hydroxide (23 g) to the pulverized product. The reaction mixture was removed from the grinder and heated at 85 ° C. for 2 hours to hydrolyze the methyl ester. Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 18% solids and mixed with (0.3%, wt / wt) Proxel GXL (sold by Arch Chemicals, Smyrna, GA). Finally, the product was filtered through a 0.7 micron GF filter.</p><p><u style="single">Examples 2-9</u> Examples 2-9 were prepared for Example 1 by the same method described above.</p><p><u style="single">Table 1. Examples of binding via reactive sulfonyl chloride intermediate</u><tables num="1"><img file="JP6946397B2_D0004.tif" /></tables>¹ Degussa (Burr Ridge, IL)² CIBA (Newport, DE) PB 15: 4³ Large particles were separated by centrifugation at 10,000 rpm for 5 minutes prior to filtration through BASF (Mount Olive, NJ) PB 15: 3, 0.7 micron TCLP. ⁴ Clariant Colors (Charlotte, NC) PB 15: 3</p><p><u style="single">Table 1 Continued</u><tables num="2"><img file="JP6946397B2_D0005.tif" /></tables></p><p> Abbreviations are used for brevity throughout the examples. "H" means time, "AP" means aminophenol, "SA" means sulfanilic acid, and "4ABA" means 4-aminobenzoic acid.</p><p><u style="single">Example 10</u><u style="single">Pigment Dispersion (Example of Forming Different Salt Forms Through Bonding-Example of Tetramethylammonium Salt)</u> Primary particle size is 20nm and BET surface area is 160m²Commercially available gas carbon black (66 g) from / g Degussa was chlorosulfonated at 122-7 ° C for 19 hours with 348 g of experimental grade chlorosulfonic acid. The reaction mixture was cooled to 74 ° C. and 30.0 g of thionyl chloride was added dropwise. After adding total thionyl chloride, the reaction product was reheated to 134 ° C and maintained at that temperature for 1 hour. The reaction mixture was then cooled to room temperature and quenched in water and ice, adjusting the quenching temperature below -5 ° C. The precipitate product was isolated by filtration and washed with ice-cold water (&lt;5 ° C) to remove lysates. The product cake (326 g) was then mixed in ice-cold DI water to give a slurry at pH = 1.5. This pH was first raised to 4.5 with tetramethylammonium hydroxide solution (25%). The pH was further adjusted to a solution of 4-aminobenzoic acid (Aldrich, experimental grade, 18 g) in 90 g DI water containing 40.3 g of tetramethylammonium hydroxide solution (25%) at 25 ° C and 8 g of Surfynol. CT-141 (Air Products &amp; Chemicals, Inc., Allentown, (Sold by PA) and increased to 6.5. It was then briefly mixed with additional tetramethylammonium hydroxide solution (25%) to a final pH of 9.6. The mixture was cooled to 4 ° C and then in a Hockmeyer media mill (sold by Hockmeyer Equipment Corp., Elizabeth City, North Carolina), 0.4 mm YTZ medium (Quackenbush Co., Inc., Crystal). Lake, It was ground at 4800 rpm using (sold by Illinois) and adjusted to a temperature of 37 ° C and a pH above 8.8 by adding a solution of tetramethylammonium hydroxide. Grinding was continued for a total of 4 hours. The reaction mixture was removed from the grinder and heated at 60-76 ° C for 15 hours. Additional tetramethylammonium hydroxide was added to raise the pH to 9.2. Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 17% solids and mixed with (0.3%, wt / wt) Proxel GXL (sold by Arch Chemicals, Smyrna, GA). Finally, a portion (112 g) of this product was filtered through a 0.7 micron GF filter.</p><p><u style="single">Example 11</u><u style="single">Pigment dispersion (chlorosulfonated PB15 in chlorosulfonic acid; examples of binding to sulfanilic acid and dispersed PB15)</u> Pigment Blue No. 15: 1 (60 g) manufactured by Newchemic (Montvale, NJ) on the market was chlorosulfonated at 110 to 118 ° C. for 1 hour with 320 g of experimental grade chlorosulfonic acid. The reaction mixture was cooled to 25 ° C and quenched in water and ice while adjusting the quenching temperature below 0 ° C. The precipitate product was isolated by filtration and washed with ice-cold water (&lt;5 ° C) below pH 4 to remove lysates. The product cake (365 g) was then sprinkled with sulfanic acid (20 g, sold by Nation Ford Chemical, Fort Mill, SC), Ca-free sodium hydroxide granules (6.4 g) and sodium bicarbonate (21.7 g). It was added to the solution in DI water (200 g) with good mixing (1100 rpm). This pH was adjusted above 8.0 with an additional 37 g of sodium bicarbonate and 21 g of sodium carbonate. This mixture was then subjected to Hockmeyer media mill (Hockmeyer Equipment Corp., Elizabeth City, Grinded at 4000 rpm using a 0.2 mm YTZ medium (sold by Quackenbush Co., Inc., Crystal Lake, Illinois) in (sold by North Carolina). The temperature was raised to 80 ° C. and the mixture was ground for 3 hours. The reaction mixture was removed from the grinder and heated to 83 ° C. Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to about 5% solids to give 1446 g of liquid. Part of the liquid product (220 g), Clariant Colors, Charlotte, Pigment Blue 15: 3 made by NC was used to disperse 40 g and crushed at 7000 rpm for 3 hours. A calcium-free sodium hydroxide solution (1.4 g, 25%) was added dropwise to constantly adjust the pH above 8. The product was removed from the grinder, heated to 86 ° C., and again removed impurities dissolved by ultrafiltration until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to approximately 12% solids and mixed with (0.3%, wt / wt) Proxel GXL (sold by Arch Chemicals, Smyrna, GA). Large particles were removed by centrifugation at 3,200 rpm for 15 minutes and the product (210 g) was filtered through a 0.7 micron GF filter.</p><p><u style="single">Example 12</u><u style="single">Pigment dispersion (Examples relating to addition of cyanuryl group and binding of sodium 4-aminobenzoate)</u> A solution of 4-aminobenzoic acid (40 g), calcium-free sodium hydroxide (14 g) and sodium bicarbonate (52 g) in DI water (600 g) from cyanul chloride (52 g, Lonza Walkersville, Inc., Walkersville, Maryland). (Sold), added to a stirred mixture of ice (880 g) and DI water (200 g). When the reaction mixture turned into a milky white dispersion, the pH rose to 3.1.</p><p> Using the prior art method of oxidizing carbon black with sodium hypochlorite described in US Pat. No. 3,347,632, the primary particle size is 20 nm and the BET surface area is 160 m.²/ g of commercially available gas carbon black (Degussa) was oxidized. Carbon black slurry (908 g at 11%) was slowly added to the milky white dispersion above, maintaining the temperature at 1-6 ° C. After 1 hour, the reaction mixture was heated to 19 ° C and the pH was maintained at 7.3 by adding calcium-free sodium hydroxide (2 g) and sodium bicarbonate (10 g) [step 1]. After adding potassium persulfate (63.6 g, experimental grade, manufactured by Fisher Scientific), the reaction mixture was heated at 57-70 ° C for 20 hours [step 2]. After diluting to 3 L, the pH was raised from 5.3 to 10.3 with calcium-free sodium hydroxide (32.3 g). Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 11% solids and mixed with (0.3%, wt / wt) Proxel GXL (sold by Arch Chemicals, Smyrna, GA). Finally, the product (832 g) was filtered through a 0.7 micron GF filter.</p><p><u style="single">Examples 13 ~ 21</u> Examples 13-21 were prepared for Example 12 by the same method described above. The additional steps in footnote 5 are specific to Example 13.</p><p><u style="single">Table 2. Examples of binding of small molecules to pigments via cyanuric acid adducts</u><tables num="3"><img file="JP6946397B2_D0006.tif" /></tables>⁵ Primary particle size is 13 nm and BET surface area is 320 m²/ g Degussa. After diluting to 3.6 L, the pH increased from 5.7 to 9.0 with 50% sodium hydroxide (20.3 g). The slurry was heat filtered (passed through a 90 ° C, 300 micron bag filter). 30 g of potassium persulfate was added to the carbon slurry which had been cooled to room temperature in advance. Solution of 4-aminobenzoic acid (15 g) in DI water (300 g), calcium-free sodium hydroxide (5 g) with cyanuric chloride (15.3 g, manufactured by Lonza Walkersville, Inc.), and sodium bicarbonate (20 g). Was added to this agitated mixture. Foam is Surfynol CT-121 (Air Products &amp; Chemicals, Inc., Allentown, It was adjusted by dropping (made by PA). The pH was adjusted to 7.7 with 50% sodium hydroxide solution (5.4 g) and mixed with a high shear mixer for an additional 15 minutes. The temperature rose above 50 ° C and was maintained for 20 hours. Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 11% solids and mixed with (0.3%, wt / wt) Proxel GXL (sold by Arch Chemicals, Smyrna, GA). Finally, the product (736 g) was filtered through a 1.0 micron Whatman POLYCAP 36 AS filter capsule.⁶ PR 122 made by CIBA (Newport, DE)⁷ PY74 made by SUN (Parsippany, NJ)⁸ CIBA PB 15: 3⁹ PR 122 made by SUN</p><p><u style="single">Table 2 Continued</u><tables num="4"><img file="JP6946397B2_D0007.tif" /></tables></p><p><u style="single">Example 22</u><u style="single">Pigment dispersion (Examples relating to the addition of a cyanuryl group and the binding of sodium 4-aminobenzoate and an alkyl polymer amine having a molecular weight of about 300)</u> A solution of 4-aminobenzoic acid (7.4 g), calcium-free sodium hydroxide (2.3 g) and sodium bicarbonate (30 g) in DI water (200 g), cyanul chloride (10 g, manufactured by Lonza Walkersville, Inc.), Added to a stirred mixture of ice (130 g) and DI water (40 g). When the reaction mixture turned into a milky white dispersion, the pH rose to 5.5.</p><p> A solution of sulfoneamine B 30 (8.6 g, manufactured by Huntsman Chemicals, Austin, TX) in DI water (60 g) containing concentrated hydrochloric acid (3.75 g) at pH 1.5 was added to cyanul chloride (5 g, manufactured by Lonza Walkersville, Inc.). ), Ice (100 g) and DI water (30 g) added to a stirred mixture. When the reaction mixture turned into a milky white dispersion, the pH rose to 2.1. The pH was gradually increased to 7.1 with 20 g of sodium bicarbonate while keeping the temperature low (5.7 ° C).</p><p> Self-dispersing carbon black dispersion formed by sulfonation and oxidation of carbon black with sulfuric acid and sodium hypochlorite (Sensijet® Black SDP 2000, 500 g at 14%, Sensient Colors Inc, St. Louis, MO) was pre-cooled in the refrigerator. The above-mentioned cooled milky white dispersion was added to the cooled carbon black dispersion while maintaining the temperature at 6 to 13.7 ° C. After 1 hour, the 4-aminobenzoic acid adduct with cyanuric chloride prepared as described above (10.7 ° C) was added with good mixing. The reaction mixture was warmed to 18.8 ° C (pH 7.4) and then 34 g of potassium persulfate was added. Immediately after this step, the reaction mixture was heated to 51-57 ° C for 20 hours [step 1]. After diluting to 2 L, the pH was raised from 7.2 to 10.9 with calcium-free sodium hydroxide (22 g). Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 14.4% solids and mixed with (0.3%, wt / wt) Proxel GXL (sold by Arch Chemicals, Smyrna, GA). Finally, the product (538 g) was filtered through a 0.7 micron GF filter.</p><p><u style="single">Examples 23 to 25</u> Examples 23-25 were prepared in the same manner as described above for Example 22.</p><p><u style="single">Table 3. Binding of linear propoxypolymers via cyanuryl intermediates</u><tables num="5"><img file="JP6946397B2_D0008.tif" /></tables>¹⁰ Made by Sensijet® Black SDP 2000, Sensient Colors Inc, St. Louis, MO¹¹ Made by Sensijet® Black SDP 1000, Sensient Colors Inc, St. Louis, MO</p><p><u style="single">Example 26</u><u style="single">Pigment dispersion (Examples relating to the preparation of cyanuryl tris adducts with sulfanilic acid and their use in surface modification of pigments)</u> A solution of sulfanic acid (114g), calcium-free sodium hydroxide (32g) and sodium bicarbonate (55g) in DI water (310g) at pH = 8.5, cyanul chloride (40.2g, Lonza Walkersville, Inc., Walkersville). , Made by Maryland), ice (570 g) and DI water (480 g) were added to a stirred mixture in three steps, adjusting the temperature to &lt;0 ° C, &lt;3 ° C and &lt;10 ° C, respectively. After the addition, the pH was 7.1 and the reaction mixture was heated to 90 ° C over 4.5 hours to give 1000 g of clear liquid.</p><p> Primary particle size is 16 nm and CTAB surface area is 255 m²/ g carbon black¹²(40 g, sold by Cabot Corporation, Billerica, MA) was slowly added to the above-mentioned reagent (using 10.55 g sulfanilic acid equivalent) and a stirred mixture of 250 g DI water. This mixture is sold in Hockmeyer media mill (sold by Hockmeyer Equipment Corp., Elizabeth City, North Carolina) and 0.2 mm YTZ medium (sold by Quackenbush Co., Inc., Crystal Lake, Illinois). ) Was used to grind. 15 g of a solution of potassium persulfate and sodium bicarbonate dissolved in DI water was added to the grinder, and grinding was continued for a total of 5 hours. Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 11.6% solids and (0.3%, wt / wt) Proxel GXL (Arch Chemicals, Smyrna, Mixed with (sold by GA). Finally, the product was filtered through a 0.7 micron GF filter.</p><p><u style="single">Examples 27-38</u> Examples 27-38 were prepared in the same manner as described above for Example 26.</p><p><u style="single">Table 4. Examples of binding small molecules to pigments via Tris sulfanilic acid-cyanuric acid adducts</u><tables num="6"><img file="JP6946397B2_D0009.tif" /></tables>¹² Cabot (Leominster, MA) Monarch® 880¹³ Cabot (Leominster, MA) Monarch® 700</p><p><u style="single">Example 39</u><u style="single">Pigment dispersion (Example of use in preparation of cyanuric tris adduct with 4-aminobenzoic acid and surface modification of pigment)</u> Solution of 4-aminobenzoic acid (90.1g), calcium-free sodium hydroxide (30g) and sodium bicarbonate (55g) in DI water (300g), pH = 7.2, cyanul chloride (40.2g, Lonza Walkersville, Inc.) ., Walkersville, Maryland), added to a stirred mixture of ice (550 g) and DI water (500 g) in 3 steps, adjusting the temperature to &lt;0 ° C, &lt;3 ° C and &lt;10 ° C, respectively. .. After the addition, the pH was 7.1 and the reaction mixture was heated to 92 ° C over 3 hours to give 901 g of a clear liquid.</p><p> Primary particle size is 20nm and BET surface area is 160m²/ g of carbon black (40 g, Degussa, Burr Ridge, IL) was slowly added to a stirred mixture of the above reagents (using 10.22 g of 4-aminobenzoic acid equivalent) and 250 g of DI water. This mixture is sold in Hockmeyer media mill (sold by Hockmeyer Equipment Corp., Elizabeth City, North Carolina) and 0.2 mm YTZ medium (sold by Quackenbush Co., Inc., Crystal Lake, IL). ) Was used to grind. 8.5 g of a solution of potassium persulfate and sodium bicarbonate dissolved in DI water was added to the grinder, and grind was continued for a total of 6 hours. Impurities dissolved by ultrafiltration were removed until the chloride and sulfate content of the feed sample was less than 50 ppm. The product was then concentrated to 10.3% solids and (0.3%, wt / wt) Proxel GXL (Arch Chemicals, Smyrna, Mixed with (sold by GA). Finally, the product was filtered through a 0.7 micron GF filter.</p><p><u style="single">Examples 40-47</u> Examples 40-47 were prepared in the same manner as described above for Example 39.</p><p><u style="single">Table 5. Examples of binding small molecules to pigments via Tris 4-ABA-cyanuric adducts</u><tables num="7"><img file="JP6946397B2_D0010.tif" /></tables></p><p><u style="single">Example 48</u> The physical characteristics of the modified pigments obtained in the above examples are shown in the table below.</p><p><u style="single">Table 6. Analysis results of pigment dispersion</u><tables num="8"><img file="JP6946397B2_D0011.tif" /></tables><img file="JP6946397B2_D0012.tif" /></p><p><u style="single">Table 6 Continued</u><tables num="9"><img file="JP6946397B2_D0013.tif" /></tables><img file="JP6946397B2_D0014.tif" />¹⁴ The sum of Ca, Mg and Fe was present as an impurity in the raw material and / or was formed during the grinding step.</p><p><u style="single">Example 49</u><u style="single">X-ray photoelectron spectroscopy (XPS) analysis</u> XPS data were collected and analyzed for black samples 1-5 (Table 7), cyan samples (6-11), magenta samples (12-16) and yellow samples (17-21). A dry sample of the purified "Tris" reagent was also analyzed to identify the properties of the groups attached to the pigment surface.</p><p><u style="single">Table 7. XPS pigment samples</u><tables num="10"><img file="JP6946397B2_D0015.tif" /></tables></p><p> XPS data were obtained by the EAG laboratory (Chanhassen, MN) using a probe beam of focused monochromatic AlKα irradiation rays. Photoelectrons were generated by X-rays, which were analyzed and counted for energy to clarify the atomic composition and chemical properties of the sample surface. The photoelectron escape depth limited the analytical depth to an outer diameter of approximately 50 Å. The data presented include low resolution exploration scans. This gives a full spectrum of binding energies from 0 to 1400 eV. The data also includes high resolution spectra obtained from selected elements, which provide information on the chemical state. The spectrum is used to integrate the region below the photoelectron peak and apply an empirical sensitivity factor to obtain the surface composition. XPS data are shown in Figures 1-14.</p><p><u style="single">Table 8. Analytical conditions</u><tables num="11"><img file="JP6946397B2_D0016.tif" /></tables></p><p><u style="single">Table on carbon black samples</u> The table below was standardized to 100% of the detected elements. XPS does not detect H or He. The detection limit is usually between 0.05% and 1.0% for other elements. A dash "-" indicates that no element was detected. Example [1] [Carbon] High S (0.6) for A-79 is the surface SO introduced by chlorosulfonate.₂Shows a bond. The high S content in Examples [20] and [31] where SA is bound is the SO present on the surface due to SA binding.₃This is due to the Na group. Both the unreacted carbon and the 4-ABA-bound carbon obtained in Example [41] had only low levels of S, as expected. The levels of N and Na present in all samples, except unreacted carbon, are a measure of the charge groups present as either aminobenzoic acid groups or benzenesulfonic acid groups as the corresponding sodium salts.</p><p><u style="single">Table 9-1. XPS surface concentration (atomic%) of carbon black sample</u><tables num="12"><img file="JP6946397B2_D0017.tif" /></tables></p><p><u style="single">Table 9-2. Carbon chemical state of carbon in carbon black sample (% of total C)</u><tables num="13"><img file="JP6946397B2_D0018.tif" /></tables></p><p><u style="single">Table 9-3. Nitrogen chemical status of carbon black sample (% of total N)</u><tables num="14"><img file="JP6946397B2_D0019.tif" /></tables></p><p><u style="single">Table 9-4. Oxygen chemical state of carbon black sample (% of total O)</u><tables num="15"><img file="JP6946397B2_D0020.tif" /></tables></p><p><u style="single">Table 9-5. Chemical status of sulfur in carbon black samples (% of total S)</u><tables num="16"><img file="JP6946397B2_D0021.tif" /></tables></p><p> The S present in the untreated carbon as a sulfide was mostly oxidized to sulfate / sulfone in all treated samples, and the surface charged groups increased.</p><p><u style="single">Table for PB 15 samples</u><u style="single">Table 10-1. XPS surface concentration (atomic%) of PB 15 sample</u><tables num="17"><img file="JP6946397B2_D0022.tif" /></tables></p><p><u style="single">Table 10-2. Chemical status of carbon in PB 15 sample (% of total C)</u><tables num="18"><img file="JP6946397B2_D0023.tif" /></tables>^*CO bonds can also contribute to the strength of this bond.</p><p><u style="single">Table 10-3. Chemical status of nitrogen in PB 15 sample (% of total N)</u><tables num="19"><img file="JP6946397B2_D0024.tif" /></tables></p><p><u style="single">Table 10-4. Chemical state of oxygen in PB 15 sample (% of total O)</u><tables num="20"><img file="JP6946397B2_D0025.tif" /></tables></p><p><u style="single">PR 122 Sample table</u><u style="single">Table 11-1. XPS surface concentration (atomic%) of PR 122 sample</u><tables num="21"><img file="JP6946397B2_D0026.tif" /></tables></p><p><u style="single">Table 11-2. Chemical status of carbon in PR 122 sample (% of total C)</u><tables num="22"><img file="JP6946397B2_D0027.tif" /></tables>^*CO bonds can also contribute to the strength of this bond. ^# C₂NH is based on:<chemistry num="4"><img file="JP6946397B2_D0028.tif" /></chemistry>Shows each C atom bonded with.</p><p><u style="single">Table 11-3. Chemical state of oxygen in PR 122 sample (% of total O)</u><tables num="23"><img file="JP6946397B2_D0029.tif" /></tables></p><p><u style="single">PY 74 Sample table</u><u style="single">Table 12-1. XPS surface concentration (atomic%) of PY 74 sample</u><tables num="24"><img file="JP6946397B2_D0030.tif" /></tables></p><p><u style="single">Table 12-2. PY 74 Chemical status of carbon in sample (% of total C)</u><tables num="25"><img file="JP6946397B2_D0031.tif" /></tables>^*CO bonds can also contribute to the strength of this bond.</p><p><u style="single">Table 12-3. Chemical status of nitrogen in PY 74 sample (% of total N)</u><tables num="26"><img file="JP6946397B2_D0032.tif" /></tables></p><p><u style="single">Table 12-4. PY 74 Chemical state of oxygen in the sample (% of total O)</u><tables num="27"><img file="JP6946397B2_D0033.tif" /></tables></p><p> The result of XPS is that by surface modification as described, modified carbon black with an increase in surface nitrogen as NH / NC = N groups distributed almost uniformly at about 0.7 to 2.7 atomic% is obtained. It suggests that it has been done.</p><p> The XPS results suggest that surface modifications as described yield modified carbon black with surface oxygen at 6.8 to 20.9% atomic% (where&gt; 51 to oxygen). 62% are present as C = O, COONa, or SOx groups, and the rest (49-38%) are present as CO groups). In contrast, surface oxygen in untreated carbon black is only about 2.4%, 32% distributed as C = O, COONa or SOx groups and the rest (68%) distributed as CO groups. SOx may be in the oxidized form of S and includes, but is not limited to, sulfones, sulfates or sulfonic acids.</p><p> XPS results suggest that surface modifications as described yield modified carbon black with an increase in surface sodium as COONa / SO3Na at approximately 0.7-2.6% atomic%. ..</p><p> XPS results suggest that surface modifications as described yield modified carbon black in which at least 90% of the S present is oxidized S (SOx).</p><p> The XPS results for the untreated carbon black and the carbon blacks obtained in Examples 1, 20, 31 and 41 are shown in Figures 1-4.</p><p> XPS results show modified Pigment Blue No. 15 with significantly higher surface oxygen content (&gt; 2.5% atomic ratio) compared to the low 1.6% in untreated pigments as described. It suggests that it has been done. XPS results for untreated Pigment Blue No. 15 and Pigment Blue No. 15 obtained in Examples 7, 9, 11, 16 and 42 are shown in Figures 5-7.</p><p> The XPS results show that with surface modifications as described, it has surface oxygen in an atomic ratio of 8.3-9.8% (in this case, only 12% is present as CO in the untreated pigment). 24-32% of all O is present as CO bonds), suggesting that modified Pigment Red No. 122 is obtained. The XPS results for untreated Pigment Red No. 122 and Pigment Red No. 122 obtained in Examples 14, 21, 37 and 45 are shown in Figures 8-11.</p><p> XPS has an atomic ratio of surface oxygen of 21.6 to 29.3% by surface modification as described, 42 to 48% of which is C = O, COONa / CSO.₃It is suggested that the modified Pigment Yellow No. 74, which exists as Na, is obtained. In contrast, with untreated pigments, surface oxygen is only about 20.8%, 41% of which is C = O, COONa / CSO.₃It exists as a Na group. Untreated Pigment Yellow No. 74 and Pigment Yellow No. 74 obtained in Examples 15, 29 and 46 are shown in FIGS. 12-14.</p><p><u style="single">Example 50</u><u style="single">Table 13. Elemental analysis (% of C, H, N and S)</u><tables num="28"><img file="JP6946397B2_D0034.tif" /></tables>¹⁵ Sodium and potassium were calculated at 100% solids from ICP metal analysis of the original dispersion.</p><p><u style="single">Table 13 Continuation Elemental analysis (% of C, H, N and S)</u><tables num="29"><img file="JP6946397B2_D0035.tif" /></tables>¹⁵ Sodium and potassium were calculated at 100% solids from ICP metal analysis of the original dispersant.</p><p> Elemental analysis results show that surface modification as described yields modified Pigment Blue No. 15 with 0.168-0.430 mmol S and 0.070-0.313 mmol active hydrogen per gram of pigment. Suggests.</p><p> Elemental analysis results show that surface modifications as described yield modified Pigment Red No. 122 with 0.062-0.187 mmol S and 0.077-0.394 mmol active hydrogen per gram of pigment. Suggests.</p><p> Elemental analysis results show that surface modifications as described yield modified Pigment Yellow No. 74 with 0.131 to 0.178 mmol S and 0.192 to 0.290 mmol of active hydrogen per gram of pigment. Suggests.</p><p> Elemental analysis results suggest that surface modifications as described yield modified carbon black with 0.103 to 0.702 mmol S and 0.203 to 1.579 mmol of active hydrogen per gram of pigment. There is.</p><p><u style="single">Example 51</u><u style="single">Measurement of particle size and stability</u> Samples containing 8-15% solids were prepared by diluting 1 drop of sample with 15 ml of deionized water and filling in a 1 cm disposable cuvette while preventing air bubbles. Next, the average particle size in the sample was measured using the Malvern Zetasizer Nano series Model ZEN3600.</p><p><u style="single">Table 14. Particle size measurement and stability data of pigment dispersion</u><tables num="30"><img file="JP6946397B2_D0036.tif" /></tables></p><p><u style="single">Examples 52 ~ 55</u><u style="single">Printing performance-Printing test with Epson C88 + printer</u> A total of 3 ink sets were prepared. The first set (SA3) constituting the ink was prepared from the dispersion prepared by the addition of sulfanilic acid (SA), as detailed below. The second and third ink sets (BA3 and BA) were prepared using 4-aminobenzoic acid (4-ABA) -added pigments. Test pages were printed on four different commonly used copy sheets using the Epson C88 + printer model B251A, which is known to use colored ink sets. Printed pages were analyzed by the Center for Integrated Manufacturing, Rochester Institute of Technology, Rochester, NY. The results are shown in Tables 17 and 20-22.</p><p><u style="single">Example 52</u> The following ink bases were prepared according to the method below and used to prepare the final ink with the black dispersion.</p><p><u style="single">Table 15. Ink Base I Formulations</u><tables num="31"><img file="JP6946397B2_D0037.tif" /></tables></p><p> First, 9.6% by weight of water was added to a clean container. The mixer was then placed inside the container to stir the water and mixed while the other ingredients were added. Mixing was performed using a magnetic stirrer. Next, 10% by weight 2-pyrrolidone, 5% by weight 1,5-pentanediol, 4% by weight PEG 600, and 1% by weight 1,2-hexanediol were added to the vessel. These were dissolved. Then 0.1 wt% Surfynol 104E solution and 0.3 wt% Nipacide BIT 20 were added and dissolved.</p><p><u style="single">Example 53</u> The following inks were prepared by the following methods.</p><p><u style="single">Table 16. Inks A to C</u><tables num="32"><img file="JP6946397B2_D0038.tif" /></tables></p><p> The second container was prepared by adding DI water of the calculated weight% based on the pigment dispersion to each container in Table 16. The magnetic stirrer was then placed in a container. Next, the ink base and then the Surfynol surfactant (Air Products &amp; Chemicals, Inc., Allentown, PA) were slowly added to the pigment dispersion in the second container. The dispersions were mixed during this step. After adding all the diluents, the inks were mixed for about 1 hour or until the inks were completely uniform. After mixing, it was filtered using a 1 micron glass filter (sold by Whatman, Kent, England).</p><p> The printing performance characteristics of black ink are identified below.</p><p> Image quality was measured by the ImageXpert Full Motion System. Absorbance was measured with an X-rite 939 Spectrodensitometer. Ozone exposure was measured using a RIT custom ozone chamber and the Sutherland Love test was performed with a Sutherland ink friction tester. The RIT was supplied with the printed pages identified by the ink set and medium. Highlighter A is Sanford Yellow Major Accent® and Highlighter B is Avery Dennison Fluorescent Yellow Hi-Liter®.</p><p><u style="single">Table 17. Printing performance characteristics</u><u style="single">SA additional ink A and 4ABA additional ink B and C</u><tables num="33"><img file="JP6946397B2_D0039.tif" /></tables></p><p><u style="single">Table 17 Continued printing performance characteristics</u><u style="single">SA Addition Ink A and 4 ABA Addition Ink B and C</u><tables num="34"><img file="JP6946397B2_D0040.tif" /></tables> $ I used Epson Photo Paper instead of The ODP 104 for Ink Set 3.</p><p><u style="single">Example 54</u> The following ink bases were prepared by the following methods and used to produce the final ink together with the color dispersion.</p><p><u style="single">Table 18. Ink Base II formulation</u><tables num="35"><img file="JP6946397B2_D0041.tif" /></tables></p><p> First, 12.3% by weight of water was added to a clean container. The mixing device was then placed inside the container to stir the water and mixed while the other ingredients were added. Mixing was performed using a magnetic stirrer. Next, 14% by weight glycerin, 2% by weight PEG 600, 3% by weight butyl carbitol, 2% by weight ethanol, and 1% by weight butanol were added to the container. These were dissolved. Then, 0.1% by weight of triethanolamine was added and dissolved. Finally, 0.3% by weight Cobratec solution and 0.3% by weight Xbinx 19G were added and dissolved.</p><p><u style="single">Example 55</u> The following inks were prepared by the following methods.</p><p><u style="single">Table 19. Ink D ~ L</u><tables num="36"><img file="JP6946397B2_D0042.tif" /></tables></p><p><u style="single">Table 19 Continued Ink D ~ L</u><tables num="37"><img file="JP6946397B2_D0043.tif" /></tables></p><p> The second container was prepared by adding DI water of the calculated weight% based on the pigment dispersion to each container in Table 19. The magnetic stirrer was then placed in a container. The ink base was then slowly added to the pigment dispersion in the second container, then Surfynol surfactant (Air Products &amp; Chemicals, Inc., Allentown, PA). The dispersion was mixed while performing this method. After adding the total diluent, the inks were mixed for about 1 hour or until the inks were completely uniform. After mixing, it was filtered using a 1 micron glass filter (sold by Whatman, Kent, England).</p><p> The printing performance characteristics of color inks have been identified as follows.</p><p><u style="single">Table 20. Ink set prepared with SA-added pigment dispersion 1</u><tables num="38"><img file="JP6946397B2_D0044.tif" /></tables></p><p><u style="single">Table 20 Continued Ink set prepared with SA-added pigment dispersion 1</u><tables num="39"><img file="JP6946397B2_D0045.tif" /></tables></p><p><u style="single">Table 21.4 Ink set prepared with ABA additive pigment dispersion 2</u><tables num="40"><img file="JP6946397B2_D0046.tif" /></tables></p><p><u style="single">Table 21. Continued 4 Ink set prepared with ABA additive pigment dispersion 2</u><tables num="41"><img file="JP6946397B2_D0047.tif" /></tables></p><p><u style="single">Table 22.4 Ink set prepared with ABA additive pigment dispersion 3</u><tables num="42"><img file="JP6946397B2_D0048.tif" /></tables></p><p><u style="single">Table 22. Continued 4 Ink set prepared with ABA additive pigment dispersion 3</u><tables num="43"><img file="JP6946397B2_D0049.tif" /></tables></p><p><u style="single">Example 56</u><u style="single">Performance for wood stain applications</u> The following wood stains were prepared and tested with a 6% dry pigment to which a resin solution consisting of 18% Joncryl 95 (sold by Johnson Polymer, Sturtevant, WI) and the balance of deionized water was added. Water resistance comparison of drawdown on Leneta Form 3 NT-3 using wound rod # 7 (sold by Paul N. Gardner Company, Pompano Beach, FL) is 1 "x 4" elongated I went in one piece. Half of each piece was immersed in deionized water for 1 minute. These pieces were dried at ambient temperature. Color difference (DE *) was recorded with a spectrophotometer. The lower the DE *, the better the water resistance.</p><p><u style="single">Table 23. Wood stain comparison</u><tables num="44"><img file="JP6946397B2_D0050.tif" /></tables></p><p><u style="single">Example 57</u><u style="single">Covering performance</u> Prepare the following coating (Masstone) and test with 6% dry pigment, adding a resin solution consisting of 25% acrylic vehicle (sold by Valspar, Wheeling, IL) and the rest of the deionized water. bottom. The drawdown was prepared on top of Leneta 2A using a 6.0 mil winding rod. Chemical resistance was measured separately by spotting 10 drops of 10% hydrochloric acid and 10 drops of 10% sodium hydroxide solution on the Massstone drawdown. The degree of chemical resistance is measured by taking the DE * values of the spot region and the control region.</p><p><u style="single">Table 24. Coating resistance to strong acid (10% hydrochloric acid)</u><tables num="45"><img file="JP6946397B2_D0051.tif" /></tables></p><p><u style="single">Table 25. Coating resistance against strong bases (10% sodium hydroxide)</u><tables num="46"><img file="JP6946397B2_D0052.tif" /></tables></p><p><u style="single">Example 58</u><u style="single">Performance for color filter applications</u> The following color filter formulations are prepared and adjusted to a total of 75% with deionized water, followed by 30% Valspar acrylic vehicle, 30% Joncryl 1972 (sold by Johnson Polymer, Sturtevant, WI). And mixed with a vehicle (25%) consisting of 40% 1-methoxy-2-propanol (propylene glycol monomethyl ether) and added, tested with 6% dry pigment. The transmittance value of the color filter coating agent on the transparent olefin polymer substrate using the wound rod # 7 (Paul N. Gardner Company, Pompano Beach, FL) was measured after drying at the ambient temperature.</p><p><u style="single">Table 26. Color filter coating transmittance values</u><tables num="47"><img file="JP6946397B2_D0053.tif" /></tables></p><p><u style="single">Example 59</u><u style="single">Performance for printing applications</u> Prepare the following printing paste and prepare Delta Ceramcoat Textile Medium¹⁶ Tested with 6% dry pigment, adding (33%), Valspar acrylic vehicle (5%) and the rest of the deionized water. The drawdown of the printing paste on the white cotton fabric was prepared using a 6.0 mil winding metering rod. After drying at ambient temperature, the prints were heated and fixed in a heater at 140 ° C. for 10 minutes. The fabric was cut into pieces of 1 "x 4" and half of each piece (1 "x 2") was immersed in boiling deionized water for 5 minutes. The exposed piece was then washed with cold tap water for 1 minute and dried at ambient temperature. Wash fastness and water resistance were assessed by measuring the total color difference (DE *) between the control and treated fibers.</p><p><u style="single">Table 27. Evaluation of washing fastness and water resistance</u><tables num="48"><img file="JP6946397B2_D0054.tif" /></tables>¹⁶ This amount was adjusted to 23% DCTM and 2% VAV for the two PB 15 pigment dispersions.<u style="single"> Some embodiments are shown below.</u><u style="single">Item 1</u><u style="single"> The step of reacting cyanuric chloride with about 3 equivalents of the second compound or a mixture of the second compounds to replace the total reactive chlorine to form substituted triazine; and</u><u style="single"> The step of reacting the substituted triazine with the surface of the pigment to form a surface-modified pigment.</u><u style="single">A method for modifying a pigment, including.</u><u style="single">Item 2</u><u style="single"> Item 2. The method according to Item 1, further comprising reacting the substituted triazine with the surface of the pigment using a radical initiator to form a surface-modified pigment.</u><u style="single">Item 3</u><u style="single"> Item 2. The method according to Item 2, wherein the radical initiator contains a persulfate.</u><u style="single">Item 4</u><u style="single"> Item 2. The method according to Item 1, wherein the mixture of the second compound may contain one, two or three different second compounds.</u><u style="single">Item 5</u><u style="single"> Item 2. The method according to Item 1, wherein the method is carried out at a temperature of about 25 ° C to about 90 ° C.</u><u style="single">Item 6</u><u style="single"> The second compound or a mixture of the second compounds is aminobenzoic acid, aminobenzenesulfonic acid, aminophenol, aminosulfonic acid, polyethoxylated amino acid, sodium sulfanilic acid, sulfanilic acid, sodium p-aminobenzoate, p-amino. Phenol, ethyl 4-aminobenzoate, tetramethylammonium 4-aminobenzoate, sodium 4-aminophenolate, taurine, oleic acid (amino), sodium aminooleate, organic polymer substrate, linear polyethoxypolymer amine Item 2. The method according to Item 1, which comprises at least one of a linear propoxypolymer amine, a diaminoaromatic compound, polyethyleneimine, polyguanidine, a quaternary ammonium compound, or a combination thereof.</u><u style="single">Item 7</u><u style="single"> Pigments are Carbon Black, Pigment Red 122, Pigment Violet 19, Pigment Violet 23, Pigment Red 202, Pigment Red 188, Pigment Yellow 155, Pigment Yellow 97, Pigment Green 7, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Item 2. The method according to Item 1, which comprises at least one of Yellow 74 and a combination thereof.</u><u style="single">Item 8</u><u style="single"> Item 2. The method of Item 1, further comprising milling the pigment to less than about 100 nm before, during or after reacting the pigment with the substituted triazine.</u><u style="single">Item 9</u><u style="single"> Item 2. The method of Item 1, wherein the surface modified pigment comprises from about 0.01 to about 1.0 mmol S and about 0.01 to about 2.0 mmol of active hydrogen per gram of pigment.</u><u style="single">Item 10</u><u style="single"> X- [Y]</u>_{<u style="single">n</u>}<u style="single">A reactive compound having a reactive group is reacted with the second compound NS-ZM to substitute a reactive intermediate [Y].</u>_{<u style="single">a</u>}<u style="single">-X- (NS-ZM)</u>_{<u style="single">b</u>}<u style="single">Steps to form; and</u><u style="single"> Pigment Substitution Reactive Intermediate [Y]</u>_{<u style="single">a</u>}<u style="single">-X- (NS-ZM)</u>_{<u style="single">b</u>}<u style="single">To form a surface-modified pigment by binding a substitution-reactive intermediate to the surface of the pigment.</u><u style="single">Pigment modification methods, including</u><u style="single"> [During the ceremony,</u><u style="single"> X is a sulfonyl, phosphoryl or 1,3,5-triazinyl group;</u><u style="single"> Y is a halogen leaving group;</u><u style="single"> N is a nucleophile;</u><u style="single"> S is an organic group;</u><u style="single"> ZM is an ionizable end group;</u><u style="single"> n is an integer from 1 to 3;</u><u style="single"> b is an integer from 1 to 3;</u><u style="single"> a = nb;</u><u style="single"> Where n is equal to or greater than b;</u><u style="single"> Also, if b is 2 or 3, the NS-ZMs may be the same or different, respectively].</u><u style="single">Item 11</u><u style="single"> Item 2. The method according to Item 10, wherein b is 2 or 3 and NS-ZM is different from each other.</u><u style="single">Item 12</u><u style="single"> Item 10. The method of item 10, wherein the pigment is in powder form or wet cake form and is ground with a milling aid prior to reaction with the substitution intermediate.</u><u style="single">Item 13</u><u style="single"> Item 10. The method of item 10, wherein Y comprises at least one of fluorine, chlorine, bromine or iodine.</u><u style="single">Item 14</u><u style="single"> Item 10. The method of Item 10, wherein N comprises at least one amine, imine, pyridine or thiol group.</u><u style="single">Item 15</u><u style="single"> Item 10. The method of Item 10, wherein S comprises a substituted or unsubstituted alkyl, aryl, and at least one polymer chain having a molecular weight range of about 300 to about 8000.</u><u style="single">Item 16</u><u style="single"> Item 10. The method of Item 10, wherein Z comprises at least one of a carboxyl, sulfonyl, phenol or phosphoryl group and M comprises at least one of a proton or cation in salt form.</u><u style="single">Item 17</u><u style="single"> Item 10. The method of Item 10, wherein the second compound NS-ZM comprises at least one of a polymer, amine, amino acid, alcohol, thiol and a combination thereof.</u><u style="single">Item 18</u><u style="single"> The second compound, NS-ZM, is aminobenzoic acid, aminobenzenesulfonic acid, aminophenol, aminosulfonic acid, polyethoxylated amino acid, sodium sulfanylate, sulfanic acid, sodium p-aminobenzoate, p-aminophenol, 4-amino. Contains at least one of ethyl benzoate, taurine, oleic acid (amino), tetramethylammonium 4-aminobenzoate, sodium 4-aminophenolate, sodium aminooleate, organic polymeric substrates, and combinations thereof. The method described in 17.</u><u style="single">Item 19</u><u style="single"> The organic polymer substrate is a linear alkyl and branched ethoxy and propoxy chain polymer having a molecular weight of about 300 to about 3000, a linear polyethoxy polymer amine, a linear propoxy polymer amine, a styrene acrylic acid copolymer, Item 18. The method of Item 18, comprising polyethyleneimine, and at least one of a combination thereof.</u><u style="single">Item 20</u><u style="single"> Item 10. The method of Item 10, wherein Z comprises at least one of ammonium, trimethylammonium or tributylammonium and M comprises at least one of a halide or loaded electroion.</u><u style="single">Item 21</u><u style="single"> Item 20. The method of Item 20, wherein the second compound NS-ZM comprises at least one of a diamino aromatic compound, polyethyleneimine, polyguanidine, a quaternary ammonium compound or a combination thereof.</u><u style="single">Item 22</u><u style="single"> Pigments are Carbon Black, Pigment Red 122, Pigment Violet 19, Pigment Violet 23, Pigment Red 202, Pigment Red 188, Pigment Yellow 155, Pigment Yellow 97, Pigment Green 7, Pigment Blue 15: 3, Pigment Blue 15: 4 and Pigment Item 10. The method of Item 10, comprising Yellow 74, and at least one combination thereof.</u><u style="single">Item 23</u><u style="single"> Item 10. The method of Item 10, further comprising the step of grinding the pigment to less than about 100 nm before, during or after reacting the pigment with the substitutionally reactive intermediate.</u><u style="single">Item 24</u><u style="single"> Substitution Reactive Intermediate [Y]</u>_{<u style="single">a</u>}<u style="single">-X- (NS-ZM)</u>_{<u style="single">b</u>}<u style="single">Is accompanied by charge-balanced counterions, which are counterions such as alkali metals, alkaline earth metals, and NR.</u>_{<u style="single">1</u>}<u style="single">R</u>_{<u style="single">2</u>}<u style="single">R</u>_{<u style="single">3</u>}<u style="single">H</u>^{<u style="single">+</u>}<u style="single">[In the formula, R</u>_{<u style="single">1</u>}<u style="single">, R</u>_{<u style="single">2</u>}<u style="single">And R</u>_{<u style="single">3</u>}<u style="single">Is independently H or substituted or unsubstituted C</u>_{<u style="single">1</u>}<u style="single">-C</u>_{<u style="single">5</u>}<u style="single">Item 10. The method of Item 10, further comprising the step of at least partially substituting with at least one of [is an alkyl group] and a combination thereof.</u><u style="single">Item 25</u><u style="single"> Counterions are K +, Li +, NH</u>_{<u style="single">4</u>}<u style="single">The method according to Item 24, wherein the method is at least partially substituted with at least one of +, monoethanolammonium, tetraethylammonium, triethanolammonium, tetramethylammonium, tetrabutylammonium and combinations thereof.</u><u style="single">Item 26</u><u style="single"> Item 10. The method of Item 10, wherein the surface modified pigment comprises from about 0.01 to about 1.0 mmol S and from about 0.01 to about 2.0 mmol active hydrogen per gram of pigment.</u><u style="single">Item 27</u><u style="single">Item 10. The method of Item 10, wherein the surface modifying pigment comprises from about 0.06 to about 0.7 mmol S and from about 0.07 to about 1.6 mmol active hydrogen per gram of pigment.</u><u style="single">Item 28</u><u style="single"> Item 10. The method of Item 10, wherein the surface modifying pigment comprises Pigment Blue 15, which comprises from about 0.168 to about 0.430 mmol S and about 0.07 to about 0.313 mmol of active hydrogen per gram of pigment.</u><u style="single">Item 29</u><u style="single"> Item 10. The method of Item 10, wherein the surface-modified pigment comprises Pigment Red 122, which comprises from about 0.062 to about 0.187 mmol S and about 0.077 to about 0.394 mmol of active hydrogen per gram of pigment.</u><u style="single">Item 30</u><u style="single"> Item 10. The method of Item 10, wherein the surface modifying pigment comprises Pigment Yellow 74, which comprises from about 0.131 to about 0.178 mmol S and about 0.192 to about 0.290 mmol of active hydrogen per gram of pigment.</u><u style="single">Item 31</u><u style="single"> Item 10. The method of Item 10, wherein the surface modified pigment comprises carbon black containing about 0.103 to about 0.702 mmol S and about 0.203 to about 1.579 mmol of active hydrogen per gram of pigment.</u><u style="single">Item 32</u><u style="single"> Item 10. The method of Item 10, wherein the surface modifying pigment comprises about 100 to about 6500 ppm of sodium and about 30 to about 1200 ppm of potassium.</u><u style="single">Item 33</u><u style="single"> Item 2. The method according to Item 10, wherein the surface modifying pigment contains an amount of sulfur in an amount of about 50 ppm to about 2600 ppm.</u><u style="single">Item 34</u><u style="single"> The surface modifier is</u><u style="single"> NH / NC = N groups of about 0.7-2.7 atomic% distributed almost uniformly;</u><u style="single"> Oxygen with an atomic ratio of about 6.8 to 20.9% (where at least about 51 to 62% of oxygen is present as a C = O, COONa or SOx group, the rest is present as a CO group, SOx is an oxidized form of S be);</u><u style="single"> Approximately 0.7-2.6 atomic% COONa / SO</u>_{<u style="single">3</u>}<u style="single">Na</u><u style="single">Is a surface-modified carbon black containing carbon black to which is bonded, and at least 90% of S present on the surface of the surface-modified carbon black is oxidized S (SO).</u>_{<u style="single">x</u>}<u style="single">), Item 10.</u><u style="single">Item 35</u><u style="single"> 34. The method of item 34, wherein SOx comprises at least one of sulfone, sulfate or sulfonic acid.</u><u style="single">Item 36</u><u style="single"> Item 10. The method of Item 10, wherein the surface-modified pigment is a surface-modified Pigment Blue 15 having a surface oxygen content of at least about 2.5 atomic%.</u><u style="single">Item 37</u><u style="single"> The surface modified pigment is surface modified pigment red 122 having a surface oxygen content of about 8.3 to about 9.8 atomic% and about 24% to about 32% of all O present as CO bonds. The method described in 10.</u><u style="single">Item 38</u><u style="single"> Surface modified pigments have a surface oxygen content of about 21.6 to about 29.3 atomic%, about 42% to about 48% with C = O, COONa / CSO</u>_{<u style="single">3</u>}<u style="single">Item 5. The method of Item 10, wherein the surface-modified Pigment Yellow 74 is present as Na.</u><u style="single">Item 39</u><u style="single"> Item 10. The method of Item 10, further comprising adding a surface modifying pigment to the aqueous pigment dispersion.</u><u style="single">Item 40</u><u style="single"> Item 10. The method of item 10, further comprising adding a surface modifier to at least one of wood stains, coatings, inkjet inks, color filters, or textile printing inks, or a combination thereof.</u><u style="single">Item 41</u><u style="single"> X- [Y]</u>_{<u style="single">n</u>}<u style="single">The reactive group is cyanul chloride, and the second compound NS-ZM is 4-aminobenzoic acid, sulfanilic acid, 4-aminophenol, taurine, oleic acid (amino), linear polyethoxypolymer amine, propoxypolymer amine. , Or at least one of a combination thereof, according to item 10.</u><u style="single">Item 42</u><u style="single"> X- [Y]</u>_{<u style="single">n</u>}<u style="single">Item 10. The method of Item 11, wherein the reactive group is cyanuric chloride and the second compound is 4-aminobenzoic acid and a polymeric amine.</u><u style="single">Item 43</u><u style="single"> Item 10. The method according to Item 10, wherein the surface modifying pigment is an autocovariant pigment.</u><u style="single">Item 44</u><u style="single"> Steps to attach reactive groups to the pigment surface; and</u><u style="single"> The step of substituting the reactive group with an organic substrate having an ionizable end group is then made.</u><u style="single">Including</u><u style="single"> In this case, the pigments are Pigment Red 122, Pigment Violet 19, Pigment Violet 23, Pigment Red 202, Pigment Red 188, Pigment Yellow 155, Pigment Yellow 97, Pigment Green 7, Pigment Blue 15: 3, Pigment Blue 15: 4 and Pigment. A pigment modification method selected from the group consisting of Yellow 74.</u><u style="single">Item 45</u><u style="single"> Steps to bond reactive group XY to pigment surface; and</u><u style="single"> A pigment modification method comprising the step of substituting Y with the organic substrate NS-ZM to form a surface-modified pigment to which XNS-ZM is bound.</u><u style="single"> [During the ceremony,</u><u style="single"> X is a sulfonyl, phosphoryl or 1,3,5-triazine group;</u><u style="single"> Y is fluorine, chlorine, bromine or iodine;</u><u style="single"> N is an amine, imine, pyridine or thiol group;</u><u style="single"> S is a substituted or unsubstituted alkyl, aryl, or polymer chain with a molecular weight range of about 300 to about 8000;</u><u style="single"> Z is a carboxyl, sulfonyl, phenol, phosphoryl, ammonium, trimethylammonium or tributylammonium group;</u><u style="single"> M is a halide, charged ion, a proton in the salt form or a cation in the salt form].</u><u style="single">Item 46</u><u style="single"> Item 45. The method of Item 45, wherein X is a sulfonyl group.</u><u style="single">Item 47</u><u style="single"> Item 46. The method of Item 46, wherein the reactive group XY is attached to the pigment surface by chlorosulfonation with a chlorosulfonate agent comprising chlorosulfonic acid, thionyl chloride or a combination thereof.</u><u style="single">Item 48</u><u style="single"> 47. The method of item 47, wherein the ratio of pigment to chlorosulfonate agent is at least about 4: 1 (wt / wt).</u><u style="single">Item 49</u><u style="single"> 47. The method of item 47, wherein the ratio of the pigment to the chlorosulfonate agent is from about 1:20 to about 1: 1 (wt / wt).</u><u style="single">Item 50</u><u style="single"> 47. The method of item 47, wherein the chlorosulfonater is a mixture of chlorosulfonic acid and thionyl chloride in a ratio of about 3: 1 to about 6: 1 (wt / wt).</u><u style="single">Item 51</u><u style="single"> 47. The method of item 47, wherein the chlorosulfonate is carried out at a temperature of about 25 ° C to about 160 ° C.</u><u style="single">Item 52</u><u style="single"> Steps to modify most of the pigment surface to form a liquid gel; and</u><u style="single"> The liquid gel is then ground with an excess of untreated pigment and water to form a stable aqueous pigment dispersion.</u><u style="single">46.</u><u style="single">Item 53</u><u style="single"> Item 52. The method of item 52, wherein most modification of the pigment surface comprises the step of chlorosulfonating the pigment at a temperature of at least about 90 ° C. for at least about 1 hour to form the pigment sulfonyl chloride.</u></p>