JP2010209258A - Color material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color material composition which is excellent in dispersibility of color material particles and further excellent in adhesion with various base materials. <P>SOLUTION: The color material composition contains a polymer having a constitution unit represented by formula (1) and a color material. In the formula (1), R represents 2-4C alkylene group or -R<SP>2</SP>-O-R<SP>3</SP>- (R<SP>2</SP>and R<SP>3</SP>may be the same or different and each represents methylene group, ethylene group or propylene group); and R<SP>1</SP>represents hydrogen atom or methyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a color material composition.

  Many colorant particles such as pigments have a weak affinity for water, organic solvents, and the like compared to the cohesive force between the particles, and therefore, the colorant composition containing such colorant particles is likely to aggregate between the colorant particles. Therefore, in order to use the color material composition for various purposes and to effectively exhibit the functions of the color material, a technique for dispersing the color material particles by incorporating a dispersant into the color material composition has been developed. Yes.

  Here, a polymer having an N-vinyl lactam structure such as polyvinyl pyrrolidone or polyvinyl caprolactam is widely used as a dispersant because it is relatively excellent in dispersibility of the coloring material. For example, Patent Document 1 discloses a fine particle dispersion composition in which fine particles are dispersed in a polar solvent using a graft polymer obtained by graft polymerization of acrylic acid or acrylate on polyvinylpyrrolidone as a dispersant. Has been. Patent Document 2 discloses a water-soluble resin dissolved in an ink in an aqueous recording ink containing at least water, a pigment and / or a carbon black coloring material, and a water-soluble resin such as polyvinylpyrrolidone. A water-based recording ink is disclosed, characterized in that is 2 to 10 wt%.

  By the way, in such a color material composition, in addition to the good dispersion of the color material particles, the coating film formed using the color material particles is excellent for various substrates such as metal plates and papers. Adhesion is also required. However, a colorant composition using a conventional polymer having an N-vinyllactam structure as a dispersant may have insufficient adhesion to a substrate.

JP 2003-49038 A JP-A-5-263029

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a color material composition that is excellent in dispersibility of color material particles and also excellent in adhesion to various substrates. There is.

  As a result of intensive studies, the inventors of the present invention have been conventionally used as a dispersant by using a polymer containing a structural unit in which a lactam ring is arranged at some distance from the polymer main chain as a colorant dispersant. Compared with polymers in which the lactam ring is directly bonded to the polymer main chain, such as polyvinylpyrrolidone, the colorant has improved adhesion to various substrates while maintaining equivalent colorant dispersibility The inventors found that a composition can be obtained and completed the present invention.

  That is, the color material composition of the present invention is characterized by containing a polymer having a structural unit represented by the following formula (1) and a color material.

[Wherein, R is an alkylene group having 2 to 4 carbon atoms, or -R ² —O—R ³ — (R ² and R ³ may be the same or different, and are a methylene group, an ethylene group, or a propylene group. R ¹ represents a hydrogen atom or a methyl group. ]

  In a preferred embodiment, the polymer further has a structural unit represented by the following formula (2).

[Wherein n represents an integer of 2 to 5. ]

  In a preferred embodiment, the colorant is a pigment.

  The present invention also includes a colorant-dispersing polymer having a structural unit represented by the above formula (1). In a preferred embodiment, the polymer further has a structural unit represented by the above formula (2).

  According to the present invention, a color material composition that exhibits a color material dispersibility equivalent to that of a color material composition using polyvinyl pyrrolidone as a dispersant and is excellent in adhesion to various substrates is provided. I was able to.

  The color material composition of the present invention contains a polymer having a structural unit represented by the above formula (1) and a color material.

  Since the color material composition of the present invention contains a polymer having a pyrrolidone ring in the polymer side chain, it can exhibit a color material dispersibility equivalent to that of polyvinyl pyrrolidone. In addition, since such a pyrrolidone ring is arranged at a position somewhat away from the polymer main chain via an ester bond and R, the coating film formed using this polymer has a rigid structure. It becomes easier to follow the base material as compared with a coating film formed using. For this reason, the color material composition of this invention can exhibit the outstanding base-material adhesiveness, hold | maintaining the outstanding color material dispersibility which polyvinylpyrrolidone had. Moreover, since the color material composition of this invention exhibits the outstanding base-material adhesiveness, the color material becomes difficult to be missing in the coating film formed using this.

  Hereinafter, the color material composition of the present invention will be described in detail.

(Polymer)
<Structural Unit Represented by Formula (1)>
The polymer used in the present invention has a structural unit represented by the above formula (1). In the formula (1), R is an alkylene group having 2 to 4 carbon atoms (ethylene group, propylene group, butylene group). ), Or —R ² —O—R ³ — (R ² and R ³ may be the same or different and each represents a methylene group, an ethylene group, or a propylene group), and may be linear or branched. It may be in the shape. This is because if the pyrrolidone ring, which is an action point for performance expression, is too far from the polymer main chain, it is presumed that the pyrrolidone ring is not efficiently used for performance expression. In particular, R is preferably an ethylene group. In the polymer, the structural unit represented by the formula (1) may be composed of the same species or a plurality of species.

<Other structural units>
The polymer used in the present invention may be composed only of the structural unit represented by the above formula (1), but includes other structural units having an N-vinyl lactam structure represented by the above formula (2). It may be constituted by. Thereby, the manufacturing cost of the polymer used by this invention can be restrained low. The structural unit represented by the formula (2) includes the following formulas (2a) to (2d).

  In particular, from the viewpoint of colorant dispersibility and production cost of the polymer of the present invention, the structural unit represented by the formula (2b) (in formula (2), n = 3), that is, derived from N-vinylpyrrolidone. It is preferable that the structural unit is contained. In the polymer, formulas (2a) to (2d) may be contained alone or in combination of two or more thereof.

  In the polymer used in the present invention, the content ratio of the structural unit of the above formula (1) and the structural unit of the above formula (2) impairs the substrate followability (adhesiveness) of the color material composition of the present invention. In general, the formula (1) / formula (2) (molar ratio) is preferably 100/0 to 5/95, more preferably 90/10 to 10/90. Is more preferable, and it is still more preferable that it is 80/20-20/80. When it is desired to give priority to colorant dispersibility, it is preferably 70/30 to 5/95, more preferably 60/40 to 5/95, and 50/50 to 5/95. Most preferred. When it is desired to give priority to the substrate adhesion, 100/0 to 30/70 is preferable, 100/0 to 40/60 is more preferable, and 100/0 to 50/50 is preferable. Most preferred.

  The polymer used in the present invention is a structural unit other than the structural units represented by the above formulas (1) and (2) as long as the colorant dispersibility is not impaired and the adhesion to the substrate is not impaired. It may be comprised including. Examples of such other structural units include (meth) acrylic acid, maleic acid, acrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, and salts thereof, (meth) acrylic acid ester, maleic acid One selected from the group consisting of ester, (meth) acrylamide, N-vinylacetamide, N-vinylformamide, N-vinylimidazole, vinylpyridine, alkyl vinyl ether, acrylonitrile, styrene, vinyl acetate, allyl alcohol, olefins, or the like Examples include structural units derived from two or more monomers. Note that (meth) acrylic acid esters include alkyl esters having 1 to 20 carbon atoms, dimethylaminomethylalkyl esters, quaternary salts thereof, hydroxyalkyl esters, and the like. The content of these other structural units is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and more preferably 0 to 10 mol% with respect to the entire structural units constituting the polymer. More preferably. It is presumed that when the other structural units are contained at such a content, the resulting polymer can more strongly exhibit the performance derived from the structural units represented by the above formulas (1) and (2).

<Molecular weight>
The weight average molecular weight of the polymer used in the present invention is preferably 1000 to 3000000, more preferably 2000 to 2000000 in terms of polystyrene as a value when measured by gel permeation chromatography (GPC). Preferably, it is 5,000 to 1,000,000. Within this range, a color material composition in which the color material is stably dispersed can be obtained. In addition, the measuring method of a polymer molecular weight is mentioned later.

<Polymer production method>
The polymer used in the present invention may be produced by any method. For example, an N- (meth) acryloyl group-containing pyrrolidone monomer represented by the following formula (3) is polymerized, or further if necessary. Thus, it can be produced by copolymerizing with an N-vinyl lactam monomer represented by the following formulas (4a) to (4d) or a monomer derived from the other structural unit described above.

[Wherein, R and R ¹ are the same as those in the above formula (1). ]

  In detail, the polymer of the N- (meth) acryloyl group-containing pyrrolidone monomer represented by the formula (3) is an N- (meth) acryloyl group-containing pyrrolidone monomer represented by the formula (3). After introducing an inert gas such as nitrogen into the monomer solution obtained by dissolving in an aqueous solvent to remove dissolved oxygen, the monomer solution is heated to a predetermined temperature in advance, and then the azo compound and / or excess It can manufacture by adding and superposing | polymerizing an oxide as a polymerization initiator.

  The aqueous solvent used in this production method is preferably water or a mixed solvent of water and a lower alcohol. Examples of the lower alcohol include methanol, ethanol, isopropanol, diethylene glycol and the like.

  The reaction temperature in the polymerization reaction may be appropriately set according to the conditions such as reaction raw materials, but is preferably 40 ° C to 100 ° C, more preferably 50 ° C to 95 ° C, and further preferably 60 ° C to 90 ° C.

  Examples of the azo compound that can be used as a polymerization initiator include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyric acid) dimethyl, 4,4′-azobis (4-cyano) Valeric acid), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, 2, 2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 1,1'-azo Such as scan (cyclohexane-1-carbonitrile) and the like. These azo compounds may be used alone or in combination of two or more. Among these azo compounds, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (isobutyric acid) dimethyl, 2,2′-azobis (2-methylpropionamidine) dihydrochloride 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate is particularly preferred.

  Examples of the peroxide that can be used as the polymerization initiator include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di () in addition to hydrogen peroxide, persulfate, and the like. t-butylperoxy) hexane, 1,1′-di-t-butylperoxy-3,3,5-trimethylenecyclohexane, 1,3-di- (t-butylperoxy) -diisopropylbenzene, di-t-butyl Examples thereof include peroxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-amyl peroxy-2-ethyl hexanoate, t-amyl hydroperoxide and the like. These peroxides may be used alone or in combination of two or more. Of these peroxides, hydrogen peroxide, ammonium persulfate, t-butyl hydroperoxide, t-amyl peroxy-2-ethylhexanoate are preferred, and hydrogen peroxide, ammonium persulfate, t-amyl peroxy-2 are preferred. -Ethylhexanoate is particularly preferred.

  Moreover, in the case of a polymerization reaction, you may start superposition | polymerization with the redox type polymerization initiator which uses together said peroxide and a reducing agent.

Examples of the reducing agent include low valences such as iron (II), tin (II), titanium (III), chromium (II), V (II), Cu (II), and the like represented by mole salts. Metal salts in the state; amine compounds such as monoethanolamine, diethanolamine, triethanolamine, hydroxylamine, hydroxylamine hydrochloride, hydrazine and their salts; sodium dithionite, sodium formaldehyde sulfoxylate, hydroxymethanesulfinic acid In addition to sodium dihydrate, etc., organic compounds and salts thereof including groups such as —SH, —SO ₂ H, —NHNH ₂ , —COCH (OH) —; sodium sulfite, sodium bisulfite, metabisulfite, etc. Alkali metal sulfites, hypophosphorous acid, sodium hypophosphite, hydro Lower oxides such as sodium sulfate and sodium hyponitrite and salts thereof; invert sugars such as D-fructose and D-glucose; thiourea compounds such as thiourea and thiourea dioxide; L-ascorbic acid (salt), L-ascorbic acid ester Erythorbic acid (salt), erythorbic acid ester, and the like.

  Specific examples of the combination of the peroxide and the reducing agent include, for example, a combination of benzoyl peroxide and an amine, and a combination of cumene hydroperoxide and a metal compound such as iron (II) or Cu (II). In particular, a combination of a water-soluble peroxide and a reducing agent is preferable. For example, a combination of hydrogen peroxide and L-ascorbic acid, a combination of hydrogen peroxide and erythorbic acid, and a combination of hydrogen peroxide and molle salt. A combination of sodium persulfate and sodium bisulfite is particularly preferred. The most preferred combination is a combination of hydrogen peroxide and L-ascorbic acid.

  The concentration of the polymerization initiator in the polymerization reaction may be appropriately adjusted according to the amount of the monomer component used, and is not particularly limited. For example, it is preferably 0 with respect to 100 parts by mass of the monomer. 0.001 to 4 parts by mass, more preferably 0.01 to 3 parts by mass. In carrying out the polymerization reaction, in addition to the polymerization initiator, any chain transfer agent, pH adjusting agent, buffering agent, and the like can be used as necessary.

  A copolymer of the N- (meth) acryloyl group-containing pyrrolidone monomer represented by the formula (3) and the N-vinyl lactam monomer represented by the formulas (4a) to (4d) has the formula A first solution in which the N-vinyllactam monomer represented by (4a) to (4d) is dissolved in an aqueous solvent, an inert gas such as nitrogen is introduced to remove dissolved oxygen, and further heated to a predetermined temperature. N- (meth) acryloyl group-containing pyrrolidone monomer represented by formula (3), N-vinyl lactam monomers represented by formulas (4a) to (4d), and a pH adjuster. A second solution dissolved in an aqueous solvent and a third solution in which a polymerization initiator is dissolved in an aqueous solvent are added dropwise to perform a polymerization reaction, and thereafter ripened for a predetermined time.

As the pH adjuster used in the present production method, known compounds can be used, for example, amine compounds such as primary amine, secondary amine, tertiary amine; NaOH, KOH, Ca (OH) _{2 and the} like. Examples include alkali (earth) metal hydroxides; carbonates such as Na ₂ CO ₃ and guanidine carbonate. These pH adjusters may be used alone or in combination of two or more.

  The aqueous solvent and polymerization initiator used in this production method, the reaction temperature in the polymerization reaction, and the concentration of the polymerization initiator may be the same as described above.

  The polymer used in the present invention is a polymer of a (meth) acrylic acid alkyl ester monomer or a (meth) acrylic acid alkyl ester monomer and the above formulas (4a) to (4d) separately from the above method. The 2-hydroxy group-containing pyrrolidone represented by the following formula (5) is reacted with the copolymer with the N-vinyllactam monomer represented by the formula: It can also be produced by introducing a ring.

[Wherein, R is the same as the above formula (1). ]

  In order to reliably introduce the pyrrolidone ring into the polymer, it is preferable to polymerize the N- (meth) acryloyl group-containing pyrrolidone monomer represented by the formula (3).

<Method for Producing N-Acryloyl Group-Containing Pyrrolidone Monomer Represented by Formula (3)>
The monomer represented by the formula (3) used in the production of the polymer may be produced by any method, for example, a transesterification reaction of (meth) acrylic acid ester or (meth) acrylic acid. It can be produced by esterification of (meth) acrylic acid halide. Specifically, as a method of producing by transesterification of (meth) acrylic acid ester, (meth) acrylic acid alkyl ester, 2-hydroxy group-containing pyrrolidone represented by the above formula (5), catalyst, The reaction mixture with the polymerization inhibitor is heated to 80 ° C. to 140 ° C. with stirring and reacted for 5 to 15 hours. Meanwhile, by-produced alkyl alcohol is azeotroped with the (meth) acrylic acid alkyl ester. There is a method of producing by removing the system outside and supplying further the (meth) acrylic acid alkyl ester corresponding to the outside system removed to the reaction system.

  Examples of the catalyst used in the above production method include dibutyltin oxide, sulfuric acid, p-toluenesulfonic acid, potassium phosphate, sodium methoxide, lithium hydroxide, ion exchange resin and the like. Of these, dibutyltin oxide is preferred. Examples of the polymerization inhibitor include phenothiazine, hydroquinone monomethyl ether, N, N-di-sec-butyl-p-phenylenediamine, and TEMPO. Of these, phenothiazine, hydroquinone monomethyl ether, or a combination thereof is preferable.

  In addition, as for the general manufacturing method of the monomer represented by Formula (3), Unexamined-Japanese-Patent No. 2008-222678, WO2008 / 098877, WO2008 / 098885, WO2007 / 051738, Unexamined-Japanese-Patent No. 2000- Although described in 234002, GB930668, etc., it is not limited to these.

(Coloring material)
As the coloring material used in the present invention, conventionally known dyes and pigments can be used, but pigments (organic pigments and inorganic pigments) are preferable from the viewpoint of durability.

  Organic pigments include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complex System, diketopyrrolopyrrole, etc.), dye lake pigments and the like.

  Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium, chrome vermilion, nickel titanium, chrome titanium) , Yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), black pigment (carbon black, bone black, graphite, iron black, titanium black, etc.) , Luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.) and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

  As dyes, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinophthalone dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, pyrodonone dyes, pyrazolone dyes, acrid dyes And dyes.

  These pigments and dyes may be used alone or in combination of two or more.

  As the color material used in the present invention, a color material having an appropriate number average particle diameter may be used according to the purpose and application. For example, when transparency is required, it is preferable to use a small color material having a number average particle diameter of 0.1 μm or less. Moreover, when hiding is required, it is preferable to use a large color material having a number average particle diameter of 0.5 μm or more. The number average particle diameter of the color material can be measured using, for example, a laser diffraction particle size distribution analyzer SALD-3000J manufactured by Shimadzu Corporation.

  The color material used in the present invention is subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc. according to the purpose and application. It may be.

  Specific examples of usable pigments are described below by color, and specific examples of dyes by structure. I. No. Although it shows by (color index number), the color material used by this invention is not limited to these. In the following, “CI” means a color index, and a number means a color index number.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 49, 53, 55, 60, 61, 61: 1, 62, 62: 1, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 127: 1, 128, 129, 130, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 157, 158, 159, 1 0, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 188, 189, 190,191,191: 1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207,208,209,209: 1,212,213, 214, 215, 219 and the like.

  Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 31, 34, 36, 38, 39, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, 81, and the like.

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 49: 1, 49: 2, 50: 1, 52, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 54, 57, 57: 1, 57: 2, 58, 58: 4, 60, 60: 1, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 89, 90: 1, 95, 101, 101: 1, 104, 105, 108, 108: 1, 109, 112, 113, 114, 122, 123, 136, 144, 146, 147, 149, 150, 151, 64, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 216, 220, 221, 224, 226, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 248, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 279 and the like.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5,5: 1, 13, 14, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 39, 42, 44, 47, 49, 50 and the like.

  Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17, 17: 1, 19, 24, 24: 1, 25, 26, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80 and the like.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like.

  Examples of the brown pigment include C.I. I. Pigment brown 5, 6, 23, 24, 25, 32, 41, 42, and the like.

  Examples of the black pigment include aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. I. Pigment black 1, 6, 7, 9, 10, 11, 12, 13, 20, 31, 32, 34, and the like.

  Examples of white pigments include C.I. I. Pigment white 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 24, 26, 27, 28, and the like.

  Examples of the azo dye include C.I. I. Acid Yellow 11, Acid Orange 7, Acid Red 37, Acid Red 180, Acid Blue 29, Direct Red 28, Direct Red 83, Direct Yellow 12, Direct Orange 26, Direct Green 28, Direct Green 59, Reactive Yellow 2, Re Active Red 17, Reactive Red 120, Reactive Black 5, Disperse Orange 5, Disperse Red 58, Disperse Blue 165, Basic Blue 41, Basic Red 18, Mordant Red 7, Mordant Yellow 5, Mordant Black 7 Etc.

  Examples of anthraquinone dyes include C.I. I. Solvent Red 52, Solvent Red 60, Solvent Red 111, Solvent Red 138, Disper Thread 1, Disper Thread 4, Disper Thread 11, Disper Thread 15, Disper Thread 60, Solvent Blue 12, Solvent Blue 21, Solvent Blue 35, Solvent Blue 36, Disperse Blue 1, Disperse Blue 3, Disperse Blue 5, Disperse Blue 6, Disperse Blue 60, Solvent Violet 11, Solvent Violet 13, Solvent Violet 14, Solvent Violet 31, Disperse Violet 1, Disperse Violet 4, Disperse Violet 6, Disperse Violet 8, Disperse Violet 17, Sol Cement Green 3, Solvent Green 26, Solvent Green 28, Disperse Green 6: 1, Pat Blue, Acid Blue 40, Acid Green 25, Reactive Blue 19, Reactive Blue 49, Disperse Orange 119, and the like.

  Examples of the phthalocyanine dye include C.I. I. Basic blue 5 etc. are mentioned.

  Examples of quinoneimine dyes include C.I. I. Basic blue 3, basic blue 9, etc. are mentioned.

  Examples of quinophthalone dyes include C.I. I. Solvent Yellow 33, Solvent Yellow 114, Solvent Yellow 128, Solvent Yellow 129, Disperse Yellow 49, Disperse Yellow 54, Disperse Yellow 149, Disperse Yellow 160, and the like.

  Examples of nitro dyes include C.I. I. Acid Yellow 1, Acid Orange 3, Disperse Yellow 1, Disperse Yellow 9, Disperse Yellow 33, Disperse Yellow 42, and the like.

  Examples of pyrodonic dyes include C.I. I. Disperse Yellow 231 and the like.

  Examples of pyrazolone dyes include C.I. I. Solvent yellow 93 etc. are mentioned.

  Examples of the acrylic dye include C.I. I. Disperse Yellow 122 etc. are mentioned.

<Coloring material content>
The content of the color material in the color material composition of the present invention may be appropriately set according to the purpose and application. -5000 mass parts is preferable, 0.1-2000 mass parts is more preferable, 1-1000 mass parts is further more preferable, and 10-500 mass parts is the most preferable. Within this range, a color material composition in which the color material is stably dispersed can be obtained.

<Other colorant composition components>
The color material composition of the present invention may comprise other polymers, the following solvents and additives in addition to the polymer and the color material.

≪Solvent≫
Examples of the solvent contained in the color material composition of the present invention include polar solvents. As the polar solvent, both an aqueous solvent and an organic solvent can be used. Examples of the aqueous solvent include water, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t- Examples include butanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and hexylene glycol. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl Examples include formamide, dimethyl sulfoxide, hexamethyl phosphortriamide, pyridine, dimethyl sulfoxide, tetramethylene sulfone, dimethyl tetramethylene sulfone and the like. These may be used alone or in combination as long as they dissolve each other. The organic solvent may be mixed with cresol, phenol, benzonitrile, dioxane, butyrolactone, xylene, cyclohexane, hexane, benzene, toluene and the like.

≪Additives≫
In the color material composition of the present invention, various known additives such as organic silanes, fillers, attrition agents, dielectrics, lubricants and the like are included as long as the effects of the present invention are not impaired, if necessary. May be.

(Use)
The following uses are mentioned as a use of the coloring material composition of this invention. For example, conductive applications include antistatic coating agents for copying machines and printers, charge carriers, toner transfer members, fixing belts, intermediate transfer belts, film-type resistors, conductive pastes, battery electrode materials, and antistatic properties. Resin, conductive adhesive layer for capacitor, conductive sliding member, circuit board substrate, heat-resistant semiconductive material, self-temperature controlled energization heating element, thermal head heating resistor, recording energization heating sheet, wire cable A covering, a planar heating element, etc. are mentioned. Examples of the electromagnetic wave absorbing application include an electromagnetic wave shielding sheet, a flexible wiring sheet, an electromagnetic wave absorbing sheet, a heat ray absorbing sheet, and an ultraviolet absorbing sheet. Examples of light shielding applications include ultraviolet light shielding materials and black matrices for color filters. Examples of sliding applications include surface treatment agents for low-noise gears, molded articles for friction materials, and the like. In addition, substrates for photovoltaic devices such as substrates for solar cells, substrates for optical sensors, substrates for optical switches, substrates for printed wiring, substrates for electronic devices such as thermal head substrates, inkjet inks, protective layers for lithographic printing, It can be applied to various uses such as a binder for a thermal transfer sheet.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

  First, the color material dispersibility of the color material composition and the method for evaluating the adhesion to the substrate will be described.

<Colorant dispersibility>
The obtained polymer was made into an aqueous solution having a solid content concentration of 1% by mass (referred to as aqueous solution P), and ion-exchanged water / coloring material (carbon black, obtained from Laundry Science Association) / aqueous solution P was 100 / 0.2 / Mix in a glass container to be 0.2 (mass ratio), and then irradiate the mixture in the glass container with ultrasonic waves for 5 minutes with an ultrasonic cleaner (VS-N100L, manufactured by Velvo Crea Co., Ltd.). did. Then, it left still at room temperature for 4 hours, and observed the sedimentation state of a coloring material (carbon black) visually.
Evaluation criteria were as follows: ◯ = almost no sediment, Δ = about half of the color material (carbon black) was sedimented, and x = mostly sedimented.

<Base material adhesion>
The obtained polymer was made into an aqueous solution with a concentration of 20% by mass, applied to various substrates using an applicator so as to have a thickness of 76 μm, and allowed to stand in an atmosphere of 25 ° C. and 60% humidity for 3 days. To obtain a coating film.

After creating 100 squares of 2 mm square on the coating film, apply adhesive tape (mending tape, MD-18 manufactured by Nichiban Co., Ltd.) to the coating film surface so as to cover the entire square part (20 mm x 20 mm). Then, grip the edge of the adhesive tape so that the angle between the substrate side (non-adhesive layer side) of the adhesive tape and the coating surface is 90 °, and then maintain the angle in about 0.5 seconds. The adhesive tape was peeled from the surface of the coating film on which the eyes were formed, and the change in the coating film surface was visually observed.
Evaluation criteria were as follows: ○ = no peeling, Δ = about half peeled, and X = most peeled.

<Conditions for measuring weight average molecular weight by GPC>
The measurement by GPC is SCL-10A VP as a system controller, SIL-10A XL as an autosampler, CTO-10A as a column oven, LC-10AT as a pump (all manufactured by Shimadzu Corporation), and a detector (differential refractometer). ) Was used under the following measurement conditions using Shodex RI-71 (manufactured by Showa Denko KK).
Columns Shodex KD-G x 1 and Shodex KD806M x 2 are connected in series (both manufactured by Showa Denko KK)
Eluent 0.1% by weight lithium bromide dimethylformamide solution Eluent flow rate 0.8 mL / min Injection volume 100 μL
Column oven 40 ° C
Sample concentration 0.5% by mass
Calibration curve Polystyrene conversion

(Production Example 1) Production of (N-acryloyloxyethyl) pyrrolidone In a 500 ml four-necked flask equipped with a stirrer, thermometer, distillation device, gas blowing tube, and liquid addition line, 258 g of methyl acrylate, 2- 194 g of hydroxyethylpyrrolidone, 11 g of dibutyltin oxide as a catalyst, 0.13 g of phenothiazine as a polymerization inhibitor, and 0.13 g of hydroquinone monomethyl ether were charged. Thereafter, mixing and stirring were performed while blowing air into the reaction solution, and the mixture was placed in an oil bath to start heating. At the same time that the azeotropic mixture of methyl acrylate and methanol was removed from the flask, a mass of methyl acrylate corresponding to methyl acrylate in the azeotrope was continuously added to the flask through the liquid addition line, and the reaction was allowed to proceed for 10 hours. went. Thereafter, unreacted methyl acrylate was distilled off. The temperature of the reaction solution at this time was 90 ° C to 110 ° C.

  When the amount of (N-acryloyloxyethyl) pyrrolidone at the time when methyl acrylate was distilled off was measured with a gas chromatograph (manufactured by Shimadzu Corporation, GC-2010), and the yield was calculated, 2-hydroxyethylpyrrolidone was It was 85.3 mol%.

  The reaction solution was distilled under reduced pressure (boiling point: 115 to 120 ° C./66.66 Pa) to obtain 210 g of (N-acryloyloxyethyl) pyrrolidone having a purity of 98.0%.

(Production Example 2) Production of (N-methacryloyloxyethyl) pyrrolidone In a 500 ml four-necked flask equipped with a stirrer, thermometer, distillation apparatus, gas blowing tube, and liquid addition line, 300 g of methyl methacrylate, 2- 194 g of hydroxyethylpyrrolidone, 11 g of dibutyltin oxide as a catalyst, 0.13 g of phenothiazine as a polymerization inhibitor, and 0.13 g of hydroquinone monomethyl ether were charged. Thereafter, mixing and stirring were performed while blowing air into the reaction solution, and the mixture was placed in an oil bath to start heating. At the same time that the azeotropic mixture of methyl methacrylate and methanol was removed from the flask, a mass of methyl methacrylate corresponding to methyl methacrylate in the azeotropic mixture was continuously added to the flask through the liquid addition line, and the reaction was allowed to proceed for 10 hours. went. Thereafter, unreacted methyl methacrylate was distilled off. The temperature of the reaction solution at this time was 100 ° C to 120 ° C.

  When the amount of (N-methacryloyloxyethyl) pyrrolidone when methyl methacrylate was distilled off was measured with a gas chromatograph (manufactured by Shimadzu Corporation, GC-2010) and the yield was calculated, 2-hydroxyethylpyrrolidone was obtained. It was 87.5 mol%.

  The reaction solution was distilled under reduced pressure (boiling point: 122-127 ° C./66.66 Pa) to obtain 220 g of (N-methacryloyloxyethyl) pyrrolidone having a purity of 98.5%.

(Example 1) Production of poly (N-acryloyloxyethyl) pyrrolidone (N-acryloyloxyethyl) pyrrolidone obtained in Production Example 1 in a 200 ml separable flask equipped with a thermometer, stirrer, dropping funnel and condenser. 17 g and ion-exchanged water 60 g were charged, and nitrogen gas was bubbled for 30 minutes at a rate of 100 ml / min while stirring. Then, it heated up until the temperature in a flask became 70 degreeC, and hold | maintained so that temperature might become fixed. Next, 3.2 g of a 10% aqueous solution of V-59 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis (2-methylpropionamidine) dihydrochloride) was added as a polymerization initiator and reacted for 120 minutes. Thus, poly (N-acryloyloxyethyl) pyrrolidone (PHEPA) was obtained.

  The weight average molecular weight after completion of the reaction was 748,000, and the conversion of (N-acryloyloxyethyl) pyrrolidone was analyzed by a liquid chromatograph (La Chrom Elite, manufactured by Hitachi High-Technologies Corporation). As a result, it was 99.9%. Met.

  The colorant dispersibility and substrate adhesion of the polymer (PHEPA) obtained were measured. The results are shown in Tables 1 and 2.

(Example 2) Production of poly (N-methacryloyloxyethyl) pyrrolidone Example 1 except that (N-methacryloyloxyethyl) pyrrolidone obtained in Production Example 2 was used instead of (N-acryloyloxyethyl) pyrrolidone. The reaction was carried out in the same manner as above to obtain poly (N-methacryloyloxyethyl) pyrrolidone (PHEPM).

  The weight average molecular weight after completion of the reaction was 809000, and the conversion rate of (N-methacryloyloxyethyl) pyrrolidone was analyzed by the above liquid chromatograph to be 99.9%.

  The colorant dispersibility and substrate adhesion of the obtained polymer (PHEPM) were measured. The results are shown in Tables 1 and 2.

(Example 3) Production of N-vinylpyrrolidone / (N-acryloyloxyethyl) pyrrolidone copolymer In a 200 ml separable flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, 4.5 g of N-vinylpyrrolidone was prepared. Then, 34 g of ion-exchanged water was charged, and nitrogen gas was bubbled at a rate of 100 ml / min for 30 minutes while stirring. Then, it heated up until the temperature in a flask became 70 degreeC, and hold | maintained so that temperature might become fixed. Next, 11 g of N-vinylpyrrolidone, 16 g of (N-acryloyloxyethyl) pyrrolidone obtained in Production Example 1, 0.072 g of triethanolamine as a pH adjuster and 73 g of ion-exchanged water, and V- 59 g (5% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 60 minutes and aged for 60 minutes. Vinylpyrrolidone / (N-acryloyloxyethyl) pyrrolidone copolymer (VPHEPA) was obtained (N-vinylpyrrolidone / (N-acryloyloxyethyl) pyrrolidone = 50/50 (mass ratio)).

  The weight average molecular weight after completion of the reaction was 445,000, and when analyzed by the above liquid chromatograph, the conversion of N-vinylpyrrolidone was 99.8%, and the conversion of (N-acryloyloxyethyl) pyrrolidone was 99. 7%.

  The obtained polymer (VPHEPA) was measured for colorant dispersibility and substrate adhesion. The results are shown in Tables 1 and 2.

(Example 4) Production of N-vinylpyrrolidone / (N-methacryloyloxyethyl) pyrrolidone copolymer A 200 ml separable flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser tube was charged with 2.0 g of N-vinylpyrrolidone. Then, 125 g of ion-exchanged water was charged, and nitrogen gas was bubbled at a rate of 100 ml / min for 30 minutes while stirring. Then, it heated up until the temperature in a flask became 70 degreeC, and hold | maintained so that temperature might become fixed. Next, 18 g of N-vinylpyrrolidone, 20 g of (N-methacryloyloxyethyl) pyrrolidone obtained in Production Example 2, 0.070 g of triethanolamine, and 27 g of ion-exchanged water, and V-59 (Wako Pure) 8 g of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (manufactured by Yakuhin Kogyo Co., Ltd.) was added dropwise over 60 minutes and aged for another 60 minutes, and N-vinylpyrrolidone / ( N-methacryloyloxyethyl) pyrrolidone copolymer (VPHEPM) was obtained (N-vinylpyrrolidone / (N-methacryloyloxyethyl) pyrrolidone = 50/50 (mass ratio)).

  After completion of the reaction, the weight average molecular weight was 225,000, and analysis by the above liquid chromatograph revealed that the conversion rate of N-vinylpyrrolidone was 99.8% and the conversion rate of (N-methacryloyloxyethyl) pyrrolidone was 100%. Met.

  The obtained polymer (VPHEPM) was measured for colorant dispersibility and substrate adhesion. The results are shown in Tables 1 and 2.

(Example 5)
A color material composition obtained by adding 0.6 parts by mass of a color material (carbon black) to an aqueous solution (100 parts by mass) of the polymer (PHEPA) obtained in Example 1 and having a solid content concentration of 20% by mass is used. In the same manner as in Example 1 except that the adhesion of the color material composition to the substrate was evaluated. The results are shown in Table 2.

(Comparative Example 1)
Instead of the polymers of Examples 1 to 4, colorant dispersibility and substrate adhesion were measured using polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., K-30).

  The results are also shown in Table 1 and Table 2.

  As is apparent from Table 1, the (co) polymer of the present invention exhibits a colorant dispersibility equivalent to that of polyvinyl pyrrolidone, and further has a substrate adhesion superior to that of polyvinyl pyrrolidone from Table 2. I understand that.

  Since the color material composition of the present invention has good color material dispersibility and excellent substrate adhesion, it can be used in various applications such as conductive coating agents and inks.

Claims (5)

A color material composition comprising a polymer having a structural unit represented by the following formula (1) and a color material.

[Wherein, R is an alkylene group having 2 to 4 carbon atoms, or -R ² —O—R ³ — (R ² and R ³ may be the same or different, and are a methylene group, an ethylene group, or a propylene group. R ¹ represents a hydrogen atom or a methyl group. ] The color material composition according to claim 1, wherein the polymer further has a structural unit represented by the following formula (2).

[Wherein n represents an integer of 2 to 5. ]   The color material composition according to claim 1, wherein the color material is a pigment.   A colorant-dispersing polymer comprising a structural unit represented by the above formula (1). Furthermore, the polymer for color material dispersion | distribution of Claim 4 which has a structural unit represented by the said Formula (2).