JP2013227360A - Dispersant containing unsaturated group-containing polycarboxylic acid resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant exhibiting good dispersibility even if the content concentration of fine particles is high, and not affecting the performance of a resin composition containing the fine particles; and to provide the resin composition containing the dispersant, and having good development property even if the pigment concentration is high.SOLUTION: There is used as a dispersant an unsaturated group-containing polycarboxylic acid resin (A) which is a reaction product of a polybasic carboxylic anhydride (c) with a reactive carboxylate compound (B) which is a reaction product of an unsaturated group-containing monocarboxylic acid (b) with an epoxy resin (a) represented by general formula (1), wherein n is an average value and the number of 0 to 10; P and R are any one of a hydrogen atom, a halogen atom, a 1-8C alkyl group and a 1-8C aryl group, and P and R may be mutually identical or different; and G is a glycidyl group.

Description

  The present invention is obtained by reacting an epoxy resin (a) with a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in a molecule represented by acrylic acid or the like. The present invention relates to a fine particle dispersant containing a reactive epoxycarboxylate compound (B) and a reactive polycarboxylic acid compound (A) which is an acid-modified product thereof. Since these reactive epoxycarboxylate compound (B) and reactive polycarboxylic acid compound (A) have good fine particle dispersibility, the resin composition containing them is a film-forming material containing fine particles as components. , Solder resist, plating resist, color resist, color filter resist, various resists such as black matrix, optical waveguide, paint, printing ink, toner, adhesive, overcoat agent, etc. A tough cured product suitable for the application can be obtained.

  It is difficult to obtain a stable dispersion by dispersing fine particles in a carrier such as varnish. This is because the fine particles agglomerate with time to cause an increase in viscosity and poor fluidity of the composition. These changes cause various problems in manufacturing operations and product values. For example, the filter segment of a color filter is generally formed by applying a colored composition in which a pigment is dispersed in a carrier containing a monomer and a resin on a transparent substrate such as glass. If a coloring composition with poor coating properties is used, a coating film having a uniform film thickness cannot be obtained due to poor coating properties, poor leveling, or the like.

  For this reason, a dispersant is used as a method for stabilizing a dispersion containing fine particles. To date, a surfactant (Patent Document 1), a resin-type dispersant (Patent Document 2), or a polymer dispersant (Patent Document 3) is used. Have been proposed.

  For example, the resin composition for black matrix described in Patent Document 4 contains an acid-modified epoxy acrylate in which carbon black is dispersed using a dispersant.

  When a colored pigment such as carbon black is blended at a high concentration, it is necessary that the pigment has good developability and can be developed without a pigment residue by dispersing the pigment in affinity with the resin. Conventionally, as in Patent Document 4, the pigment is dispersed by a dispersant. However, the amount of the dispersant used in the resin composition is naturally limited, and high pigment dispersibility cannot be realized with the dispersant alone. On the other hand, there has been a demand for a resin composition exhibiting excellent developability even when the pigment concentration is high, that is, a resin composition exhibiting higher pigment dispersibility.

JP 2000-98608 A JP 2000-95992 A JP-A-4-139262 JP 2005-55814 A

  An object of the present invention is to provide a dispersant that exhibits good dispersibility even when the content concentration of fine particles is high and does not affect the performance of a resin composition containing fine particles.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that an epoxy resin having a specific structure, that is, an unsaturated group-containing polymer derived from an epoxy resin having a structure represented by the general formula (1). It has been found that carboxylic acid resins are excellent fine particle dispersants.

  That is, the present invention relates to the general formula (1)

(In formula, n shows an average value and shows the number of 0-10. P and R represent either a hydrogen atom, a halogen atom, a C1-C8 alkyl group, and a C1-C8 aryl group. Individual P and R may be the same or different from each other, G represents a glycidyl group.) Reaction product of epoxy resin (a) represented by unsaturated group-containing monocarboxylic acid (b) It is related with the dispersing agent of the microparticles | fine-particles containing the unsaturated group containing polycarboxylic acid resin (A) which is a reaction material of the reactive carboxylate compound (B) which is and polybasic acid carboxylic acid anhydride (c).

  Further, the present invention relates to a dispersant in which fine particles are pigments.

  Furthermore, the present invention relates to a dispersant in which the pigment is an inorganic pigment and / or an organic pigment.

  Furthermore, the present invention relates to a dispersant in which the inorganic pigment is carbon black or titanium black.

  Furthermore, it is related with the resin composition containing the dispersing agent in any one of the said.

  Furthermore, it is related with the resin composition containing the dispersing agent and microparticles | fine-particles in any one of the said.

  The dispersant of the present invention includes an unsaturated group-containing polycarboxylic acid resin and / or a reactive carboxylate compound having a specific structure, and the unsaturated group-containing polycarboxylic acid resin and / or reactive carboxylate compound includes: It is a binder resin having crosslinkability by itself and a dispersant. Therefore, not only a tough cured product can be obtained, but also fine particles can be sufficiently dispersed without using a dispersant, and fine particles can be dispersed at a high concentration by using other dispersants in combination. The cured product obtained from the resin composition containing the dispersant of the present invention is a film-forming material that is required to have thermal and mechanical toughness, a solder resist for printed wiring boards, and more preferably a color resist and a color filter. In addition to these resist materials, particularly black matrix materials, they can also be suitably used for optical waveguides, paints, printing inks, toners, adhesives, overcoat agents, and the like.

  The dispersant of the present invention is a reaction of a reactive carboxylate compound (B), which is a reaction product of an epoxy resin (a) and an unsaturated group-containing monocarboxylic acid (b), with a polybasic acid carboxylic acid anhydride (c). The unsaturated group-containing polycarboxylic acid resin (A) and / or the reactive carboxylate compound (B).

  The synthesis of the unsaturated group-containing polycarboxylic acid resin (A) will be described below. First, it starts from the synthesis of the reactive carboxylate compound (B). The reactive carboxylate compound (B) can be obtained by reacting the epoxy resin (a) with an unsaturated group-containing monocarboxylic acid (b).

  The epoxy resin (a) can be obtained by epoxidizing a phenol aralkyl resin. The phenol aralkyl resin used as a raw material is a resin in which an aromatic ring has a substituent via a methylene bond.

  Such a phenol aralkyl resin can also be obtained as a commercial product. Specifically, MEH-7851 manufactured by Meiwa Kasei Co., Ltd., KAYAHARD GPH65 manufactured by Nippon Kayaku Co., Ltd. can be exemplified, but not limited thereto. .

  Moreover, although the epoxy resin (a) which epoxidized these phenol aralkyl type resins can mention NC-3000 and NC-3000H by Nippon Kayaku Co., Ltd. as a commercial item, it is not limited to these.

  Next, a carboxylation step for the purpose of obtaining a reactive carboxylate compound (B) that is a reaction product of the unsaturated group-containing monocarboxylic acid (b) by imparting reactivity to the epoxy resin (a) Will be described.

  In this reaction, the reactive carboxylate compound (B) is obtained by reacting the epoxy group (a) with the unsaturated group-containing monocarboxylic acid (b).

  The unsaturated group-containing monocarboxylic acid (b) shown here reacts to impart reactivity to active energy rays to the reactive carboxylate compound (B) and the unsaturated group-containing polycarboxylic acid resin (A). It is what you want to do. Specific examples include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound.

  Most preferably, (meth) acrylic acid in terms of sensitivity when the reactive carboxylate compound (B) and the unsaturated group-containing polycarboxylic acid resin (A) become one component of the active energy ray-curable resin composition. , Reaction products of (meth) acrylic acid and ε-caprolactone or cinnamic acid.

  The charging ratio of the epoxy resin (a) and the unsaturated group-containing monocarboxylic acid (b) in this reaction can be appropriately changed. For example, when all the epoxy groups of the epoxy resin (a) are carboxylated, unreacted epoxy groups do not remain, so that the storage stability of the resulting reactive carboxylate compound (B) is increased. In this case, the curing reaction by the active energy ray of the reactive carboxylate compound (B) uses only the reactivity due to the introduced double bond.

  On the other hand, by reducing the amount of the carboxylic acid compound charged and leaving an unreacted residual epoxy group in the epoxy resin (a), a curing reaction by active energy rays was introduced into the curing of the reactive carboxylate compound (B). It becomes possible to use in combination the reactivity due to the unsaturated bond and the reaction due to the remaining epoxy group, for example, a polymerization reaction or a thermal polymerization reaction with a photocationic catalyst. However, in this case, since the temporal stability of the resulting reactive carboxylate compound (B) is lowered, attention must be paid to the examination of storage and production conditions.

  When manufacturing the reactive carboxylate compound (B) which does not leave an epoxy group, it is preferable that unsaturated group containing monocarboxylic acid (b) is 90-120 equivalent% with respect to 1 equivalent of epoxy resins (a). Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the carboxylic acid compound charged is larger than this, an excess of the unsaturated group-containing monocarboxylic acid (b) remains, which is not preferable.

  Moreover, when leaving an epoxy group, it is preferable that unsaturated group containing monocarboxylic acid (b) is 20-90 equivalent% with respect to 1 equivalent of epoxy resins (a). When deviating from this range, the effect of the composite curing is reduced. Of course, in this case, sufficient attention must be paid to gelation during the reaction and stability with time of the carboxylate compound (B).

  The carboxylation reaction may be either a solventless reaction or a reaction diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is inert to the carboxylation reaction.

  A preferable amount of the solvent to be used should be appropriately adjusted depending on the viscosity and usage of the obtained reactive carboxylate compound (B), but preferably 90 to 30 parts by mass with respect to the reactive carboxylate compound (B). More preferably, it is used so that it may become 80-50 mass parts.

  Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, and the like.

  During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is the reaction product, that is, the epoxy compound (a), the unsaturated group-containing monocarboxylic acid (b), and optionally a solvent or the like. It is 0.1-10 mass parts with respect to the total amount of the reaction material which added. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples thereof include known general basic catalysts such as zirconium acid.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 1 mgKOH / g or less, preferably 0.5 mgKOH / g or less, while sampling appropriately. The acid value is measured by a method according to JIS K 0070: 1992. In this way, the reactive carboxylate compound (B) can be obtained.

  Next, the acid addition step will be described in detail. The acid addition step is performed for the purpose of obtaining an unsaturated group-containing polycarboxylic acid resin (A) by introducing a carboxyl group into the carboxylate compound (B) obtained in the previous step as necessary. That is, a carboxyl group is introduced through an ester bond by adding a polybasic acid carboxylic acid anhydride (c) to a hydroxyl group generated by a carboxylation reaction.

  As specific examples of the polybasic acid carboxylic acid anhydride (c), for example, any compound having an acid anhydride structure in the molecule can be used, but alkali aqueous solution developability, heat resistance, hydrolysis resistance, etc. Excellent succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or anhydrous Maleic acid is particularly preferred.

  In the reaction for adding the polybasic acid carboxylic acid anhydride (c), the reaction solution containing the carboxylate compound (B) or the carboxylate compound (B) obtained by the carboxylation reaction is added to the polybasic acid carboxylic acid anhydride ( This can be done by adding c). The amount added should be changed as appropriate according to the application.

  During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is the carboxylate obtained from the reaction product, that is, the epoxy compound (a) and the unsaturated group-containing monocarboxylic acid (b). It is 0.1-10 mass parts with respect to the total amount of the reaction material which added the compound (B), polybasic acid carboxylic acid anhydride (c), and the solvent etc. depending on the case. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples include zirconium acid.

  This acid addition reaction may be either a solventless reaction or a reaction diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is inert to the acid addition reaction. In addition, when it is produced using a solvent in the carboxylation reaction that is the previous step, it must be subjected to the acid addition reaction that is the next step without removing the solvent, provided that it is inert to both reactions. You can also. The solvent that can be used may be the same as that used in the carboxylation reaction.

  In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling. The acid value is measured by a method according to JIS K 0070: 1992 as described above. In this way, the unsaturated group-containing polycarboxylic acid resin (A) can be obtained.

  The unsaturated group-containing polycarboxylic acid resin (A) and / or the reactive carboxylate compound (B) can be purified or used as the dispersant of the present invention in the form of a solution at the time of synthesis. Depending on the handling property at the time of use, the purified product may be used again as a solution. Moreover, you may use as a composition containing a well-known dispersing agent as needed.

  When the dispersant of the present invention is used as a solution, the organic solvent is appropriately selected according to the fine particles or the resin composition of the present invention, in addition to the solvent used during synthesis. For example, benzene such as benzene, toluene, xylene, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Propylene glycol monoalkyl ether acetates such as ethyl ether acetate and propylene glycol monobutyl ether acetate, propionate esters such as methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, methyl lactate, lactic acid Lactic acid esters such as ethyl and butyl lactate, ester solvents, ketone solvents, etc. It is below.

  Examples of ester solvents include alkyl acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, and diethylene glycol monoethyl ether monoacetate. Monoethylene ether such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether monoacetates, dialkyl glutarate, dialkyl succinate, Alkyl polycarboxylates such as dialkyl adipates Ester, and the like can be mentioned.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, and isophorone.

  In addition, alcohol solvents, ether solvents, and acetate solvents can be used. Examples of alcohol solvents include alkyl alcohols such as ethanol and isopropyl alcohol, 3-methyl-3-methoxybutanol, 3-methyl-3-ethoxybutanol, 3-methyl-3-n-propoxybutanol, and 3-methyl- 3-isopropoxybutanol, 3-methyl-3-n-butoxysibutanol, 3-methyl-3-isobutoxysibutanol, 3-methyl-3-sec-butoxybutanol, 3-methyl-3-tert-butoxy Examples include alkoxy alcohols such as butanol.

  Examples of ether solvents include alkyl ether solvents, monohydric alcohol ether solvents, alkylene glycol monoalkyl ether solvents, alkylene glycol dialkyl ether solvents, dialkylene glycol alkyl ether solvents, trialkylene glycol alkyl ether solvents, Examples include cyclic ether solvents.

  Examples of the alkyl ether solvent include dimethyl ether, diethyl ether, ethyl butyl ether and the like.

  Examples of monohydric alcohol ether solvents include 3-methyl-3-methoxybutanol methyl ether, 3-methyl-3-ethoxybutanol ethyl ether, 3-methyl-3-n-butoxysibutanol ethyl ether, 3-methyl- Examples include 3-isobutoxysibutanol propyl ether, 3-methyl-3-sec-butoxybutanol-isopropyl ether, and 3-methyl-3-tert-butoxybutanol-n-butyl ether.

  Examples of the alkylene glycol monoalkyl ether solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol Mono-sec-butyl ether, propylene glycol mono-tert-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether Ethylene glycol monobutyl -sec- butyl ether, and ethylene glycol monobutyl -tert- butyl ether.

  Examples of the alkylene glycol dialkyl ether solvent include propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol diisobutyl ether, propylene glycol di-sec-butyl ether. , Propylene glycol di-tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl ether, ethylene glycol di-sec Ether, and ethylene glycol di -tert- butyl ether.

  Dialkylene glycol alkyl ether solvents include, for example, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol diisopropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol diisobutyl ether. , Dipropylene glycol di-sec-butyl ether, dipropylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diisopropyl ether, diethylene glycol di-n-butyl ether, diethylene glycol diisobutyl Ether, diethylene glycol di -sec- butyl ether, diethylene glycol di -tert- butyl ether, and the like.

  Examples of the trialkylene glycol alkyl ether solvent include tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tridipropylene glycol dipropyl ether, tripropylene glycol diisopropyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol diisobutyl ether, Tripropylene glycol di-sec-butyl ether, tripropylene glycol di-tert-butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol diisopropyl ether, triethylene glycol di-n-butyl ether , Triethylene Recall diisobutyl ether, triethylene glycol di -sec- butyl ether, alkylene glycol dialkyl ethers such as triethylene glycol di -tert- butyl ether, and the like.

  Examples of acetate solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-sec-butyl ether. Acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol mono-tert-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monopropyl ether acetate, Pyrene glycol mono-n-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Ethoxybutyl acetate, 3-methyl-3-propoxybutyl acetate, 3-methyl-3-isopropoxybutyl acetate, 3-methyl-3-n-butoxyethyl acetate, 3-methyl-3-isobutoxybutyl acetate, 3 -Alkylene glycol monoalkyl ether acetates such as methyl-3-sec-butoxy butyl acetate and 3-methyl-3-tert-butoxy butyl acetate; Glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, butyl acetate and the like.

  Examples of the cyclic ether solvent include tetrahydrofuran and dioxane.

  These organic solvents can be used alone or in combination of two or more. Further, in the present invention, the content of the organic solvent is appropriately adjusted according to the fine particles, viscosity, handleability, etc., but is usually 50 to 2000 mass per 100 mass parts of the purified dispersant of the present invention. Parts, preferably 100 to 1000 parts by mass.

  When the total amount with the fine particles is 100% by mass, the dispersant of the present invention can usually be used in the range of 0.1 to 99% by mass, and preferably in the range of 1 to 50% by mass.

  Examples of the dispersant other than the dispersant of the present invention that can be used in combination with the dispersant of the present invention include a surfactant, a resin-type dispersant, and a polymer dispersant, but are not particularly limited.

  Examples of the polymer dispersant include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, Naphthalene sulfonic acid formalin condensate is exemplified, and further, polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like can be mentioned. The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the fine particles and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (Azo face) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 6 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  In the case of using a dispersant other than the dispersant of the present invention, the amount used thereof can be usually used in the range of 0.1 to 100% by mass when the fine particles are 1% by mass, like the dispersant of the present invention. The range of 1-50 mass parts is preferable. In addition, the use ratio with the dispersing agent of this invention can be adjusted suitably.

  Examples of the fine particles in the present invention include organic substances (wood powder, etc.), metal oxides, ceramics, color pigments and the like, but are not particularly limited. The resin composition of the present invention can be appropriately selected according to the use and purpose of the resin composition.

  The color pigment used in the present invention is used for using the resin composition of the present invention as a coloring material. In the present invention, organic, inorganic or metal pigments can be used alone or in admixture of two or more.

  Examples of the color pigment include phthalocyanine-based, azo-based, and quinacridone-based organic pigments. Specific examples of organic pigments are shown below by color index numbers.

  For example, C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, Red pigments such as H.264, 272, or 279 can be used. These are suitably used for the coloring composition for red color filters. In this case, a yellow pigment or an orange pigment can be used in combination.

  For example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Yellow pigments such as 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, or 214 can be used. These are suitably used for the coloring composition for yellow color filters.

  For example, C.I. I. Orange pigments such as Pigment orange 36, 43, 51, 55, 59, 61, 71, or 73 can be used. These are suitably used for the coloring composition for orange color filters.

  For example, C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, or 58 can be used. These are suitably used for the coloring composition for green color filters, and in this case, the yellow pigment can be used in combination.

  For example, C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, or 80 can be used. These are suitably used for the coloring composition for blue color filters, and in this case, a purple pigment described later can be used in combination.

  For example, C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, or 81 can be used. These are suitably used for the coloring composition for cyan color filters.

  For example, C.I. I. Pigment Violet 1, or 19, or C.I. I. Purple pigments such as Pigment Red 81, 144, 146, 177, or 169, and red pigments can be used. These are suitably used for the coloring composition for a magenta color filter, and in this case, the yellow pigment can be used in combination.

  Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic Metal oxide powder such as iron black, titanium oxide or iron tetroxide, metal sulfide powder, metal powder, titanium black, carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, perylene black And cyanine black. In the resin composition of the present invention, an inorganic pigment may be used in combination with an organic pigment in order to ensure good coatability, sensitivity, developability and the like while balancing the saturation and lightness.

  As the metal pigment used in the present invention, base metal powders such as aluminum, zinc, iron, magnesium, copper, nickel, and alloy powders thereof can be used.

In addition, metal oxide particles can be used as the fine particles of the present invention. Examples of the metal oxide particles include silica, hollow silica, fumed silica, and hydrophobic fumed silica, fused silica, crystals obtained by surface treatment of fumed silica with hexamethyldisilazane, methylchlorosilanes, silicone oils, and the like. Silica, titanium oxide, zirconium oxide, zinc oxide, cerium oxide, tin oxide, antimony doped tin oxide (ATO), phosphorus doped tin oxide (PTO), tin doped indium oxide (ITO), aluminum doped zinc oxide, gallium doped zinc oxide, Metal oxide particles such as antimony pentoxide and zinc antimonate can be used. These metal oxide particles may be used alone or in combination of two or more. For example, silica (SiO ₂ ) used in the present invention is not particularly limited, and powdered silica and colloidal silica can be used alone or in combination.

  Examples of the powder silica include AEROSIL 90 and OX 50 manufactured by Nippon Aerosil Co., Ltd., E-200A, E-220A, K-500, E-1009, E-1011, E-1030, and E- manufactured by Tosoh Silica Co., Ltd. 150J, E-170, etc. can be used. Examples of colloidal silica include Snowtex S, OS, XS, OXS, 20, 30, 40, 50, O, AK, O-40, CM, 20L, C, ZL, XL, N, manufactured by Nissan Chemical Industries, Ltd. Quatron PL-1, PL-3, PL-7, PL-20 manufactured by Fuso Chemical Industry Co., Ltd., silicaloid, silicaloid-LL, silicaloid-A manufactured by Sanko Colloid Chemical Co., Ltd. can be used. . These can be used alone or in combination.

  In addition, composite particles including aggregates of metal particles and inorganic oxide particles, and composite particles provided with an inorganic coating layer, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate , Calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, two Molybdenum sulfide can also be cited as the fine particles used in the present invention.

Moreover, a glass filler can also be used in the present invention as fine particles. The glass filler is formed by the glass composition. Examples of the composition of the glass composition used for the glass filler of the present invention include those containing SiO ₂ , Al ₂ O ₃ , CaO, and MgO, and those containing B ₂ O ₃ .

  In the present invention, it is also possible to use a dielectric (a substance that generates dielectric polarization when an electric field is applied) as the fine particles. Examples thereof include dielectric ceramics, dielectric resin, metal powder, and magnetic powder.

  In the present invention, a dye may be used as the fine particles. Examples of the dye include C.I. I. Acid Yellow 79, C.I. I. Acid Red 249, C.I. I. Acid Red 289, C.I. I. Acid Black 52, C.I. I. Acid Black 52: 1 or water soluble dyes such as water soluble copper phthalocyanine dyes.

  The fine particles can be used alone or in combination of two or more. The fine particles may be used in the form of a powder or a dispersion thereof, but when used as a dispersion, if the total amount of the dispersion is 100% by mass, one containing 5 to 60% by mass of fine particles should be used. Is preferred. In the present invention, the average particle size of the fine particles is at most 5 μm.

  Since the dispersion of the fine particles proceeds satisfactorily by the dispersant of the present invention, the pigment concentration can be increased without using a known dispersant or by using it together with a known dispersant. Furthermore, if the dispersant of the present invention is used in a composition that requires development, a resin composition with good dispersion can be obtained. For example, a photosensitive resin composition that is excellent in patterning characteristics and has few development residues in the development-dissolved part can be obtained with the dispersant of the present invention.

  The resin composition of the present invention contains at least the dispersant of the present invention, and preferably further contains fine particles. In the present invention, a binder polymer, a photopolymerizable monomer, and a photopolymerization initiator can further be included depending on the application. For this reason, the resin composition of the present invention includes a film forming material, a printed wiring board solder resist, a color resist, a color filter resist material, a black matrix material, and the like that are required to have thermal and mechanical toughness. It can also be suitably used for optical waveguide materials, paints, printing inks, toners, adhesives, overcoat agents and the like.

  Although it can select suitably as a binder polymer according to the use of a resin composition, alkali-soluble resin or water-soluble resin can be mentioned, for example.

  As the alkali-soluble resin, for example, a polymer having a carboxyl group is preferable as long as it is a resin that can be dissolved in an alkaline (water) solution. Examples of the alkaline (water) solution include a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a tetramethylammonium hydroxide aqueous solution, a diethanolamine aqueous solution, and an ethanolamine aqueous solution. And those obtained by appropriately mixing a surfactant with these, but the present invention is not limited thereto. As the polymer having a carboxyl group, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “unsaturated monomer having a carboxyl group”) and other copolymerizable ethylenically unsaturated monomers ( Hereinafter, a copolymer of a monomer mixture consisting of simply “other unsaturated monomer” (hereinafter simply referred to as “copolymer having a carboxyl group”) is preferable. Specific examples of the unsaturated monomer having a carboxyl group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid , Unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, or acid anhydrides thereof; and trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof. . These unsaturated monomers having a carboxyl group can be used alone or in admixture of two or more.

  Specific examples of the other unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene. Aromatic vinyl compounds such as p-methoxystyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, i-propyl acrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl acrylate, i -Butyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate Salts, unsaturated carboxylic acid esters such as 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-amino Unsaturated carboxylic acid aminoalkyl esters such as propyl acrylate and 3-aminopropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxyl such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Acid vinyl esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and methallyl glycidyl ether; acrylonite Vinyl cyanide compounds such as ril, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacryl Unsaturated amides or unsaturated imides such as amide and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n- Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as butyl methacrylate and polysilicon. These other unsaturated monomers can be used alone or in admixture of two or more.

  Preferred combinations of unsaturated monomers having these carboxyl groups and other unsaturated monomers include acrylic acid and / or methacrylic acid and methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and styrene. And at least one other unsaturated monomer selected from the group of polystyrene macromonomers and polymethylmethacrylate macromonomers. Preferable specific examples of the polymer having a carboxyl group include acrylic acid / benzyl acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / polystyrene. Macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic Acid / benzyl methacrylate copolymer, acrylic acid / benzyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / styrene copolymer, acrylic acid / ben Methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer Acrylic acid copolymer such as polymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer; Methacrylic acid / benzyl acrylate copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylic Styrene / styrene copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid Acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / Polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl Methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxy Examples thereof include methacrylic acid copolymers such as ethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer.

  A polymer in which an unsaturated double bond is further introduced into the side chain of the polymer having a carboxyl group is also useful in the present invention. Examples of such a polymer include, for example, hydroxyethyl in the maleic anhydride part of a copolymer of maleic anhydride and a copolymer of styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide and the like copolymerizable therewith. A compound obtained by reacting an acrylate having an alcoholic hydroxyl group such as an acrylate or an acrylate having an epoxy group such as glycidyl methacrylate and an acrylate having an alcoholic hydroxyl group such as acrylic acid, acrylate ester and hydroxyethyl acrylate And a compound obtained by further reacting acrylic acid with the hydroxyl group of the copolymer.

  Next, examples of water-soluble resins include acrylic resins, methacrylic resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, acryloyl morpholine resins, and the like. Examples of acrylic resins include polymers and copolymers such as acrylic acid, sodium acrylate, and acrylamide. Examples of methacrylic resins include polymers such as methacrylic acid, sodium methacrylate, and 2-hydroxymethacrylic acid. Or a copolymer is mentioned, respectively.

  Examples of the photopolymerizable monomer that can be used in the present invention include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol, methoxytetraethylene glycol, and polyethylene. Glycol mono- or di (meth) acrylates such as glycol, N, N-dimethyl (meth) acrylamide, (meth) acrylamides such as N-methylol (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate Such as aminoalkyl (meth) acrylates such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate Polyol or adducts of ethylene oxide or propylene oxide of phenols such as polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts, phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A ( (Meth) acrylates, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, (meth) acrylates of glycidyl ether such as triglycidyl isocyanurate, and ε-caprolactone modified (meta) such as caprolactone-modified tris (acryloxyethyl) isocyanurate ) Acrylates and melamine (meth) acrylates.

  These photopolymerizable monomers can be used alone or in combination of two or more. A photopolymerizable monomer can be used in the ratio which occupies 5-60 mass% normally in the resin composition of this invention, Preferably 10-50 mass%.

  The photopolymerization initiator that can be used in the resin composition of the present invention is not particularly limited as long as it has sufficient sensitivity to ultraviolet rays emitted from an ultrahigh pressure mercury lamp generally used as an exposure light source. Specific examples of the photopolymerization initiator that can be used include, for example, benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, and esterified products of benzoylbenzoic acid. 4-benzoyl-4′-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylamino Methylbenzoate, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydro Cycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate, 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4-bis (trichloro Methyl) -6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-bis ( Tribromomethyl) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5 s-triazine, 2,4-bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid, 1- (4- Phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4 -Methylsulfanylphenyl) butan-1-oneoxime-O-acetate, 4,4'-bis (diethylamino) benzophenone, P-dimethylaminobenzoic acid isoamyl ester, P-dimethylaminobenzoic acid ethyl ester, 2,2'-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, Benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl Acetophenones such as ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, anthraquinones such as 2-aminoanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Thioxanthones such as chlorothioxanthone and 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone Benzophenones such as 4-benzoyl-4′-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.

  These are Kaya Cure DMBI, Kaya Cure BDK, Kaya Cure BP-100, Kaya Cure BMBI, Kaya Cure DETX-S, Kaya Cure EPA (all manufactured by Nippon Kayaku), Daro Cure 1173, Daro Cure 1116 (all from Merck Japan), Irgacure 907, Iruga Cure Cure 369 (manufactured by Ciba Specialty Chemicals), biimidazole (manufactured by Kurokin Kasei), STR-110, STR-1 (all manufactured by Respe Chemical) are easily available from the market.

  These photopolymerization initiators can be used alone or in combination of two or more. These contents are 0.5-30 parts by mass, preferably 1-30 parts, when the total amount of the binder polymer, photopolymerizable monomer, dispersant of the present invention, and fine particles of the resin composition of the present invention is 100 parts by mass. 25 parts by mass.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a part shows a mass part.

The epoxy equivalent was measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JIS K-7236: 2001.
2) Acid value: measured by a method according to JIS K 0070: 1992.
3) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min. 40 ° C
Detector: Differential refractometer
Molecular weight standard: polystyrene

Example 1: Preparation of dispersant of the present invention (reactive polycarboxylic acid compound (A-1))
As epoxy resin (a), phenol-biphenyl novolac type epoxy resin (Nippon Kayaku Co., Ltd. NC-3000H epoxy equivalent 288g / eq., Softening point 70 degreeC) 288 parts, unsaturated group containing monocarboxylic acid (b) A reactive carboxylate compound (hereinafter simply referred to as “solid content”) obtained by calculation of 72 parts of acrylic acid (abbreviation AA, Mw = 72), 0.5 part of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent ), And reacted at 100 ° C. for 24 hours to obtain a reactive carboxylate compound (B-1) solution.

  The carboxylate compound (B-1) solution thus obtained has a polybasic acid carboxylic acid anhydride (c) of 84 parts of tetrahydrophthalic anhydride (abbreviated as THPA) and a solid content of 65 parts by mass as a solvent. Propylene glycol monomethyl ether monoacetate was added, and the mixture was heated to 100 ° C. for acid addition reaction to obtain a reactive polycarboxylic acid compound (A-1) solution which is a dispersant of the present invention.

Comparative Example 1: Preparation of reactive polycarboxylic acid compound (A-2)
170 parts of trisphenolmethane type epoxy resin (Nippon Kayaku Co., Ltd. EPPN-502H epoxy equivalent 170 g / eq., Softening point 67 ° C.) as epoxy resin (a), acrylic as unsaturated group-containing monocarboxylic acid (b) 72 parts of acid (abbreviation AA, Mw = 72), 0.5 part of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 80% by mass, and reacted at 100 ° C. for 24 hours To obtain a carboxylate compound (B-2) solution.

  The resulting carboxylate compound (B-2) solution has a polybasic acid carboxylic acid anhydride (c) of propylene so as to have 66 parts of tetrahydrophthalic anhydride (abbreviated as THPA) and a solid content of 65 parts by weight as a solvent. Glycol monomethyl ether monoacetate was added and heated to 100 ° C. to carry out an acid addition reaction to obtain a reactive polycarboxylic acid compound (A-2) solution.

Comparative Example 2: Preparation of reactive polycarboxylic acid compound (A-3)
199 parts of cresol novolac-type epoxy resin (EOCN-1020 epoxy equivalent 199 g / eq., Softening point 62 ° C., manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin (a), acrylic acid as unsaturated group-containing monocarboxylic acid (b) (Abbreviation AA, Mw = 72) 72 parts, 0.5 parts of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent so as to be 80% by mass of solid content, and reacted at 100 ° C. for 24 hours. The carboxylate compound (B-3) solution was obtained.

  Propylene glycol so that the resulting carboxylate compound (B-3) solution has 73 parts of tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid carboxylic acid anhydride (c) and 65 parts of solid content as a solvent. Monomethyl ether monoacetate was added, and the mixture was heated to 100 ° C. for acid addition reaction to obtain a reactive polycarboxylic acid compound (A-3) solution.

  Table 1 shows the mass average molecular weight (Mw) and solid content acid value of the resin thus obtained.

Table 1: Preparation of reactive polycarboxylic acid compound (A)
Reactive polycarboxylic acid compound (A) Mw Solid content acid value Example 1 A-1 4500 101.1 mg KOH / g
Comparative Synthesis Example 1 A-2 3500 100.8 mg KOH / g
Comparative Synthesis Example 2 A-3 4200 101.5 mgKOH / g

Example 2
20 parts of the reactive polycarboxylic acid compound (A-1), which is the dispersant of the present invention obtained in Synthesis Example 1, and DPHA (trade name: Nippon Kayaku Co., Ltd. acrylate) as the other reactive compound (C) Monomer) 5.0 parts, propylene glycol monomethyl ether acetate 10 parts as an organic solvent, and Mitsubishi carbon black MA-100: 80 parts as a color pigment were mixed and stirred. 115 parts of glass beads were put therein, dispersed for 1 hour with a paint shaker, and then coarse particles were removed by ultracentrifugation to obtain a carbon black dispersion (D-1) which is a resin composition of the present invention. .

Comparative Example 1 and Comparative Example 2
Similarly, a carbon black dispersion liquid (D-2) and a carbon black dispersion liquid (D-3) were obtained from the reactive polycarboxylic acid compound (A-2) and the reactive polycarboxylic acid compound (A-3). .

Example 3, Comparative Example 3 and Comparative Example 4
The dispersions of Example 3, Comparative Example 3 and Comparative Example 4 were coated on a polyethylene terephthalate film with a wire bar coater # 2, and dried for 10 minutes with a hot air dryer at 80 ° C.
The gloss of the coating film surface after drying was measured using a 60 ° reflection gloss meter to evaluate the dispersibility of the carbon black. At this time, a higher gloss indicates better pigment dispersibility.

Table 2: Evaluation of carbon black dispersibility
Carbon black dispersion (D) Glossy
Example 3 D-1 42
Comparative Example 3 D-2 35
Comparative Example 4 D-3 31

  From the above, it is clear that the dispersant of the present invention can disperse fine particles satisfactorily even when used alone.

  The dispersant of the present invention is, for example, an active energy ray curable film forming material, a solder resist, a plating resist, a color resist, a color filter resist, and a black matrix as a dispersant exhibiting good pigment dispersibility. It can be suitably used for various resists, optical waveguides, paints, printing inks, toners, adhesives, overcoat agents and the like.

Claims (6)

General formula (1)

(In formula, n shows an average value and shows the number of 0-10. P and R represent either a hydrogen atom, a halogen atom, a C1-C8 alkyl group, and a C1-C8 aryl group. Individual P and R may be the same or different from each other, G represents a glycidyl group.) Reaction product of epoxy resin (a) represented by unsaturated group-containing monocarboxylic acid (b) A fine particle dispersant comprising an unsaturated group-containing polycarboxylic acid resin (A) which is a reaction product of the reactive carboxylate compound (B) and the polybasic acid carboxylic acid anhydride (c). The dispersant according to claim 1, wherein the fine particles are pigments. The dispersant according to claim 2, wherein the pigment is an inorganic pigment and / or an organic pigment. The dispersant according to claim 3, wherein the inorganic pigment is carbon black or titanium black. The resin composition containing the dispersing agent as described in any one of Claims 1 thru | or 5. A resin composition comprising the dispersant according to any one of claims 1 to 5 and fine particles.