JP5610764B2 - Color material dispersion composition - Google Patents

Description

The present invention relates to a resin for a color material dispersion composition used for various inks, paints, and the like, and a color material dispersion composition containing the resin. More specifically, it can be used in, for example, automobiles, coated steel sheets, building materials, cans, gravure, flexo, ink jet printers, color filters, etc., and can be used for dispersibility, adhesion, heat resistance, surface curability, transparency, The present invention relates to a colorant dispersion composition resin having excellent solubility and the like, and a colorant dispersion composition containing the resin.

Resin for colorant dispersion composition has various properties such as adhesion, heat resistance, transparency, curability, transparency, dry resolubility, light resistance, weather resistance, etc. Performance is required. In particular, high-performance inks such as inkjet inks and resist inks for color filters are required to have both dispersibility and other performance at a high level. To improve dispersibility, for example, amino groups and urethanes are used. When a resin having a group is used, durability and transparency tend to decrease, and a resin having an alicyclic structure such as an isobornyl group or a tricyclodecanyl group that improves durability and transparency is not dispersible. It tends to be enough.

  By the way, it is known that a resin having a ring structure in the main chain is excellent in durability, particularly heat resistance, and is mainly obtained by a method of polymerizing a monomer having a ring structure, but has a ring structure. It can also be obtained by a method of polymerizing while cyclizing a monomer that is not present. As one of such methods, there is known a method of cyclopolymerizing 1,6-dienes to obtain a resin having a tetrahydropyran ring which is a 6-membered ether ring in the main chain (for example, non-patent Reference 1). It has been disclosed that a colorant dispersion using this resin is excellent in dispersibility and dry re-dissolvability (see, for example, Patent Document 1).

  Further, the monomer represented by the formula (2) which is a 1,6-diene is polymerized at a high cyclization rate depending on conditions, and has a structural unit represented by the formula (1) in the main chain. Although it is known that a polymer can be obtained (see, for example, Non-Patent Document 2 and Non-Patent Document 3), there is no description about the application method and use of the polymer.

JP 2006-161035 A

Takashi Tsuda, Lon J. et al. Mathias, POLYMER, 1994, 35, p. 3317-3328 Robert D. Thompson, William L. Jarrett, Lon J. et al. Mathias, Macromolecules, 1992, 25, p. 6455-6459 Michio Urushizaki, Toshiyuki Kodaira, Takeji Furuta, Yutaka Yamada, Shoji Oshitani, Macromolecules, 1999, Vol. 32, p. 322-327

The resins described in Non-Patent Document 1 and Patent Document 1 are prone to abnormally high molecular weight during polymerization (molecular weight distribution becomes very wide) or gelation, and have problems in production stability and quality control. In addition, there is still room for improvement in achieving both dispersibility and other performance at a high level.

  The present invention has been made in view of the above problems, and a resin for a colorant dispersion composition capable of achieving both dispersibility and other performance such as adhesion and curability at a high level, and the resin. It aims at providing the coloring material dispersion composition using this.

The present inventor pays attention to a polymer having a structural unit represented by the formula (1) in the main chain, and this polymer is not only excellent in colorant dispersibility, but also particularly in adhesion and curability. It has been found that it is excellent, and has been conceived that it can be suitably used for a highly functional color material dispersion composition used for various inks, paints, and the like, and has reached the present invention.

  That is, the present invention provides a colorant dispersion composition comprising a colorant, a dispersant, a binder resin, and a liquid medium, wherein the binder resin includes a structural unit represented by formula (1) in the main chain, It is a coloring material dispersion composition characterized by being. The binder resin is also a binder resin for a colorant dispersion composition, wherein the binder resin is a resin containing a structural unit represented by the formula (1) in the main chain.

According to the present invention, there is provided a color material dispersion composition capable of achieving both dispersibility and other performance such as adhesion and curability at a high level, and is a constituent of the color material dispersion composition. A certain binder resin of the present invention has good production stability.

A ¹ H-NMR chart measured using the resin powder obtained in Example 1-2 is shown in FIG. The measured ¹ H-NMR chart using the resin powder obtained in Example 1-10 is shown in FIG.

The present invention will be described in detail below, but these are examples of embodiments of the present invention, and the present invention is not limited to these contents.

  First, each component of the color material dispersion composition of the present invention will be described. The essential components of the color material dispersion composition of the present invention are (A) a color material, (B) a dispersant, (C) a binder resin, and (D) a liquid medium, and (C) the binder resin has the formula ( It is a resin containing the structural unit represented by 1) in the main chain. Moreover, according to the objective and required characteristic of each use, (E) other components other than the above may be further blended. Hereinafter, each component constituting the color material dispersion composition of the present invention will be described.

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(A) The coloring material coloring material is for coloring the coloring material dispersion composition of the present invention, and conventionally known dyes and pigments can be used, but pigments (organic pigments and inorganic pigments) are preferred 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, etc. can be used. 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.) Bright pigments (pearl pigments, aluminum pigments, bronze pigments, etc.) and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used. As the dye, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like can be used.

  Specific examples of usable pigments are described below by color, and specific examples of dyes by structure. I. No. Although indicated by (color index number), the color material of the present invention is not limited thereto. 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, 116117, 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, 16 161, 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.

  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. And CI pigment brown 5, 6, 23, 24, 25, 32, 41, 42.

  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, 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. Examples include bat blue 4, acid blue 40, acid green 25, reactive blue 19, reactive blue 49, disperse thread 60, disperse blue 56, disperse blue 60, and the like.

Examples of the phthalocyanine dye include C.I. I. Basic blue 5 etc. can be mentioned.
Examples of quinoneimine dyes include C.I. I. Examples include Basic Blue 3 and Basic Blue 9.

Examples of quinoline dyes include C.I. I. Solvent yellow 33, acid yellow 3, disperse yellow 64, etc. are mentioned.
Examples of nitro dyes include C.I. I. Acid yellow 1, acid orange 3, disperse yellow 42, etc. can be mentioned.

  The above-mentioned color materials can be used alone or in combination of two or more. As the above-mentioned color material, those having an appropriate average particle diameter can be used according to the purpose and application. For example, when transparency is required, a small average particle size of 0.1 μm or less is preferable, and when concealability is required, a large average particle size of 0.5 μm or more is preferable. In addition, the above-described coloring material 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., depending on the purpose and application. Also good.

  The proportion of the color material in the color material dispersion composition of the present invention may be appropriately set according to the purpose and application, but in the color material dispersion composition in terms of balancing the coloring power and dispersion stability, It is 0.1-70 mass%, Preferably it is 0.5-60 mass%, More preferably, it is 1-50 mass%.

(B) Dispersant The dispersant has an interaction site with the color material and an interaction site with the dispersion medium (liquid medium or binder resin), and functions to stabilize the dispersion of the color material into the dispersion medium. A conventionally known dispersant can be used. Generally, it is classified into a resin type dispersant (polymer dispersant), a surfactant (low molecular dispersant), and a pigment derivative.

  Specific examples of the resin-type dispersant include, for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, Polysiloxane, long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide and salt formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, (meth) acrylic acid -Styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct And the like.

  In addition, as a structure, a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a coloring material and the graft chain is a compatible chain having an interaction property with a dispersion medium, A resin having a compatible chain in a block structure is particularly preferably used.

  Specific examples of the surfactant include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, Anionic surfactants such as ammonium lauryl sulfate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate Nonionic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Thione surfactant; alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazoline, and the like.

  The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, and a phthalimide group. Examples of the structure of the dye as a base include, for example, azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, and perylene. , Diketopyrrolopyrrole and the like.

  Although the commercially available dispersing agent which can be used is illustrated by a brand name below, the dispersing agent of this invention is not limited to these.

  For example, EFKA-46, 47, 48, 745, 1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 1525070, 5207 (above, manufactured by EFKA ADDITIVES), Anti-Terra-U, Ant -Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, 160, 161, 162 163, 164, 166, 182, P-104, P-104S, P105, 220S, 203, 204, 205, 2000, 2001, 9075, 9076, 9077 (above, manufactured by Big Chemie), SOLPERSE 3000, 5000, 9000, 12000 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000, 28000 (manufactured by Nihon Lubrizol), Disperlon 7301, 325, 374, 234, 1 220, 2100, 2200, KS260, KS273N, 152MS (above, manufactured by Enomoto Kasei), Ajisper PB-711, 821, 822, 880, PN-411, PA-111 (above, manufactured by Ajinomoto Fine Techno), KP series (Shin-Etsu) Chemical Industry), Polyflow Series (manufactured by Kyoeisha Chemical Co., Ltd.), Mega Fuck Series (manufactured by DIC), Dispaid Aid Series (manufactured by San Nopco), and the like.

  These dispersants can be used alone or in combination of two or more. The proportion of the dispersant in the color material dispersion composition of the present invention may be set as appropriate according to the purpose and application, but the dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency In order to achieve a balance, the content is usually 0.01 to 60% by mass, preferably 0.1 to 50% by mass, and more preferably 0.5 to 40% by mass with respect to the color material.

(C) Binder resin The binder resin is a dispersion medium that uniformly holds the color material dispersed by the dispersant, assists the dispersion stability of the color material, and affects the coatability and coating performance after drying. It is an ingredient. The binder resin of the present invention is a resin containing the structural unit represented by the formula (1) in the main chain, has excellent colorant dispersibility, and in particular, adhesion, heat resistance, curability, and transparency. Excellent coating performance after drying, such as properties.

(R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.)
The expression of the above-described characteristics in the binder resin of the present invention is presumed to be caused by the tetrahydrofuran ring contained in the structural unit represented by the formula (1) and the methylene groups on both sides of the tetrahydrofuran ring. Tetrahydrofuran ring acts as a so-called Lewis base (donor of lone pair), and its action is not as strong as amines that are strong bases, and has moderate basicity, and therefore interferes with the action of the dispersant. It is considered that the coloring material interacts with the coloring material and the dispersing agent and stabilizes the coloring material dispersed by the dispersing agent. In addition, this Lewis basicity facilitates the interaction between the tetrahydrofuran ring and the functional group on the surface of the base material, and it is considered that good adhesion is also exhibited. Furthermore, it is considered that the oxygen scavenging property of the tetrahydrofuran ring reduces the inhibition of curing by oxygen in radical curing using heat or active energy rays, and exhibits excellent surface curability and thin film curability.

  It is known that the tetrahydrofurfuryl group, which is a functional group containing a tetrahydrofuran ring, captures oxygen by the mechanism represented by the following formula (3) and reduces the inhibition of curing by oxygen in radical curing using heat and active energy rays. Thus, the binder resin of the present invention is considered to exhibit excellent curability by the same mechanism as shown in the following formula (4). In addition, tetrahydrofuran is a solvent that has the ability to dissolve a very wide range of substances, and is a solvent that is often used not only for industrial use but also for analysis and research purposes. However, the binder resin of the present invention has excellent compatibility and dry re-dissolution. The reason for this is considered to be that it has a tetrahydrofuran structure.

  The binder resin of the present invention has a high heat resistance because it has a ring structure in the main chain, and has good transparency because it does not contain a nitrogen atom. Resins having a ring structure in the main chain have high heat resistance, but in most cases lack flexibility, but the repeating unit containing a tetrahydrofuran ring in the binder resin of the present invention represented by formula (1) is located on both sides of the tetrahydrofuran ring. Since the methylene group is present, flexibility is high, and it is considered that each performance derived from the tetrahydrofuran ring such as dispersibility, adhesion, curability, compatibility, and dry re-dissolvability is effectively expressed. The performance derived from these tetrahydrofuran rings can be expressed to some extent even in a (meth) acrylic copolymer having a tetrahydrofurfuryl group in the side chain such as a tetrahydrofurfuryl copolymer of (meth) acrylic acid, It is difficult to develop high heat resistance like the binder resin of the present invention.

  R of the structural unit represented by the formula (1) in the binder resin of the present invention represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As described above, since the development of each performance of the binder resin of the present invention is caused by the tetrahydrofuran ring in the main chain and the methylene group on both sides of the tetrahydrofuran ring, R is appropriately selected according to the purpose and application. do it.

  Specific examples of R include, for example, a hydrogen atom; methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-amyl, s-amyl, t-amyl, n- Hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, Chain saturated hydrocarbon groups such as eicosyl, ceryl, and melyl; chain saturated hydrocarbons such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl, phenoxyethyl, and phenoxyethoxyethyl A part of the hydrogen atom of the hydrogen group Alkoxy-substituted chain saturated hydrocarbon group substituted with a di group; hydroxy-substituted chain saturated hydrocarbon group in which part of the hydrogen atoms of a chain saturated hydrocarbon group such as hydroxyethyl, hydroxypropyl, hydroxybutyl, etc. is replaced with a hydroxy group A halogen-substituted chain saturated hydrocarbon group in which a part of hydrogen atoms of a chain saturated hydrocarbon group such as fluoroethyl, difluoroethyl, chloroethyl, dichloroethyl, bromoethyl, dibromoethyl and the like is replaced by halogen; vinyl, allyl, methallyl, Chain unsaturated hydrocarbon groups such as crotyl and propargyl, and chain unsaturated hydrocarbon groups in which part of the hydrogen atoms are replaced with alkoxy groups, hydroxy groups or halogens; cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4- t-butylcyclohexyl, tricyclodecanyl Cycloaliphatic hydrocarbon groups such as isobornyl, adamantyl and dicyclopentadienyl, and alicyclic hydrocarbon groups in which part of the hydrogen atoms are replaced by alkoxy groups, hydroxy groups or halogens; phenyl, methylphenyl, dimethylphenyl , Trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthranyl and the like, and some of the hydrogen atoms are alkoxy groups, hydroxy groups, And aromatic hydrocarbon groups substituted with halogen. Further, a substituent may be further bonded to these organic groups. Two or more of R in formula (1) may be the same or different.

  The content of the structural unit represented by the formula (1) in the binder resin of the present invention may be appropriately set according to the purpose, application and molecular weight of the binder resin of the present invention. 1-100 mol%, preferably 2-100 mol%, more preferably 5-100 mol%. In particular, with respect to the colorant dispersibility, when the binder resin of the present invention has a high molecular weight, there is a tendency that even if the content of the structural unit represented by the formula (1) is small, the performance is manifested. In some cases, increasing the content tends to facilitate performance. This is considered to be related to the number of structural units represented by the formula (1) contained per main chain (hereinafter referred to as the average number of functional groups), and the average number of functional groups is 0.5 or more. Preferably, it is 1.0 or more, more preferably 2.0 or more.

The average number of functional groups is represented by the following formula.
Average number of functional groups = A / P
A: Number of moles of the structural unit represented by the formula (1) included in the unit mass [mol / g]
P: Number of moles of the binder resin of the present invention contained in unit mass [mol / g]
A can be calculated as the following equation, including the case where there are two or more types of structural units represented by the equation (1).
A = ΣA _x (X = 1, 2, 3,...)
A _x = unit mass × (C _x / 100) / F _x
A _x : Number of moles of the structural unit represented by the formula (1) of the X (X = 1, 2, 3,...) Type contained in the unit mass [mol / g]
C _x : the mass ratio [% by mass] of the structural unit represented by the formula (1) of the X (X = 1, 2, 3,...) Type contained in the unit mass.
F _x : X (X = 1, 2, 3,...) Molecular weight [g / mol] of the structural unit represented by the formula (1) of the type
P can be approximated by the following formula using the number average molecular weight (Mn) of the binder resin of the present invention.
P = unit mass / Mn
Mn: Number average molecular weight of the binder resin of the present invention Therefore, the average number of functional groups is represented by the following formula using C _x , F _x , and Mn.
Average number of functional groups = Mn × Σ {(C _x / 100) × (1 / F _x )}.

In addition, when obtaining by the manufacturing method including the process of superposing | polymerizing the monomer component containing the monomer represented by Formula (2), the binder resin of this invention is represented by Formula (2) so that it may mention later. Since the cyclization rate of the monomer (the ratio at which the structural unit represented by the formula (1) is formed from the monomer represented by the formula (2)) is high, C _x and F _x are It can be approximated as follows.
C _x : Mass ratio of the monomer represented by the formula (2) of the X (X = 1, 2, 3,.
F _x : X (X = 1, 2, 3,...) Molecular weight [g / mol] of the monomer represented by the formula (2) of the type
Further, when the reaction rate of each monomer used in the polymerization is similarly high (for example, the reaction rate of each monomer is 90 mol% or more), C _x is as follows: Can be approximated.
C _x : Mass ratio [mass%] of the monomer represented by the formula (2) of the X (X = 1, 2, 3,...) Type in the monomer component.

  It is preferable that the binder resin of this invention is a thing obtained by the manufacturing method including the process of superposing | polymerizing the monomer component containing the monomer represented by Formula (2). This is because the monomer represented by the formula (2) is polymerized to produce the structural unit represented by the formula (1) at a high rate, and is unlikely to cause abnormal high molecular weight or gelation. .

式（２）で表される単量体のＲは、水素原子、または炭素数が１〜３０の有機基を表し、目的や用途に合わせて、適宜選択すればよい。Ｒの具体例としては、前記式（１）のＲと同じである。

R of the monomer represented by the formula (2) represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be appropriately selected according to the purpose and application. Specific examples of R are the same as R in the formula (1).

  Moreover, when the monomer represented by formula (2) is exemplified by the compound name, α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, α-allyloxymethyl ethyl acrylate, α- N-propyl allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate t -Butyl, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate n-hexyl, α-allyl S-hexyl oxymethyl acrylate, α-allyloxymethyl acrylate n-heptyl, α-allyl N-octyl dimethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, capryl of α-allyloxymethyl acrylate, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl decyl acrylate, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl lauryl acrylate, α-allyloxymethyl acrylate tridecyl, α-allyloxymethyl Myristyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, α-allyloxymethyl acetate Nonadecyl oxalate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, methoxyethyl α-allyloxymethyl acrylate, methoxyethoxy α-allyloxymethyl acrylate Ethyl, methoxyethoxyethoxyethyl α-allyloxymethyl acrylate, 3-methoxybutyl α-allyloxymethyl acrylate, ethoxyethyl α-allyloxymethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, α-allyl Phenoxyethyl oxymethyl acrylate, α-allyloxymethyl acrylate phenoxyethoxyethyl, α-allyloxymethyl acrylate hydroxyethyl, α-allyloxymethyl acrylate hydroxypropyl α-allyloxymethyl acrylate hydroxybutyl, α-allyloxymethyl acrylate fluoroethyl, α-allyloxymethyl acrylate difluoroethyl, α-allyloxymethyl acrylate acrylate, α-allyloxymethyl acrylate acrylate, α -Bromoethyl allyloxymethyl acrylate, dibromoethyl α-allyloxymethyl acrylate, vinyl α-allyloxymethyl acrylate, allyl α-allyloxymethyl acrylate, methallyl α-allyloxymethyl acrylate, α-allyloxymethyl Crotyl acrylate, propargyl α-allyloxymethyl acrylate, cyclopentyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 4 Methylcyclohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyl Dicyclopentadienyl oxymethyl acrylate, phenyl α-allyloxymethyl acrylate, methyl phenyl α-allyloxymethyl acrylate, dimethyl phenyl α-allyloxymethyl acrylate, trimethyl phenyl α-allyloxymethyl acrylate, α -4-t-butylphenyl allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate, diphenylethyl α-allyloxymethyl acrylate, - allyloxymethylacrylate triphenylmethyl, alpha-allyloxymethylacrylate cinnamyl, alpha-allyloxymethylacrylate naphthyl, alpha-allyloxymethylacrylate anthranyl. These monomers represented by the formula (2) can be used alone or in combination of two or more.

  In addition to the monomer represented by the formula (2), the monomer component may contain another copolymerizable monomer. The type and amount of the monomer component are the colorant dispersion composition of the present invention. What is necessary is just to select and adjust suitably according to the objective and use of a thing.

  Examples of such other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, ( N-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, (meth) acrylic t -Amyl, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, Octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, ( T) Phenyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid glycidyl, (meth) acrylic acid β-methylglycidyl, (meth) acrylic acid β -Ethyl glycidyl, (meth) acrylic acid (3,4-epoxy (Meth) acrylic acid esters such as cyclocyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate; N, N-dimethyl (meta ) (Meth) acrylamides such as acrylamide and N-methylol (meth) acrylamide; Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid Unsaturated polyvalent carboxylic acids such as citraconic acid and mesaconic acid; chain extension between unsaturated group and carboxyl group such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate Unsaturated monocarboxylic acids, such as maleic anhydride and itaconic anhydride Anhydrides; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, methoxystyrene; N-substituted maleimides such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide; Macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam; 1,3-butadiene, isoprene Conjugated dienes such as chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; methyl vinyl ether, ethyl vinyl ether Propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxy Vinyl ethers such as butyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide; isocyanatoethyl (meth) acrylate, allyl And unsaturated isocyanates such as isocyanate. These other copolymerizable monomers can be used alone or in combination of two or more.

  The content ratio of the monomer represented by the formula (2) contained in the monomer component may be appropriately set according to the purpose, application, and molecular weight of the binder resin of the present invention. It is 1-100 mol% in a monomer component, Preferably it is 2-100 mol%, More preferably, it is 5-100 mol%.

  As the polymerization method of the monomer component, known polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used, and may be appropriately selected according to the purpose and application. It is advantageous, and the structure adjustment such as molecular weight is easy and preferable. As a polymerization mechanism, a polymerization method based on a known mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. The ratio of the structural unit represented by formula (1) produced from the monomer represented by

  A known method can be used as a method for initiating polymerization, provided that energy necessary for initiating polymerization is supplied to the monomer component from an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams or the like. In addition, it is preferable to use a polymerization initiator in combination, because the energy required for the initiation of polymerization can be greatly reduced and the reaction can be easily controlled.

  As a method for controlling the molecular weight, a known method can be used. For example, it can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

  When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, and the polymerization mechanism and the type of monomer used. May be appropriately set according to the polymerization conditions such as the amount, the polymerization temperature, and the polymerization concentration, but it is efficient and preferable to include a liquid medium to be used later when the colorant dispersion composition is formed.

  For example, monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, glycol monoethers such as 3-methoxybutanol; ethylene glycol dimethyl ether; Ethylene glycol Diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and other glycol ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Salts, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, esters of glycol monoether such as 3-methoxybutyl acetate; methyl acetate, ethyl acetate , Propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Alkyl esters such as methyl, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone And water. These may be used alone or in combination of two or more.

  As a usage-amount of a solvent, 40-1000 mass% is preferable with respect to 100 mass% of all monomer components, and 100-400 mass% is more preferable.

  When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate.

  For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, azo Bisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), Known peroxides and azo compounds such as hydrogen peroxide and persulfate may be used, and these may be used alone or in combination of two or more. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

  The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.1 to 20% by mass is preferable with respect to 100% by mass of all monomer components, and 0.5 to 15% by mass is more preferable.

  When the monomer component is polymerized by a radical polymerization mechanism, a known chain transfer agent may be used as necessary, and it is more preferable to use in combination with a radical polymerization initiator. When a chain transfer agent is used at the time of polymerization, there is a tendency that increase in molecular weight distribution and gelation can be suppressed. Specific examples of such chain transfer agents include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, N-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), di Mercaptocarboxylic esters such as pentaerythritol hexakis (3-mercaptopropionate); ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane, etc. Alkyl mercaptans; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3 -Mercaptopropionyloxy) -ethyl] mercaptoisocyanurates such as isocyanurate; disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; simple units such as α-methylstyrene dimer Monomeric dimers; alkyl halides such as carbon tetrabromide; Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercaptoalcohols, aromatic mercaptans; mercaptoisocyanurates in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. Compounds having a mercapto group, such as catechol, are preferred. These may be used alone or in combination of two or more.

  The amount of chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of monomers used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.1 to 20% by mass is preferable with respect to 100% by mass of all monomer components, and 0.5 to 15% by mass is more preferable.

  The polymerization temperature when the monomer component is polymerized using a polymerization initiator that generates radicals by heat by a radical polymerization mechanism includes the type and amount of the monomer used, the type and amount of the polymerization initiator, etc. However, it is preferably 50 to 200 ° C, more preferably 70 to 150 ° C.

  Examples of steps other than the step of polymerizing the monomer component include steps performed by known polymer production methods, such as polymer modification treatment steps, purification steps such as reprecipitation and liquid separation, and two steps. A solvent removal / pelletizing step using a screw extruder or the like, a step of adjusting the concentration of the polymer by removing or adding the solvent, and the like can be used as necessary. The polymer modification treatment process will be described below.

  The binder resin of the present invention may be obtained by polymerizing a monomer component containing the monomer represented by the formula (2) and then performing a modification treatment. By performing the modification treatment, it is possible to obtain a structure that is difficult to obtain only by performing a normal polymerization step such as introduction of a radically polymerizable unsaturated group or introduction of a graft chain.

  Such a modification treatment method is not particularly limited as long as the constitutional unit represented by the formula (1) in the binder resin is not completely lost. For example, a monomer having a functional group X And a method of reacting a compound having a functional group Y capable of reacting with the functional group X after polymerizing the monomer component containing.

  Examples of such combinations of functional groups X and Y include, for example, carboxyl group and hydroxy group, carboxyl group and epoxy group, carboxyl group and isocyanate group, hydroxy group and isocyanate group, acid anhydride group and hydroxy group, acid anhydride Groups and amino groups. Specifically, for example, it is possible to obtain a binder resin having a radically polymerizable unsaturated group by reacting glycidyl (meth) acrylate after polymerizing a monomer component containing (meth) acrylic acid, A binder resin having polycaprolactone in the graft chain can be obtained by polymerizing a monomer component containing glycidyl (meth) acrylate and then reacting one terminal carboxyl group-based polycaprolactone.

  The weight average molecular weight of the binder resin of the present invention may be appropriately set according to the purpose and application, but is usually 2000 to 250,000, preferably 3000 to 200000, and more preferably 4000 to 150,000.

  The proportion of the binder resin of the present invention in the color material dispersion composition of the present invention may be appropriately set according to the purpose and application, but is usually 0.1 to 90% by mass in the color material dispersion composition, preferably Is 0.5 to 80% by mass, more preferably 1 to 70% by mass.

(D) Liquid medium The liquid medium is a dispersion medium that uniformly holds the color material dispersed by the dispersant, and is a liquid that mainly functions to adjust the viscosity, coating characteristics, drying characteristics, and the like of the color material dispersion composition. It is a substance. As such a liquid medium, a conventionally known liquid medium can be appropriately selected and used according to the purpose and application.

  For example, monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, glycol monoethers such as 3-methoxybutanol; ethylene glycol dimethyl ether; Ethylene glycol Diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and other glycol ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Salts, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, esters of glycol monoether such as 3-methoxybutyl acetate; methyl acetate, ethyl acetate , Propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Alkyl esters such as methyl, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Class: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, s- (meth) acrylic acid Butyl, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, isodecyl (meth) acrylate, tri (meth) acrylate Sil, cyclohexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate , Tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , (Meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid allyl, (meth) acrylic acid 2-methoxyethyl (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic Glycidyl acid, β-methylglycylic acid (meth) acrylate Liquid (meth) acrylic acid esters such as zil, (meth) acrylic acid β-ethylglycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl; liquid unsaturated monocarboxylic acids such as (meth) acrylic acid Liquid aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene; liquid conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; liquid vinyls such as vinyl acetate, vinyl propionate and vinyl butyrate Esters: Liquid oligomers and liquid polymers such as alkylene oxide acrylate and butadiene; ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) Accel Relay Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Polyfunctional monomers such as acrylate and triallyl isocyanurate; dry oils such as linseed oil, sunflower oil, soybean oil, tung oil; water, and the like. These may be used alone or in combination of two or more.

  The amount of the liquid medium used may be appropriately set depending on the purpose and application, but is usually 10 to 95% by mass, preferably 20 to 90% by mass, and more preferably 30 to 30% in the colorant dispersion composition. It is 85 mass%.

(E) Other components The color material-dispersed composition of the present invention may further contain components other than the essential components according to the purpose and required characteristics of each application. For example, in a photocurable ink, it is preferable to add a photopolymerizable monomer and a photoinitiator in addition to the above essential components. In an air curable paint, in addition to the above essential components, dryness such as linseed oil is used. It is preferable to blend a dryer such as oil or cobalt octylate.

  In alkali developing resist inks such as solder resists and color filter resists, in addition to the above essential components, an alkali-soluble binder resin, epoxy resin, radical-curable unsaturated group-containing resin, polyfunctional acrylate, and photoinitiator It is preferable to add an agent.

  Moreover, you may mix | blend stabilizers, such as antioxidant and a ultraviolet absorber, a leveling agent, coupling agents, such as a silane type | system | group, an aluminum type, and a titanium type, as needed.

  The color material dispersion composition of the present invention can be prepared by a known dispersion method, and may be appropriately selected according to the purpose and application. Examples of the disperser that can be used include a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, and a blender. In order to reduce the particle size of the color material, it is preferable to carry out a kneading and dispersing process with a roll mill, a kneader, a blender, etc., and then a finely dispersing process with a media mill such as a bead mill. It is preferable to remove fine dust by performing a filtration process or the like.

  The method of adding the constituents of the dispersion to the disperser may be batch or sequential, the order is arbitrary, and may be appropriately selected according to the type of the disperser. In addition, it is not necessary to add all of the components (coloring material, dispersant, binder resin, liquid medium, and other components) to the disperser, but the minimum color required to disperse the coloring material with the coloring material and the disperser. Components other than the colorant may be added to and mixed with components other than the colorant after preparing the colorant dispersion composition containing the colorant at a high concentration by introducing the component other than the material into the disperser.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Synthesis of monomer represented by formula (2)>
[Synthesis Examples 1 to 5]
As shown in Table 1, each α-allyloxymethyl acrylate ester (AMA-R), which is a monomer represented by the formula (2), is used as a catalyst according to Japanese Patent Laid-Open No. 10-226669. -Diazabicyclo [2.2.2] octane was synthesized from allyl alcohol and the corresponding α-hydroxymethyl acrylate ester (HMA-R).

<Synthesis of Resin Containing Structural Unit Represented by Formula (1) in Main Chain>
Hereinafter, the synthesis of a resin containing the structural unit represented by the formula (1) in the main chain will be described. In addition, measurement of solid content of the obtained resin solution, measurement of resin weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), and structural unit represented by formula (1) Calculation of the average number of functional groups, extraction of the resin powder, measurement of ¹ H-NMR, and the like were performed as follows.

(Solid content)
About 0.3 g of the resin solution was weighed into an aluminum cup, dissolved by adding about 2 g of acetone, and then naturally dried at room temperature. After drying at 140 ° C. for 3 hours using a hot air dryer, the product was allowed to cool in a desiccator and the weight was measured. The solid content of the resin solution was calculated from the weight loss.

(Mw, Mn, Mw / Mn)
What diluted the resin solution with tetrahydrofuran and filtered with the filter of the hole diameter 0.45 micrometer was measured with the following gel permeation chromatography (GPC) apparatus and conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh)
Elution solvent: Tetrahydrofuran standard: Standard polystyrene (manufactured by Tosoh)
Separation column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation).

(Average number of functional groups)
Average number of functional groups = Mn × {(weight ratio of AMA-R in monomer component [mass%] / 100) × (1 / AMA-R molecular weight)}.

(Resin removal)
A part of the resin solution was diluted with tetrahydrofuran and poured into excess hexane for reprecipitation. The precipitate was taken out by filtration and then vacuum dried at 70 ° C. (for 5 hours or more) to obtain a white resin powder.

⁽¹ H-NMR measurement)
200 mg of the white powder obtained as described above was dissolved in 3 g of heavy dimethyl sulfoxide containing tetramethylsilane and measured with a nuclear magnetic resonance apparatus (200 MHz, manufactured by Varian).

[Example 1-1]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 223.7 parts of propylene glycol monomethyl ether acetate (PGMEA) was charged into the reaction vessel, and the temperature was raised to 90 ° C. On the other hand, in dropping tank A, 20.0 parts of AMA-M obtained in Synthesis Example 1, 110.0 parts of benzyl methacrylate (BZMA), 41.4 parts of methyl methacrylate (MMA), 28.6 parts of methacrylic acid (MAA) In the dropping tank B, 4.7 parts of t-butylperoxy-2-ethylhexanoate (PBO) and 37.3 parts of PGMEA are stirred and mixed. -A product obtained by stirring and mixing 3.0 parts of mercaptopropionic acid (MPA) and 39.0 parts of PGMEA was prepared.

  After confirming that the internal temperature of the reaction tank was stabilized, the dropping of each mixture was started simultaneously from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C. From the dropping tanks B and C, the polymerization reaction was carried out by dropping over 3.5 hours. 30 minutes after the completion of dropping, the temperature was raised and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Table 3.

[Example 1-2]
Example 1-1 except that the mixture prepared in the dropping tank A was changed to a well-mixed mixture of AMA-M 60.0 parts, BZMA 110.0 parts, MMA 1.4 parts, and MAA 28.6 parts. A resin solution was obtained in the same manner. Also, a white powder of resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 3.
Moreover, < ¹ > H-NMR was measured using the obtained resin powder. ^{A 1} H-NMR chart is shown in FIG.

[Example 1-3]
Except that the liquid mixture prepared in the dropping tank A was changed to a well-mixed mixture of AMA-M 60.0 parts, cyclohexyl methacrylate (CHMA) 110.0 parts, MMA 1.4 parts, MAA 28.6 parts, A resin solution was obtained in the same manner as in Example 1-1. The analysis results are shown in Table 3.

[Example 1-4]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 208 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, 96.8 parts of styrene (ST) is added to the dropping tank A, and 60.0 parts of AMA-M, 1.4 parts of MMA, 28.6 parts of MAA, and 5.0 parts of PBO are well stirred and mixed in the dropping tank B. The dropping tank C was prepared by thoroughly stirring and mixing 3.0 parts of MPA and 92.0 parts of PGMEA.

  After confirming that the internal temperature of the reaction vessel was stable, 13.2 parts of ST1 was charged into the reaction vessel. Immediately thereafter, dropwise addition of each mixture from the addition tanks A, B, and C was started simultaneously, While adjusting to ° C., the polymerization reaction was carried out by dropping from the dropping tank A over 8 hours and dropping from the dropping tanks B and C over 10 hours. One hour after the completion of dropping, the temperature was raised and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. Also, a white powder of resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 3.

[Examples 1-5 to 1-8]
A resin solution was obtained in the same manner as in Example 1-2 except that the type of the cyclic monomer prepared in the dropping tank A was changed to that shown in Table 2. The analysis results are shown in Table 3.

[Example 1-9]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 213.5 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, in the dropping tank A, 121.8 parts of AMA-M and 78.2 parts of MMA obtained in Synthesis Example 1 were stirred and mixed, and in the dropping tank B, 4.7 parts of PBO and 42.0 parts of PGMEA were stirred and mixed. The dropping tank C was prepared by stirring and mixing 3.5 parts of methyl 3-mercaptopropionate (MPM) and 44.5 parts of PGMEA.

  After confirming that the internal temperature of the reaction tank was stabilized, the dropping of each mixture was started simultaneously from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C. From the dropping tank B, the polymerization reaction was carried out by dropping over 3.5 hours and from the dropping tank C over 4 hours. After completion of the dropwise addition, the temperature was increased and the temperature was increased to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. Also, a white powder of resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 3.

[Example 1-10]
A resin solution and a white resin powder were obtained in the same manner as in Example 1-9 except that 200.0 parts of AMA-M was prepared in the dropping tank A. The analysis results are shown in Table 3.
Moreover, < ¹ > H-NMR was measured using the obtained resin powder. ^{A 1} H-NMR chart is shown in FIG.

[Examples 1-11 to 1-14]
A resin solution and a white powder of resin were obtained in the same manner as in Example 1-10 except that the type of the cyclic monomer prepared in the dropping tank A was changed to that shown in Table 2. The analysis results are shown in Table 3.

[Comparative Example 1-1]
A resin solution was obtained in the same manner as in Example 1-1 except that the mixture prepared in the dropping tank A was changed to a mixture obtained by stirring and mixing 110.0 parts of BZMA, 61.4 parts of MMA, and 28.6 parts of MAA. . Also, a white powder of resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 3.

[Comparative Example 1-2]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 111.8 parts of PGMEA and 111.8 parts of 2-propanol (IPA) were charged into the reaction vessel, and the temperature was increased until IPA was refluxed and the internal temperature reached 89 ° C. On the other hand, in the dropping tank A, 20.0 parts of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (MD), 110.0 parts of BZMA, 41.4 parts of MMA, and 28.6 parts of MAA are well stirred. In the dropping tank B, 4.7 parts of t-butylperoxy-2-ethylhexanoate (PBO), 18.6 parts of PGMEA, and 18.6 parts of IPA were added to the dropping tank C. Prepared by stirring and mixing 3.0 parts of 3-mercaptopropionic acid (MPA), 19.5 parts of PGMEA and 19.5 parts of IPA.

After confirming that the internal temperature and reflux state of the reaction tank were stabilized, the dropping of each mixture was started simultaneously from the dropping tanks A, B, and C. From the dropping tank A, the dropping tanks B and C were taken over 3 hours. Was added dropwise over 3.5 hours to conduct a polymerization reaction. After 30 minutes from the end of dropping, the temperature was started to evaporate the solvent containing IPA, and at the same time, PGMEA in the same amount as the amount of the distilled solvent was supplied to the reaction vessel. When the internal temperature reached 115 ° C., the heating was temporarily stopped, and the pressure in the system was gradually reduced to 37.3 kPa to maintain this pressure. When the pressure in the system reaches 37.3 kPa, the heating is resumed, and the internal temperature lowered by depressurization is again set to 115 ° C., then the pressure is released and the pressure in the system is returned to the normal pressure. The supply of was stopped. Furthermore, it cooled to room temperature and obtained the resin solution. The analysis results are shown in Table 3.
MD is a monomer capable of obtaining a resin having a tetrahydropyran ring in the main chain described in Non-Patent Document 1 and Patent Document 2.

[Comparative Example 1-3]
The amount of PGMEA charged in the reaction tank is 163.7 parts, and the mixture prepared in the dropping tank A is preferably 60.0 parts MD, 110.0 parts BZMA, 1.4 parts MMA, 28.6 parts MAA, and 60.0 parts PGMEA. A resin solution was obtained in the same manner as in Example 1-1 except that the mixture was changed to a mixture obtained by stirring. The analysis results are shown in Table 3.

[Comparative Example 1-4]
Other than changing the mixed solution prepared in the dropping tank A to 60.0 parts of benzylmaleimide (BZMI), 110.0 parts of BZMA, 1.4 parts of MMA, 28.6 parts of MAA, 60.0 parts of PGMEA and well mixed with stirring. Obtained a resin solution in the same manner as in Comparative Example 1-1. Also, a white powder of resin was obtained by the above reprecipitation operation. The analysis results are shown in Table 3.
BZMI is a monomer capable of obtaining a resin having an imide ring structure in the main chain, which is known as a resin having high heat resistance.

[Comparative Example 1-5]
Except for preparing 200.0 parts of MMA in the dropping tank A, a resin solution and a white powder of resin were obtained in the same manner as in Example 1-9. The analysis results are shown in Table 3.

[Comparative Example 1-6]
The polymerization reaction was carried out in the same manner as in Example 1-9 except that 128.1 parts of MD was used instead of 121.8 parts of AMA-M. However, gelation occurred during the polymerization to obtain a resin solution and a resin powder. I couldn't.

(Effect on the production stability of the binder resin of the present invention)
From the comparison between Example 1-3 and Comparative Example 1-3 and the comparison between Example 1-9 and Comparative Example 1-6, a tetrahydropyran ring was added to the main chain described in Non-Patent Document 1 and Patent Document 2. It can be seen that the resin having the polymer tends to cause abnormal high molecular weight or gelation during polymerization, whereas the binder resin of the present invention hardly causes such a phenomenon and is excellent in production stability.

<Preparation of colorant dispersion composition and evaluation of dispersion stability>
[Example 2-1]
(Preparation of colorant dispersion composition)
First, SOLSPERSE24000GR (manufactured by Nippon Lubrizol) as a dispersant was dissolved in PGMEA to 20%, and a binder resin solution prepared by diluting the resin solution obtained in Example 1-1 to 20% with PGMEA was prepared. did.
Next, C.I. I. Pigment Green 36 (Monastral Green 6Y-CL, manufactured by Heubach) 3.75 parts, and C.I. I. Pigment Yellow 150 (Yellow Pigment E4GN-GT, manufactured by Lanxess) 2.5 parts and 0.2 part of SOLPERSE 12000 (manufactured by Nihon Lubrizol) as a dispersant were weighed in a 225 ml mayonnaise bottle. Further, 3.75 parts of the 20% dispersant solution prepared in advance, 14.0 parts of the 20% binder resin solution, 25.8 parts of PGMEA, and 50 parts of zirconia beads having a diameter of 1.0 mm were added to a 225 ml mayonnaise bottle. Weighed and covered. This was shaken with a paint shaker for 3 hours for dispersion treatment, and then the color material dispersion composition and zirconia beads were fractionated to obtain a color material dispersion composition.

(Confirmation of distributed status)
The median diameter of the colorant dispersion composition immediately after the dispersion treatment was measured with a dynamic light scattering type particle size distribution measuring device (LB-500, manufactured by Horiba, Ltd.), and the median system was 100 nm or less. What exceeded 100 nm was set as x. The results are shown in Table 4.

(Evaluation of dispersion stability)
The one with a good dispersion state immediately after the dispersion treatment (one with a median diameter of 100 nm or less) is stored in a thermostatic chamber (23 ° C.), and after the dispersion treatment, the viscosity after 1 week, 2 weeks, and 4 weeks It measured using the plate-type rotational viscometer (TVE22LT, the Toki Sangyo make). The viscosity increase rate was calculated according to the following formula. The results are shown in Table 4.
Viscosity increase rate [%] = viscosity after 2 weeks (or after 4 weeks) / viscosity after 1 day × 100-100
[Examples 2-2 to 2-8]
Except having changed the binder resin solution as shown in Table 4, it carried out similarly to Example 2-1, and prepared the color material dispersion composition, and evaluated dispersion stability. The results are shown in Table 4.

[Example 2-9]
Preparation of the color material dispersion composition and dispersion stability were the same as in Example 2-1, except that the types and amounts of the components of the color material dispersion composition to be filled in the mayonnaise bottle were changed as follows. Evaluation was performed. The results are shown in Table 4.
C. I. Pigment Blue 15: 6 (Heliogen Blue L6700F, manufactured by BASF): 5.0 parts C.I. I. Pigment Violet 23 (Hostaperm Violet RL-NF, manufactured by Clariant): 1.25 parts SOLSPERSE24000GR in 20% PGMEA solution: 3.75 parts SOLPERSE12000: 0.2 parts The resin solution obtained in Example 1-2 by 20 PGMEA % Diluted: 14.0 parts PGMEA: 25.8 parts.

[Example 2-10]
Preparation of the color material dispersion composition and dispersion stability were the same as in Example 2-1, except that the types and amounts of the components of the color material dispersion composition to be filled in the mayonnaise bottle were changed as follows. Evaluation was performed. The results are shown in Table 4.
C. I. Pigment Red 254 (Irgaphor Red BT-CF, manufactured by Ciba Specialty Chemicals): 4.4 parts C.I. I. Pigment Red 177 (Chromophthal Red A3B, manufactured by Ciba Specialty Chemicals): 1.85 parts 20% PGMEA solution of SOLSPERSE24000GR: 5.0 parts What is obtained by diluting the resin solution obtained in Example 1-2 to 20% with PGMEA: 13.75 parts PGMEA: 25.0 parts.

[Example 2-11]
Preparation of the color material dispersion composition and dispersion stability were the same as in Example 2-1, except that the types and amounts of the components of the color material dispersion composition to be filled in the mayonnaise bottle were changed as follows. Evaluation was performed. The results are shown in Table 4.
Carbon black (MA220, manufactured by Mitsubishi Chemical Corporation): 6.25 parts SOLPERSE 24000GR in 20% PGMEA solution: 3.75 parts SOLPERSE12000: 0.2 part The resin solution obtained in Example 1-2 was diluted to 20% with PGMEA. Things: 14.0 parts PGMEA: 25.8 parts.

[Comparative Examples 2-1 to 2-3]
Except having changed the binder resin solution as shown in Table 4, it carried out similarly to Example 2-1, and prepared the color material dispersion composition, and evaluated dispersion stability. The results are shown in Table 4.

(Effect on the dispersion stability of the binder resin of the present invention)
From the comparison between Examples 2-1 to 2-2 and Comparative Example 2-1, it can be seen that the inclusion of the structural unit represented by the formula (1) improves the dispersion stability over a general binder resin. Further, from the comparison between Examples 2-1 to 2-2 and Comparative Examples 2-2 to 2-3, the effect is more than that of a resin having a tetrahydropyran ring in the main chain described in Non-Patent Document 1 and Patent Document 2. It can be seen that it is expensive. In addition, it is considered that the dispersion failure in Comparative Example 2-3 is caused by the binder resin (Comparative Example 1-3) having an abnormally high molecular weight. Furthermore, from Examples 2-3 to 2-8, it can be seen that the dispersion stability is excellent even if other copolymerization components are changed or R in the structural unit represented by the formula (1) is changed. .

<Evaluation of adhesion>
Adhesiveness is one of the coating film performances after drying greatly contributed by the binder resin, and was evaluated only with the binder resin in order to clearly evaluate the effect on the adhesiveness of the structural unit represented by the formula (1). . The resin structure is a resin structure that does not contain an acid group such as a carboxyl group or a strong base such as an amine.

[Example 3-1]
The binder resin powder obtained in Example 1-9 was dissolved in IPAC to make a 39% solution. This was applied to a float plate glass using a bar coater, naturally dried at room temperature for 10 minutes, and then dried at 70 ° C. for 5 minutes using a hot air dryer to obtain a binder resin coating film having a thickness of 10 μm. The adhesion of this coating film was evaluated on a scale of 0 to 5 according to JIS K 5600-5-6 (cross cut method). The results are shown in Table 5.

[Examples 3-2 to 3-6, Comparative Example 3-1]
Adhesion was evaluated in the same manner as in Example 3-1, except that the binder resin powder used was changed as shown in Table 5. The results are shown in Table 5.

<Evaluation of the effect of reducing polymerization inhibition by oxygen (surface curability)>
As an index for evaluating the effect of reducing polymerization inhibition by oxygen, surface curability in photo radical curing was used. The surface curability is one of the coating film performance after drying, which is greatly contributed by the binder resin, and in order to clearly evaluate the effect on the surface curability of the structural unit represented by the formula (1), A photocurable resin composition not containing an agent was prepared and evaluated.

[Example 4-1]
1.2 parts of binder resin powder obtained in Example 1-9, 2.8 parts of trimethylolpropane triacrylate (TMPTA), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur) 1173 (manufactured by Ciba Specialty Chemicals) 0.2 parts and 6.0 parts IPAC were stirred and mixed to obtain a uniform solution, which was applied to the float glass using a bar coater. After naturally drying at room temperature for 10 minutes, it was dried at 70 ° C. for 5 minutes using a hot air drier to obtain a photo-radical curable coating film having a thickness of 10 μm. Next, UV was irradiated using an ultra-high pressure mercury lamp capable of irradiating the coating film with a certain amount of light, and the surface was touched to confirm tackiness. UV irradiation and finger touch were repeated, and the UV integrated irradiation dose [J / cm ² ] when the surface was tackless was recorded. The smaller the UV integrated irradiation amount, the better the surface curability. The results are shown in Table 6.

[Examples 4-2 to 4-6, Comparative Example 4-1]
Surface curability was evaluated in the same manner as in Example 4-1, except that the binder resin powder used was changed as shown in Table 6. The results are shown in Table 6.

(Effects on adhesion and surface curability of the binder resin of the present invention)
From the comparison between Examples 3-1 to 3-2 and 4-1 to 4-2, and Comparative Examples 3-1 and 4-1, the adhesiveness is obtained by including the structural unit represented by the formula (1). It can also be seen that the surface curability is improved. Further, Examples 3-3 to 3-6 and 4-3 to 4-6 show that the effect is exhibited even when R in the structural unit represented by the formula (1) is changed.

<Evaluation of thermal decomposition resistance>
Thermal decomposition resistance is one of the coating film performance after drying, which is greatly contributed by the binder resin. In order to clearly evaluate the effect of the structural unit represented by the formula (1) on the thermal decomposition resistance, only the binder resin is used. evaluated.

[Example 5-1]
The binder resin powder obtained in Example 1-2 was measured under the following measuring equipment and conditions to obtain a dynamic TG curve. A 5% weight loss temperature was obtained from the obtained TG curve. The results are shown in Table 7.
Device: Thermo Plus TG8120 (Rigaku)
Atmosphere: Nitrogen flow 100 ml / min Temperature rising condition: Step-like isothermal control (SIA mode), Temperature rising rate = 10 ° C./min, Mass change rate value = 0.005% / sec.

[Example 5-2, Comparative Examples 5-1 to 5-2]
In the same manner as in Example 5-1, the 5% weight reduction temperature of each binder resin was measured. The results are shown in Table 7.

<Evaluation of transparency>
Transparency is one of the coating film performances after drying greatly contributed by the binder resin. In order to clarify the difference in transparency, only the binder resin was evaluated.

[Example 6-1]
The binder resin powder obtained in Example 1-2 was dissolved in PGMEA to form a 30% solution, and the transmittance [%] at a wavelength of 400 nm of this solution was measured with a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). It was set as the transmittance before heating. On the other hand, the binder resin powder is put in a glass container and heated at 230 ° C. for 1.5 hours, and then dissolved in PGMEA to form a 30% solution. The transmittance [%] at a wavelength of 400 nm is measured, and this is transmitted after heating. Rate. Moreover, the transmittance | permeability retention [%] was computed according to following Formula using the transmittance | permeability before and after a heating. The results are shown in Table 8.
Transmittance retention [%] = transmittance after heating / transmittance before heating × 100.

[Comparative Example 6-1]
Transparency was evaluated in the same manner as in Example 6-1 using the binder resin powder obtained in Comparative Example 1-4. The results are shown in Table 8.

(Effects on heat decomposability and transparency of binder resin of the present invention)
From the comparison between Examples 5-1 to 5-3 and Comparative Example 5-1, the thermal decomposition resistance is improved by including the structural unit represented by Formula (1), and Examples 5-1 to 5-3 From comparison with Comparative Example 5-2, it can be seen that the level is comparable to that of known heat resistant resins (resins containing an imide ring in the main chain). Moreover, from contrast with Example 6-1 and Comparative Example 6-2, it has transparency higher than resin which contains an imide ring in a principal chain, and is compatible with heat-resistant decomposability and transparency at a high level. I understand that.

The colorant-dispersed composition of the present invention can achieve both high dispersibility and other performances such as adhesion, heat resistance, surface curability, transparency, etc. Suitable for paints, for example, can be used for automobiles, painted steel sheets, building materials, cans, gravure, flexo, ink jet printers, color filters, and the like.

Claims (4)

In the color material dispersion composition containing a color material, a dispersant, a binder resin, and a liquid medium, the binder resin is a resin containing a structural unit represented by the following formula (1) in the main chain. A color material dispersion composition.

(R is a hydrogen atom or carbon atoms to Table 1-30 organic group, the organic group, is excluded chain saturated hydrocarbon group, an alkoxy (provided that the alkoxy containing an unsaturated group) substituted chained saturated hydrocarbon A part of hydrogen atoms of a hydrogen group, a hydroxy-substituted chain saturated hydrocarbon group, an alicyclic hydrocarbon group (excluding an alicyclic hydrocarbon group containing an unsaturated group), or an alicyclic hydrocarbon group is alkoxylated Group, hydroxy group substituted alicyclic hydrocarbon group (excluding alicyclic hydrocarbon group including unsaturated group), aromatic hydrocarbon group, aromatic hydrocarbon group part of the hydrogen atom is alkoxy A group (excluding an alkoxy group containing an unsaturated group) or an aromatic hydrocarbon group substituted with a hydroxy group. The colorant dispersion composition according to claim 1, wherein the binder resin is obtained by a production method including a step of polymerizing a monomer component containing a monomer represented by the following formula (2).

(R is a hydrogen atom or carbon atoms to Table 1-30 organic group, the organic group, is excluded chain saturated hydrocarbon group, an alkoxy (provided that the alkoxy containing an unsaturated group) substituted chained saturated hydrocarbon A part of hydrogen atoms of a hydrogen group, a hydroxy-substituted chain saturated hydrocarbon group, an alicyclic hydrocarbon group (excluding an alicyclic hydrocarbon group containing an unsaturated group), or an alicyclic hydrocarbon group is alkoxylated Group, hydroxy group substituted alicyclic hydrocarbon group (excluding alicyclic hydrocarbon group including unsaturated group), aromatic hydrocarbon group, aromatic hydrocarbon group part of the hydrogen atom is alkoxy A group (excluding an alkoxy group containing an unsaturated group) or an aromatic hydrocarbon group substituted with a hydroxy group. It is binder resin used for the color material dispersion composition of Claim 1 or 2, Comprising: The said binder resin is resin which contains the structural unit represented by following formula (1) in a principal chain. Binder resin for color material dispersion composition characterized.

(R is a hydrogen atom or carbon atoms to Table 1-30 organic group, the organic group, is excluded chain saturated hydrocarbon group, an alkoxy (provided that the alkoxy containing an unsaturated group) substituted chained saturated hydrocarbon A part of hydrogen atoms of a hydrogen group, a hydroxy-substituted chain saturated hydrocarbon group, an alicyclic hydrocarbon group (excluding an alicyclic hydrocarbon group containing an unsaturated group), or an alicyclic hydrocarbon group is alkoxylated Group, hydroxy group substituted alicyclic hydrocarbon group (excluding alicyclic hydrocarbon group including unsaturated group), aromatic hydrocarbon group, aromatic hydrocarbon group part of the hydrogen atom is alkoxy A group (excluding an alkoxy group containing an unsaturated group) or an aromatic hydrocarbon group substituted with a hydroxy group. A binder resin used in the color material dispersion composition according to claim 2 , wherein the binder resin comprises a step of polymerizing a monomer component containing a monomer represented by the following formula (2). A binder resin for a colorant-dispersed composition, characterized in that the resin is a resin containing a structural unit represented by the following formula (1) in the main chain.

(R is a hydrogen atom or carbon atoms to Table 1-30 organic group, the organic group, is excluded chain saturated hydrocarbon group, an alkoxy (provided that the alkoxy containing an unsaturated group) substituted chained saturated hydrocarbon A part of hydrogen atoms of a hydrogen group, a hydroxy-substituted chain saturated hydrocarbon group, an alicyclic hydrocarbon group (excluding an alicyclic hydrocarbon group containing an unsaturated group), or an alicyclic hydrocarbon group is alkoxylated Group, hydroxy group substituted alicyclic hydrocarbon group (excluding alicyclic hydrocarbon group including unsaturated group), aromatic hydrocarbon group, aromatic hydrocarbon group part of the hydrogen atom is alkoxy A group (excluding an alkoxy group containing an unsaturated group) or an aromatic hydrocarbon group substituted with a hydroxy group.

(R is a hydrogen atom or carbon atoms to Table 1-30 organic group, the organic group, is excluded chain saturated hydrocarbon group, an alkoxy (provided that the alkoxy containing an unsaturated group) substituted chained saturated hydrocarbon A part of hydrogen atoms of a hydrogen group, a hydroxy-substituted chain saturated hydrocarbon group, an alicyclic hydrocarbon group (excluding an alicyclic hydrocarbon group containing an unsaturated group), or an alicyclic hydrocarbon group is alkoxylated Group, hydroxy group substituted alicyclic hydrocarbon group (excluding alicyclic hydrocarbon group including unsaturated group), aromatic hydrocarbon group, aromatic hydrocarbon group part of the hydrogen atom is alkoxy A group (excluding an alkoxy group containing an unsaturated group) or an aromatic hydrocarbon group substituted with a hydroxy group.

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