WO2016098578A1 - Pigment-dispersed resin and pigment-dispersed paste - Google Patents

Abstract

The present invention addresses the problem of providing: a pigment-dispersed resin that exhibits excellent pigment dispersibility even at a high pigment concentration; and a pigment-dispersed paste that exhibits excellent stability. The present invention provides a pigment-dispersed resin characterized by containing a polycyclic aromatic hydrocarbon-containing monomer at a quantity of 1-70 mass % relative to the total quantity of solid content, and in that the polycyclic aromatic hydrocarbon-containing monomer is a polymerizable unsaturated monomer having a specific polycyclic aromatic hydrocarbon.

Description

Pigment dispersion resin and pigment dispersion paste

[Cross-reference of related applications]
This application claims priority based on Japanese Patent Application No. 2014-252648 filed on Dec. 15, 2014, the entire disclosure of which is incorporated herein by reference.
The present invention relates to a pigment dispersion resin suitable for dispersing various pigments even at a high pigment concentration, and a pigment dispersion paste containing the pigment dispersion resin.

Conventionally, a pigment-like pigment dispersion in which a pigment is dispersed in a mixture of a pigment-dispersing resin, a solvent, and, in some cases, a dispersion aid, is a paint, a colored film, a colored sheet, a printing ink, a cosmetic, a magnet modifier, Widely used in fields such as LED sealing materials, various rubber products, and resin molded products.

In these fields, there is an ever-increasing demand for performance improvements such as color developability, sharpness, conductivity, finish, etc. Therefore, excellent pigment dispersion ability and pigment particles in the formed pigment dispersion Development of pigment dispersion resins having excellent pigment dispersion stability that does not cause re-aggregation has been underway.

In designing the pigment dispersion resin, it is important to achieve both the wettability to the pigment and the dispersion stability of the pigment dispersion resin in the solvent. Regarding wettability, it is said that the pigment-dispersed resin has a low viscosity and a low molecular weight, and that it is advantageous that there is an interaction between the hydrophobic part of the pigment surface and the hydrophobic part of the pigment-dispersed resin. It is said that it is advantageous that the solid repulsion layer is formed on the pigment surface and the solubility of the pigment-dispersed resin in the continuous phase is good.

It is also important that a small amount of the pigment-dispersed resin exerts the above effects so that the pigment-dispersed resin does not adversely affect the performance of the final product itself such as a coating film, film or printed matter.

For example, Patent Document 1 discloses that specific carbon black is dispersed with a pigment dispersant, and the pigment dispersant is a styrene-α-methylstyrene-acrylic acid copolymer and / or a styrene-maleic anhydride copolymer. An electrically conductive high concentration carbon black dispersion is disclosed. However, when the pigment dispersion paste is stored for a long period of time, the pigment stability is inferior and the pigment may reaggregate.
Patent Document 2 discloses the use of a reaction product of an amine and a dicarboxylic anhydride group-containing polymer as a pigment dispersion additive. However, due to the high polarity of the pigment-dispersed resin, performance such as water resistance and weather resistance may deteriorate in the final product such as a coating film or film.

Japanese Patent Laid-Open No. 11-158321 Special table 2011-521019 gazette

An object of the present invention is to provide a pigment dispersion resin having excellent pigment dispersibility and a pigment dispersion paste having excellent stability even at a high pigment concentration.

As a result of intensive studies to solve the above problems, the inventors have found that the above problems can be solved by a pigment dispersion resin containing a monomer having a polycyclic aromatic hydrocarbon, and to complete the present invention. It came.

That is, the present invention provides the following pigment dispersion resin and pigment dispersion paste.

Item 1. A pigment dispersion resin, which is a copolymer of a raw material monomer containing 1 to 70% by mass of a monomer (A) having a polycyclic aromatic hydrocarbon.

Item 2. Item 1 above, wherein the monomer (A) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon represented by the following formula (1): The pigment-dispersed resin described in 1.

(Wherein R represents a hydrogen atom or a methyl group, A represents a polycyclic aromatic hydrocarbon group, W may or may not be present. When W is present, W is a carbon atom, In the case where the number of nitrogen atoms and / or oxygen atoms is 1 to 20 and W is not present, W is directly bonded to A.)
Item 3. The polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer having a naphthyl group represented by the following formula (2) or a derivative (A-2) thereof: Item 3. The pigment-dispersed resin according to Item 2.

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, Represents a nitro group, a halogen atom, an aryloxy group, an alkylthio group or an arylthio group, and W may or may not be present, and when W is present, W is a carbon atom, a nitrogen atom and / or When the organic group has 1 to 20 oxygen atoms and W does not exist, W is directly bonded to the naphthyl group.)
Item 4. Item 3. The polymerizable unsaturated monomer having a naphthyl group or a derivative (A-2) thereof is a naphthyl (meth) acrylate represented by the following formula (3) or a derivative (A-3) thereof: The pigment-dispersed resin described in 1.

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, sulfonic acid group, carboxyl group, alkoxycarbonyloxy group) Group, phosphoryloxy group, amino group, nitro group, halogen atom, aryloxy group, alkylthio group or arylthio group, when W is present, W is the number of carbon atoms, nitrogen atoms and / or oxygen atoms Is an organic group of 1 to 20 or a single bond.)
Item 5. The naphthyl (meth) acrylate or derivative (A-3) thereof is 4-substituted-1-naphthyl (meth) acrylate (A-4) represented by the following formula (4) or a derivative thereof: Item 5. A pigment-dispersed resin according to Item 4.

Wherein R represents a hydrogen atom or a methyl group, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, phosphoryloxy Group.)
Item 6. Item 6. The pigment dispersion resin according to any one of Items 2 to 5, which contains 5 to 65% by mass of styrene based on the total amount of the polymerizable unsaturated monomer components.

Item 7. Item 7. The pigment dispersion resin according to any one of Items 2 to 6, further comprising 1 to 30% by mass of a polyalkylene glycol macromonomer based on the total amount of the polymerizable unsaturated monomer component.

Item 8. Item 8. The pigment-dispersed resin according to any one of Items 2 to 7, further comprising at least one (meth) acrylamide compound.

Item 9. 9. A pigment dispersion paste comprising the pigment dispersion resin according to any one of items 1 to 8 and a pigment.

Item 10. 9. A conductive pigment dispersion paste comprising the pigment dispersion resin according to any one of items 1 to 8 and a conductive pigment.

Item 11. A method for producing a pigment-dispersed resin, comprising a step of copolymerizing a raw material monomer containing 1 to 70% by mass of a monomer (A) having a polycyclic aromatic hydrocarbon.

Item 12. Item 11 above, wherein the monomer (A) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon represented by the following formula (1): The method described in 1.

(Wherein R represents a hydrogen atom or a methyl group, A represents a polycyclic aromatic hydrocarbon group, W may or may not be present. When W is present, W is a carbon atom, In the case where the number of nitrogen atoms and / or oxygen atoms is 1 to 20 and W is not present, W is directly bonded to A.)
Item 13. The polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer having a naphthyl group represented by the following formula (2) or a derivative (A-2) thereof: Item 13. The method according to Item 12.

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, Represents a nitro group, a halogen atom, an aryloxy group, an alkylthio group or an arylthio group, and W may or may not be present, and when W is present, W is a carbon atom, a nitrogen atom and / or When the organic group has 1 to 20 oxygen atoms and W does not exist, W is directly bonded to the naphthyl group.)
Item 14. Item 13. The polymerizable unsaturated monomer having a naphthyl group or a derivative (A-2) thereof is a naphthyl (meth) acrylate represented by the following formula (3) or a derivative (A-3) thereof: The method described in 1.

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, sulfonic acid group, carboxyl group, alkoxycarbonyloxy group) Group, phosphoryloxy group, amino group, nitro group, halogen atom, aryloxy group, alkylthio group or arylthio group.)
Item 15. Item 14 is characterized in that the naphthyl (meth) acrylate or derivative (A-3) thereof is 4-substituted-1-naphthyl (meth) acrylate (A-4) represented by the following formula (4): The method described.

Wherein R represents a hydrogen atom or a methyl group, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, phosphoryloxy Group.)
Item 16. Item 16. The method according to any one of Items 12 to 15, which contains 5 to 65% by mass of styrene based on the total amount of the polymerizable unsaturated monomer components.

Item 17. Item 17. The method according to any one of Items 12 to 16, further comprising 1 to 30% by mass of a polyalkylene glycol macromonomer based on the total amount of the polymerizable unsaturated monomer component.

Item 18. Item 18. The method according to any one of Items 12 to 17, further comprising at least one (meth) acrylamide compound.

Item 19. 19. A method for producing a pigment dispersion paste, comprising: a step of obtaining a pigment dispersion resin by the method according to any one of items 11 to 18; and a step of mixing the pigment dispersion resin and the pigment obtained in the step.

Item 20. An electrically conductive pigment dispersion paste comprising the steps of obtaining a pigment dispersion resin by the method according to any one of items 11 to 18 and mixing the pigment dispersion resin obtained in the step and the electrically conductive pigment. Production method.

The pigment dispersion resin of the present invention makes it possible to obtain a pigment dispersion paste excellent in pigment dispersibility and stability even at a high pigment concentration.

Pigment-dispersed resin The pigment-dispersed resin of the present invention contains 1 to 70% by mass, preferably 5 to 60% by mass, more preferably 10 to 10% by mass of the monomer (A) having a polycyclic aromatic hydrocarbon, based on the total solid content. It is characterized by containing ˜50 mass%. In the present specification, “the resin contains the monomer X as a raw material” means that the resin is a (co) polymer of the raw material monomer containing the monomer X, unless otherwise specified. means. In the present specification, the (co) polymer means a polymer or a copolymer. The pigment dispersion resin of the present invention is a copolymer of raw material monomers containing 1 to 70% by mass, preferably 5 to 60% by mass, more preferably 10 to 50% by mass of the monomer (A) having a polycyclic aromatic hydrocarbon. It is characterized by being.

Examples of the pigment dispersion resin include acrylic resin, polyester resin, epoxy resin, polyether resin, alkyd resin, urethane resin, silicone resin, polycarbonate resin, silicate resin, chlorine resin, fluorine resin, and these. Examples include composite resins, and acrylic resin is particularly preferable.

In the present specification, “(meth) acrylate” means acrylate and / or methacrylate, and “(meth) acrylic acid” means acrylic acid and / or methacrylic acid. “(Meth) acryloyl” means acryloyl and / or methacryloyl. “(Meth) acrylamide” means acrylamide and / or methacrylamide. In this specification, a “derivative” is obtained by changing a small part (or a plurality of parts) in a molecule by introducing a functional group, substituting an atom, or other chemical reaction with respect to a certain compound. Means a compound. For example, naphthalene has one or more functional groups such as an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a nitro group, a halogen atom, an aryloxy group, an alkylthio group, and an arylthio group. The introduced compound is a naphthalene derivative (for example, one or two). The number of functional groups to be introduced in such derivatives is not limited, and one or more functional groups can be introduced, preferably 1 to 3, more preferably 1 to 2.

Monomer having polycyclic aromatic hydrocarbon (A)
Examples of the polycyclic aromatic hydrocarbon of the monomer (A) having a polycyclic aromatic hydrocarbon that can be used in the pigment dispersion resin of the present invention include a naphthalene ring, an anthracene ring, a triphenylene ring, a tetraphen ring, and a tetracene ring. , A hydrocarbon group having a chrysene ring, a pyrene ring, a pentacene ring, a hexacene ring, a heptacene ring, a coronene ring, a ketrene ring, and the like, and derivatives thereof.

Among them, the monomer (A) having a polycyclic aromatic hydrocarbon is preferably a polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon represented by the following formula (1). .

(Wherein R represents a hydrogen atom or a methyl group, A represents a polycyclic aromatic hydrocarbon group, W may or may not be present. When W is present, W is a carbon atom, In the case where the number of nitrogen atoms and / or oxygen atoms is 1 to 20 and W is not present, W is directly bonded to A.)
The case where W does not exist can be paraphrased as the case where W is a single bond. Accordingly, in the formula (1), “W may or may not be present. When W is present, W is an organic group having 1 to 20 carbon atoms, nitrogen atoms and / or oxygen atoms. Yes, when W is not present, W is directly bonded to A. “W is a single bond or an organic group having 1 to 20 carbon atoms, nitrogen atoms and / or oxygen atoms. In other words.

The “polymerizable unsaturated monomer” means a monomer having a polymerizable unsaturated group capable of radical polymerization, and examples of the polymerizable unsaturated group include (meth) acryloyl group, acrylamide group, vinyl group, Examples include an allyl group, a (meth) acryloyloxy group, and a vinyl ether group.

Specific examples of the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon include, for example, vinyl naphthalene, naphthyl (meth) acrylate, naphthylalkyl (meth) acrylate, vinylanthracene, anthracenyl ( Examples include meth) acrylate, anthracenylalkyl (meth) acrylate, vinylpyrene, pyrenyl (meth) acrylate, pyrenylalkyl (meth) acrylate, vinyl chrysene, vinyl naphthacene, vinyl pentacene, and derivatives thereof. Also included are those obtained by reacting a polymerizable unsaturated group monomer having a reactive functional group such as a glycidyl group or an isocyanate group with a polycyclic aromatic hydrocarbon having a functional group that reacts with the reactive functional group. . Any combination of functional groups that react with each other can be suitably used, but a combination of a carboxyl group and a glycidyl group, an amino group and a glycidyl group, or a hydroxyl group and an isocyanate group is more preferable. Specifically, for example, glycidyl (meth) acrylate and 1-naphthylacetic acid, 2- (meth) acryloyloxyethyl isocyanate and 1-naphthol, 2- (meth) acryloyloxyethyl isocyanate and 1- (2-naphthyl) ethanol The combination etc. are mentioned.
These can be used alone or in combination of two or more.

In the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon and the polycyclic aromatic hydrocarbon of the monomer, the derivative is, for example, a hydroxyl group in the polycyclic aromatic moiety and a carbon number of 1 to 8 1 to 3 substituents such as an alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, or a phosphoryloxy group (for example, 1, 2, 3, etc.) Means a replacement.

Among them, the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer having a naphthyl group represented by the following formula (2) or a derivative (A-2) thereof. Preferably there is.

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, Represents a nitro group, a halogen atom, an aryloxy group, an alkylthio group or an arylthio group, and W may or may not be present, and when W is present, W is a carbon atom, a nitrogen atom and / or When the organic group has 1 to 20 oxygen atoms and W does not exist, W is directly bonded to the naphthyl group.)
Examples of the polymerizable unsaturated monomer having a naphthyl group or derivative (A-2) thereof include vinylnaphthalene, naphthyl (meth) acrylate, naphthylalkyl (meth) acrylate, and derivatives thereof. These can be used alone or in combination of two or more.

Of these, naphthyl (meth) acrylate or a derivative thereof (A-2) is preferably naphthyl (meth) acrylate or a derivative thereof (A-3) represented by the following formula (3).

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, sulfonic acid group, carboxyl group, alkoxycarbonyloxy group) Group, phosphoryloxy group, amino group, nitro group, halogen atom, aryloxy group, alkylthio group or arylthio group.)
Examples of the naphthyl (meth) acrylate or its derivative (A-3) include 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, and derivatives thereof. Or in combination of two or more.

Among them, naphthyl (meth) acrylate or a derivative thereof (A-3) is preferably 4-substituted-1-naphthyl (meth) acrylate (A-4) or a derivative thereof represented by the following formula (4). .

Wherein R represents a hydrogen atom or a methyl group, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, phosphoryloxy Group.)
Examples of the 4-substituted-1-naphthyl (meth) acrylate (A-4) or derivatives thereof include, for example, 4-substituted-1-naphthyl (meth) acrylate (A-5) represented by the following formula (5): Is mentioned.

Wherein R represents a hydrogen atom or a methyl group, X ′ represents a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms. Group, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, or a phosphoryloxy group. In the 4-substituted-1-naphthyl (meth) acrylate (A-5), X ′ is preferably substituted at the 2-position of the naphthyl group.

More specifically, examples of the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon include 4-methyl-1-naphthyl (meth) acrylate, 4-ethyl-1-naphthyl. (Meth) acrylate, 4-methoxy-1-naphthyl (meth) acrylate, 4-ethoxy-1-naphthyl (meth) acrylate, 4-hydroxy-1-naphthyl (meth) acrylate, 2-methoxy-4-hydroxy-1 -Naphtyl (meth) acrylate, 2-ethoxy-4-hydroxy-1-naphthyl (meth) acrylate, 2-hydroxy-4-methoxy-1-naphthyl (meth) acrylate, 2-hydroxy-4-ethoxy-1-naphthyl (Meth) acrylate, 4-methoxycarbonyloxy-1-naphthyl (meth) acrylate, 4-pheno Aryloxycarbonyl-1-naphthyl (meth) acrylate, and 4-phosphoryloxy-1-naphthyl (meth) acrylate, or a derivative thereof, and the like. These can be used alone or in combination of two or more.

The reason why the dispersion resin having the polycyclic aromatic hydrocarbon of the present invention is effective in the dispersibility and stability of the pigment is not known in detail, but for example, when the pigment has an aromatic ring This is thought to be due to the π-π interaction between the pigment and the dispersion resin. The π-π interaction is a dispersion force acting between the aromatic rings, and is also called a stacking interaction because it tends to be stabilized in an arrangement in which two aromatic rings are stacked with coins.

Further, the reason why the substituent of 4-substituted-1-naphthyl (meth) acrylate (A-4) is effective in the dispersibility and stability of the pigment is not known in detail, but for example, It is speculated that this is because the electrostatic potential of the aromatic ring is increased and the affinity with the pigment is increased.

Polymerizable unsaturated monomer other than polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon The pigment dispersion resin of the present invention comprises a polymerizable unsaturated monomer having a polycyclic aromatic hydrocarbon (A-1). ) And a polymerizable unsaturated monomer other than (A-1). As the polymerizable unsaturated monomer other than the polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon, any polymerizable unsaturated monomer usually used in the synthesis of an acrylic resin can be used without particular limitation. For example, alkyl (meth) acrylates having 3 or less carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) Acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) Acrylate, lauryl (meth) acrylate, stearyl ( ) Acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate, etc. Alkyl or cycloalkyl (meth) acrylate; polymerizable unsaturated compound having an isobornyl group such as isobornyl (meth) acrylate; polymerizable unsaturated compound having an adamantyl group such as adamantyl (meth) acrylate; benzyl (meth) acrylate, styrene Monocyclic aromatic ring-containing polymerizable unsaturated monomers such as α-methylstyrene, vinyltoluene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 A monoesterified product of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, such as hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate, the (meth) acrylic acid and 2 to 8 carbon atoms Hydroxyl-containing compounds such as ε-caprolactone modified product of monoesterified with dihydric alcohol of 8, N-hydroxymethyl (meth) acrylamide, allyl alcohol, (meth) acrylate having a polyoxyalkylene chain whose molecular terminal is a hydroxyl group Polymerizable unsaturated monomers; carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate; (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylamino Ethyl (meth) acrylate, N, N-diethylamino Nitrogen-containing polymerizable unsaturated monomers not containing urethane bonds, such as ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, adducts of glycidyl (meth) acrylate and amines; isocyanate group-containing polymerizability Polymerizable unsaturated monomer having a urethane bond such as a reaction product of an unsaturated monomer and a hydroxyl group-containing compound or a reaction product of a hydroxyl group-containing polymerizable unsaturated monomer and an isocyanate group-containing compound; glycidyl (meth) acrylate, β- Epoxy such as methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether Containing polymerizable unsaturated monomer; (meth) acrylate having a polyoxyethylene chain whose molecular end is an alkoxy group; 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4- Polymerizable unsaturated monomers having a sulfonic acid group such as sodium salt and ammonium salt of these sulfonic acids such as styrene sulfonic acid; 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate Polymerizable unsaturated monomers having a phosphate group, such as 2-methacryloyloxypropyl acid phosphate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) Polymerizable unsaturated monomers having an alkoxysilyl group such as silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctyl Perfluoroalkyl (meth) acrylate such as ethyl (meth) acrylate; polymerizable unsaturated monomer having a fluorinated alkyl group such as fluoroolefin; polymerizable unsaturated monomer having a photopolymerizable functional group such as maleimide group; (Meth) acrylate having a polyoxyethylene chain in which is an alkoxy group; allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (me ) Acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, 1,1 , 1-trishydroxymethylethanetri (meth) acrylate, 1,1,1-trishydroxymethylpropanetri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc. Such polymerizable unsaturated monomer having two or more in one molecule thereof. These can be used alone or in combination of two or more.

Among these, it is preferable to contain at least one styrene, and it is more preferable to contain 5 to 65% by mass of styrene based on the total amount of the polymerizable unsaturated monomer components.

Furthermore, from the viewpoint of forming a resin steric repulsion layer and ensuring the stability of the pigment dispersion paste, it preferably contains at least one polyalkylene glycol macromonomer, based on the total amount of polymerizable unsaturated monomer components. More preferably, the polyalkylene glycol macromonomer is contained in an amount of 1 to 30% by mass.

Further, the polyalkylene glycol macromonomer is a nonionic polymerizable unsaturated monomer represented by the following formula (5). Specific examples of such a monomer include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate and the like can be mentioned. Of these, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate are particularly preferable.
CH ₂ = C (R ¹ ) COO (C _n H _2n O) _m -R ² Formula (5)
[Wherein, R ¹ represents a hydrogen atom or CH ₃ , R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 4 to 60, particularly 4 to 55, and n is 2 Is an integer of ˜3, where the m oxyalkylene units (C _n H _2n O) may be the same or different from each other. ]

Moreover, it is preferable to contain at least one (meth) acrylamide compound. As the (meth) acrylamide compound, those known per se can be used without particular limitation. Specific examples include acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, N-methylacrylamide. N-methyl methacrylamide, N-methylol acrylamide butyl ether, N-methylol methacrylamide butyl ether, N-ethyl acrylamide, N-ethyl methacrylamide, Nn-propyl acrylamide, Nn-propyl methacrylamide, N-isopropyl acrylamide N-isopropyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, N-hydroxy Methyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxypropyl acrylamide, N-hydroxybutyl acrylamide, N-hydroxypentyl acrylamide, N-hydroxymethyl-N-ethyl acrylamide, N-methyl-N- Hydroxyethyl acrylamide, N, N-dihydroxymethyl acrylamide, N, N-dihydroxyethyl acrylamide, N, N-dihydroxypropyl acrylamide, N, N-dihydroxybutyl acrylamide, N, N-dihydroxypentyl acrylamide, N-hydroxymethyl methacrylamide N-hydroxyethyl methacrylamide, N-hydroxypropyl methacrylamide, N-hydroxybutyl methacryl Amide, N-hydroxypentyl methacrylamide, N-hydroxymethyl-N-ethyl methacrylamide, N-methyl-N-hydroxyethyl methacrylamide, N, N-dihydroxymethyl methacrylamide, N, N-dihydroxyethyl methacrylamide, N , N-dihydroxypropyl methacrylamide, N, N-dihydroxybutyl methacrylamide, N, N-dihydroxypentyl methacrylamide, N, N-dihydroxybutyl (meth) acrylamide, and N- [tris (hydroxymethyl) methyl) acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-methyl, N-ethylacrylamide, N-methyl, N- Ethyl methacrylamide, N-methylol acrylamide methyl ether, N-methylol methacrylamide methyl ether, N-methylol acrylamide ethyl ether, N-methylol methacrylamide ethyl ether, N-methylol acrylamide propyl ether, N-methylol methacrylamide propyl ether, N -Methylol acrylamide butyl ether, N-methylol methacrylamide butyl ether, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N -Amino group-containing (meth) acrylamide compounds such as dipropylaminoethyl (meth) acrylamide, methacryloyloxy Tilt trimethyl ammonium chloride (ACRYESTER DMC, tradename, manufactured by Mitsubishi Rayon Co., Ltd.) Quaternary ammonium salt group-containing acrylamide compounds such as, and the like acryloyl morpholine. These can be used alone or in combination of two or more.

Especially, it is preferable that it is a (meth) acrylamide compound represented by following formula (6).
CH ₂ = C (—R ¹ ) —C (═O) —N (—R ² ) —R ³ (6)
R ¹ in the above formula (6) is a hydrogen atom or a methyl group, and R ² and R ³ may be different or the same, and are at least one selected from a hydrogen atom, an organic group having a hydroxyl group, and an alkyl group. Preferably there is. Further, it is more preferable that both or one of R ² and R ³ is an organic group having a hydroxyl group. Specifically, for example, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- Hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxymethyl-N-ethyl (meth) acrylamide, N-methyl-N-hydroxyethyl (meth) acrylamide, N-ethyl-N-hydroxyethyl (Meth) acrylamide, N-hydroxyethyl-N-butyl (meth) acrylamide, N-hydroxybutyl-N-butyl (meth) acrylamide, N, N-dihydroxymethyl (meth) acrylamide, N, N-dihydroxyethyl (meta) ) Acrylamide, N, N-di Particularly preferred is at least one selected from hydroxypropyl (meth) acrylamide, N, N-dihydroxybutyl (meth) acrylamide, and N- [tris (hydroxymethyl) methyl) acrylamide.

The content of the (meth) acrylamide compound is preferably 1 to 30% by mass based on the total amount of polymerizable unsaturated monomer components.

Synthesis of Pigment Dispersion Resin The pigment dispersion resin of the present invention is a radical polymerization method known per se, such as a solution polymerization method in an organic solvent or an emulsion polymerization method in an aqueous medium in the presence of a radical polymerization initiator. Can be obtained by:

Examples of the radical polymerization initiator used for polymerization include cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2 , 5-Dihydroperoxide, 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide , Tert-butyl cumyl peroxide, decanoyl -Oxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-amyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2,5- Peroxide polymerization initiators such as dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1 , 1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisdimethylvaleronitrile, 4,4′-azobis (4- Cyanovaleric acid), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis And azo polymerization initiators such as (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2'-azobis (2-methylpropionate), and the like. it can. These can be used alone or in combination of two or more.

The solvent used for the above polymerization or dilution is not particularly limited, and examples thereof include water, an organic solvent, or a mixture thereof. Examples of the organic solvent include hydrocarbon solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cyclobutane; aromatic solvents such as toluene and xylene; methyl isobutyl ketone and the like Ketone solvents; ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol; ethyl acetate, n-butyl acetate, isobutyl acetate, Ester solvents such as ethylene glycol monomethyl ether acetate and butyl carbitol acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone; Alcohol solvents such as ethanol, isopropanol, n-butanol, sec-butanol, isobutanol, etc .; Ecamide (trade name, manufactured by Idemitsu Kosan Co., Ltd., amide solvent), N, N-dimethylformamide, N, N-dimethyl Conventionally known solvents such as amide solvents such as acetamide, N-methylformamide, N-methylacetamide, N-methylpropioamide and N-methyl-2-pyrrolidone can be exemplified. These can be used alone or in combination of two or more.

In solution polymerization in an organic solvent, a polymerization initiator, a polymerizable unsaturated monomer component, and an organic solvent are mixed and heated while stirring, and the organic solvent is added to the reaction vessel to suppress the temperature rise of the system due to reaction heat. While being stirred at a temperature of 60 ° C. to 200 ° C. while introducing an inert gas such as nitrogen or argon as necessary, the polymerizable unsaturated monomer component and the polymerization initiator are mixed or dropped over a predetermined time. The method to do is used.

Polymerization can be generally performed for about 1 to 10 hours. You may provide the additional catalyst process which heats a reaction tank, dripping a polymerization initiator as needed after superposition | polymerization of each step.

The pigment-dispersed resin of the present invention obtained as described above preferably has a weight average molecular weight in the range of 1,000 to 100,000, more preferably 3,000 to 50,000.

In the present specification, the number average molecular weight and the weight average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) and the retention time of a standard polystyrene having a known molecular weight measured under the same conditions. (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene. Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” are used as columns. ”And“ TSKgel G-2000HXL ”(trade names, all manufactured by Tosoh Corporation), and can be measured under the conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, and detector RI. it can.

Pigment Dispersion Paste The pigment dispersion paste of the present invention contains the above pigment dispersion resin, pigment, pigment derivative, solvent, and, if necessary, other additives.

In the present invention, as the pigment dispersed by the pigment dispersion resin, conventionally known pigments can be used without limitation. For example, white pigments such as titanium white and zinc white; blue colors such as cyanine blue and induslen blue Pigments; Green pigments such as cyanine green and patina; Organic red pigments such as azo and quinacridone; Red pigments such as Bengala; Organic yellow pigments such as benzimidazolone, isoindolinone, isoindoline, and quinophthalone Yellow pigments such as titanium yellow and yellow lead; black pigments such as carbon and pine smoke; bright pigments such as aluminum powder, copper powder, nickel powder, titanium oxide-coated mica powder, iron oxide-coated mica powder, and glitter graphite Can be mentioned. Among these, a pigment having an aromatic hydrocarbon is preferable.

The pigment dispersion resin of the present invention is suitable for dispersing conductive pigments that require particularly severe performance because the pigment can be dispersed finely and uniformly and the pigment dispersion paste can be stabilized over a long period of time.

Examples of the conductive pigment having an aromatic hydrocarbon include acetylene black, furnace black, thermal black, channel black, ketjen black, vulcan, carbon nanotube, graphene, vapor grown carbon fiber (VGCF), and graphite. It is done.

Regarding the solvent, the solvent used for the polymerization or dilution of the pigment dispersion resin described above can be suitably used.

Other additives include neutralizers, pigment dispersants, binders, antifoaming agents, antiseptics, rust inhibitors, plasticizers, and the like. Examples of the pigment dispersant and / or binder include acrylic resins other than the above-described pigment dispersion resins, polyester resins, epoxy resins, polyether resins, alkyd resins, urethane resins, silicone resins, polycarbonate resins, silicate resins, and chlorine-based resins. Examples thereof include resins, fluorine resins, polyvinyl pyrrolidone resins, polyvinyl alcohol resins, polyvinyl acetal resins, and composite resins thereof. These resins can be used alone or in combination of two or more.

The content of the pigment-dispersed resin solid content in the pigment-dispersed paste is usually 30% by weight or less, preferably 20% by weight or less, such as viscosity during pigment dispersion, pigment dispersibility, dispersion stability, and production efficiency. From the aspect, it is preferable. In particular, in the case of a conductive pigment dispersion paste, from the viewpoint of the conductivity of the coating film, the content of the pigment dispersion resin solid content in the conductive pigment dispersion paste solid content is usually 20% by mass or less, preferably 0.1%. It is suitable that it is ˜15% by mass, more preferably 1.0 to 10% by mass.

In the pigment dispersion paste, each of the above-described components can be prepared by using conventionally known components such as a paint shaker, a sand mill, a ball mill, a pebble mill, an LMZ mill, a DCP pearl mill, a planetary ball mill, a homogenizer, a twin-screw kneader, and a thin film swirl type high-speed mixer. It can be prepared by uniformly mixing and dispersing using a disperser.

Hereinafter, the present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited thereto. In each example, “parts” indicates mass parts, and “%” indicates mass%.

Production and Production Example 1 of Naphthyl Group-Containing Monomer Production of Naphthyl Group-Containing Monomer In a reaction vessel equipped with a stirrer and a cooling tube, 373 parts of butyl acetate, 202 parts of 1-naphthylacetic acid, 0.1 part of hydroquinone monomethyl ether, and tetra After charging 0.3 part of butylammonium bromide, the temperature was raised to 120 ° C. with stirring. Next, 154 parts of glycidyl methacrylate was dropped over 1 hour while blowing dry air into the solution, and the reaction was allowed to proceed at 120 ° C. for 2 hours to obtain a naphthyl group-containing monomer solution 1.

Production Example 2 Production of naphthyl group-containing monomer In a reaction vessel equipped with a stirring heating apparatus and a cooling tube, 208 parts of butyl acetate, 100 parts of 1-naphthol and 0.1 part of hydroquinone monomethyl ether were charged, and then stirred at 60 ° C. The temperature was raised to. Next, while blowing dry air into the solution, 107.6 parts of 2-methacryloyloxyethyl isocyanate was added dropwise over 1 hour, and the reaction was allowed to proceed at 60 ° C. for 2 hours to obtain a naphthyl group-containing monomer solution 2.

Production Example 1 of Pigment Dispersing Resin Manufacture of Pigment Dispersing Resin 300 parts of propylene glycol monomethyl ether was charged into a reaction vessel equipped with a stirring heating device and a cooling tube, and maintained at 110 ° C. after nitrogen substitution. Into this, the monomer mixture shown below was dripped over 3 hours.
9-anthracenylmethyl methacrylate 300 parts styrene 200 parts n-butyl methacrylate 300 parts 2-ethylhexyl acrylate 100 parts 2-hydroxyethyl methacrylate 100 parts 2,2′-azobis (2-methylbutyronitrile) 40 parts 1 hour later, a solution prepared by dissolving 5 parts of 2,2′-azobis (2-methylbutyronitrile) in 100 parts of propylene glycol monomethyl ether was added dropwise thereto over 1 hour. After completion of the dropwise addition, this was further maintained at 110 ° C. for 1 hour and then adjusted with methyl isobutyl ketone to obtain a pigment dispersion resin X-1 solution having a solid content of 70%. The pigment dispersion resin X-1 had a weight average molecular weight of 10,000.

Examples 2 to 33 and Comparative Examples 1 to 6 Production of Pigment Dispersion Resin Pigment Dispersion Resin X with the same composition and production method as Example 1 except that the monomer composition of Example 1 is the types and blending amounts shown in Table 1 below. -2 to X-39 solutions were prepared.
In addition, since MPEG2000 in the table is not mixed with other monomers, it was dropped in parallel separately from the monomer mixture.

(Note 1) MPEG2000: trade name, manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, number average molecular weight of about 2000.
In addition, the compounding quantity in a table | surface is a value of an active ingredient. Therefore, when the product etc. which contain additives, such as a solvent, are used as a component in a table | surface, the compounding quantity in a table | surface means the compounding quantity of the component in a table | surface except those additives.

Production Example 34 of Pigment Dispersion Paste Production of Conductive Pigment Dispersion Paste 8.6 parts of pigment dispersion resin X-1 solution obtained in Example 1 (solid content 6 parts), Denka Black HS-100 (trade name, 99 parts of carbon black manufactured by Denki Kagaku Kogyo Co., Ltd., 1 part of ketjen black ECP300 (trade name, manufactured by Lion Co., Ltd., ketjen black) and 580 parts of propylene glycol monomethyl ether are added and dispersed in a ball mill for 5 hours. Pigment dispersion paste Y-1 was obtained.

Examples 35 to 59 and Comparative Examples 7 to 9 Production of conductive pigment dispersion pastes Conductive pigment dispersion pastes Y-2 to Y-26 and Y-35 in the same manner as in Example 34 except those shown in Table 2 below. To 37 were obtained.

Example 60 Production of Conductive Pigment Dispersion Paste 8.6 parts of pigment dispersion resin X-26 solution obtained in Example 26 (solid content 6 parts), Denka Black HS-100 (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) 99 parts of carbon black), 1 part of Ketjen Black ECP300 (trade name, manufactured by Lion Corporation, Ketjen Black) and 580 parts of deionized water were added and dispersed in a ball mill for 5 hours. 27 was obtained.

Examples 61 to 67 and Comparative Examples 10 to 12 Production of Conductive Pigment Dispersion Paste Conductive pigment dispersion pastes Y-28 to Y-34 and Y-38 were carried out in the same manner as in Example 60 except that they were shown in Table 2 below. ~ 40 were obtained.

Table 2 below shows the results (dispersibility, conductivity) of the evaluation test described later.
In the present invention, it is important that both the dispersibility and the electroconductivity are excellent, and when either one has an evaluation of “D (very inferior)”, the pigment dispersion paste is rejected. is there.

(Note 2) Graphite: Natural graphite particles having a particle diameter of 50 to 600 μm. The blending amount in the table is a solid content value.

Example 68 Production of Colored Pigment Dispersion Paste In a stirring and mixing vessel, 143 parts of pigment dispersion resin X-31 solution obtained in Example 31 (solid content: 100 parts), “Raven5000UIII” (trade name, manufactured by Columbian Carbon Co., Ltd., carbon Black pigment) 60 parts and deionized water 800 parts were added and mixed uniformly. Next, the obtained mixed liquid was put into a wide-mouth glass bottle having a capacity of 225 cc, and zirconia beads having a diameter of about 0.5 mmφ were added as a dispersion medium and sealed, and dispersed with a paint shaker for 5 hours to disperse the colored pigment dispersion paste Y-41. Got.

Examples 69 to 72, Comparative Examples 13 to 17 Production of Colored Pigment Dispersion Pastes Colored pigment dispersion pastes Y-42 to Y-50 were obtained in the same manner as in Example 68 except that the pigments were shown in Table 3 below. In addition, the result (coloring property) of the evaluation test described later is also described.

(Note 3) Cyanine Blue 5206: Trade name, manufactured by Dainichi Seika Kogyo Co., Ltd., organic blue pigment.
(Note 4) RT355D: trade name, manufactured by BASF, organic red pigment.
In addition, the compounding quantity in a table | surface is a value of solid content.

Evaluation test <dispersibility>
Dispersibility of the obtained pigment dispersion paste was evaluated according to the following criteria using a tube gauge in accordance with the dispersity test of JISK-5600-2-5.
A: The pigment is dispersed below 10 μm. Dispersibility is very good.
B: The pigment is dispersed at 10 μm or more and less than 15 μm. Dispersibility is good.
C: Although the pigment is dispersed at 15 μm or more, no aggregate can be visually confirmed. Dispersibility is slightly inferior.
D: Aggregates are confirmed visually. Dispersibility is very poor.

<Conductivity>
Two aluminum foil tapes (manufactured by Sumitomo 3M, No. 425) were attached in parallel at intervals of 3 cm on a polypropylene plate (10 cm × 15 cm × 3 mm). Next, the obtained conductive pigment dispersion paste was coated with an applicator so as to have a length of 5 cm and a dry film thickness of 15 μm between aluminum foil tapes, allowed to stand at room temperature for 2 minutes, and then heat-dried at 80 ° C. for 10 minutes. did. (A dry coating film having a width of 3 cm, a length of 5 cm, and a film thickness of 15 μm was prepared.)
The resistivity of the dried coating film applied between the aluminum foil tapes was measured in a 20 ° C. atmosphere using “Digital Multimeter Model 7401” (trade name, manufactured by Yokogawa Meter & Instruments), and the conductivity was evaluated according to the following criteria. did.
S: The resistivity is less than 0.005 Ωm, and the conductivity is the best.
A: The resistivity is 0.005 Ωm or more and less than 0.0065 Ωm, and the conductivity is very good.
B: The resistivity is 0.0065 Ωm or more and less than 0.008 Ωm, and the conductivity is good.
C: The resistivity is 0.008 Ωm or more and less than 0.01 Ωm, and the conductivity is slightly inferior.
D: The resistivity is 0.01 Ωm or more, and the conductivity is very poor.

<Color development>
The obtained colored pigment dispersion paste was applied onto a transparent PET film so as to have a dry film thickness of 25 μm, and baked at 140 ° C. for 30 minutes to obtain a coating film “MA-68II” (trade name, X-Rite). A multi-angle spectrocolorimeter (manufactured by Kogyo Co., Ltd.) was used, and the coating film was irradiated with standard light D65 from an angle of 45 ° with respect to an axis perpendicular to the measurement object surface, and the reflected light was perpendicular to the measurement object surface L * values (L * 45) were measured for light in various directions (light received at an angle of 45 ° with respect to specularly reflected light). For pigments other than black, the color developability was evaluated with a value of L * 45.
For black pigment, in addition to the L * 45 value, the L * value (L * 25 and L * 75, respectively) when standard light D65 is irradiated from 25 ° and 75 ° angles is measured, and the sum of the three values It was evaluated with.
The lower the value, the better the color developability. In the present invention, a black pigment is 0.3 or less, a blue pigment is 1.5 or less, and a red pigment is 7 or less.

Claims (10)

A pigment dispersion resin characterized by being a copolymer of raw material monomers containing 1 to 70% by mass of a monomer (A) having a polycyclic aromatic hydrocarbon. The monomer (A) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon represented by the following formula (1): The pigment-dispersed resin described in 1.

(Wherein R represents a hydrogen atom or a methyl group, A represents a polycyclic aromatic hydrocarbon group, W may or may not be present. When W is present, W is a carbon atom, In the case where the number of nitrogen atoms and / or oxygen atoms is 1 to 20 and W is not present, W is directly bonded to A.) The polymerizable unsaturated monomer (A-1) having a polycyclic aromatic hydrocarbon is a polymerizable unsaturated monomer having a naphthyl group represented by the following formula (2) or a derivative (A-2) thereof: The pigment-dispersed resin according to claim 2.

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, Represents a nitro group, a halogen atom, an aryloxy group, an alkylthio group or an arylthio group, and W may or may not be present, and when W is present, W is a carbon atom, a nitrogen atom and / or When the organic group has 1 to 20 oxygen atoms and W does not exist, W is directly bonded to the naphthyl group.) The polymerizable unsaturated monomer having a naphthyl group or a derivative (A-2) thereof is a naphthyl (meth) acrylate represented by the following formula (3) or a derivative (A-3) thereof: The pigment-dispersed resin described in 1.

(In the formula, R represents a hydrogen atom or a methyl group, X and Y may be the same or different, and a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, sulfonic acid group, carboxyl group, alkoxycarbonyloxy group) Group, phosphoryloxy group, amino group, nitro group, halogen atom, aryloxy group, alkylthio group or arylthio group.) The naphthyl (meth) acrylate or a derivative thereof (A-3) is a 4-substituted-1-naphthyl (meth) acrylate (A-4) or a derivative thereof represented by the following formula (4): Item 5. A pigment-dispersed resin according to Item 4.

Wherein R represents a hydrogen atom or a methyl group, Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyloxy group having 1 to 8 carbon atoms, phosphoryloxy Group.) 6. The pigment-dispersed resin according to claim 2, which contains 5 to 65% by mass of styrene based on the total amount of polymerizable unsaturated monomer components. The pigment-dispersed resin according to any one of claims 2 to 6, further comprising 1 to 30% by mass of a polyalkylene glycol macromonomer based on the total amount of the polymerizable unsaturated monomer component. The pigment-dispersed resin according to any one of claims 2 to 7, further comprising at least one (meth) acrylamide compound. A pigment dispersion paste comprising the pigment dispersion resin according to any one of claims 1 to 8 and a pigment. 9. A conductive pigment dispersion paste comprising the pigment dispersion resin according to any one of claims 1 to 8 and a conductive pigment.