JP2024064331A - Photosensitive coloring composition, optical filter, image display device, and solid-state image pickup device - Google Patents

Abstract

[Problem] To provide a photosensitive composition that has good developability in unexposed areas and can form a pattern with excellent shape, adhesion, heat resistance, and solvent resistance. [Solution] A photosensitive coloring composition containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the alkali-soluble resin (B) contains an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by the following general formula, and the photopolymerization initiator (D) contains a compound (D1) represented by a specific formula. JPEG2024064331000042.jpg31138 (R1 is a hydrogen atom or the like, R2 is an alkylene group having 2 or 3 carbon atoms, R3 is hydrogen or the like, and n is an integer from 1 to 15.) [Selected Figure] None

Description

The present invention relates to a photosensitive coloring composition and its uses.

Color filters, which are a type of optical filter used in image display devices, solid-state imaging devices, etc., are produced, for example, by applying a photosensitive composition to a transparent substrate such as glass, removing the solvent from the coating by drying, irradiating the coating with radiation through a photomask having a desired pattern shape and curing it (hereinafter referred to as exposure), then cleaning and removing the unexposed parts of the coating (hereinafter referred to as development), and then, if necessary, heating the cured film to sufficiently harden it (hereinafter referred to as post-baking), thereby obtaining a filter segment pattern of a first color. Filter segment patterns of other colors can then be produced by carrying out similar operations.

In the above-mentioned development step, an alkaline developer is used as the developer to wash and remove the unexposed portion. If the coating film has insufficient solubility in the developer, the film that is not completely dissolved in the developer and that is detached from the coating film may adhere to the manufacturing equipment and contaminate it, which causes a productivity problem in which the manufacturing process must be stopped for cleaning. In addition, in recent years, there has been a demand for shortening production time to reduce costs and environmental load, and a shortening of development time is desired. On the other hand, if the resistance of the exposed portion to the alkaline developer is insufficient, there is a problem of poor pattern shape and adhesion. Therefore, there is a demand for a photosensitive composition in which the coating film dissolves uniformly in the developer in the development step, the development time does not affect productivity, and the pattern shape and adhesion do not occur. In addition, there is also a problem that the color changes due to the solvent of the coating liquid or the heating step when forming a filter segment pattern of another color or forming an overcoat film, etc.

As an effort to improve developability, Patent Document 1 discloses a photosensitive coloring composition that includes a colorant, a binder resin that includes a structural unit derived from a monomer (b) that has a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, a polymerizable compound, and a polymerization initiator. In addition, Patent Document 2 discloses a coloring composition that includes a polymerizable compound having an alkylene oxide structure as an effort to improve pattern chipping during development.

JP 2016-145977 A JP 2014-142582 A

However, neither of the compositions described in Patent Documents 1 and 2 was able to satisfy all of the following requirements at a certain level or higher: developer solubility, pattern shape and adhesion, and heat resistance and solvent resistance.

The present invention aims to provide a photosensitive coloring composition that has good solubility in the developer of unexposed areas and can form a pattern with excellent shape, adhesion, and resistance.

The present invention relates to a photosensitive coloring composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a dispersant (E) (excluding the case of an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by the following general formula (1)),
The alkali-soluble resin (B) contains an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by the following general formula (1),
The present invention relates to a photosensitive coloring composition, in which the photopolymerization initiator (D) contains a compound (D1) represented by the following general formula (2).

General formula (1)

In general formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n is an integer of 1 to 15.

General formula (2)

In formula (2), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₆ represents a hydrogen atom or a monovalent substituent.

The present invention also relates to the above-mentioned photosensitive coloring composition, which is characterized by containing a dispersant (E1) having an acidic group.

The present invention also relates to the photosensitive coloring composition, characterized in that the dispersant (E1) having an acidic group is a polyester dispersant (E1a), the polyester dispersant (E1a) has a main chain containing an aromatic carboxylic acid ester moiety having an ester bond formed by an esterification reaction of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety, the amount of the acid anhydride groups per mole of the hydroxyl groups is 0.9 to 1.5 moles, and the main chain containing the aromatic carboxylic acid ester moiety has a blocking moiety derived from a monoalcohol.

The present invention also relates to the photosensitive coloring composition, characterized in that the content of the monomer units (b1) based on the monomer represented by general formula (1) is 10 to 70 mass % of the total monomer units of the alkali-soluble resin (B1).

The photosensitive coloring composition is also characterized in that the dispersant (E1) having an acidic group has an acid value of 40 to 140 mg KOH/g.

The present invention also relates to a color filter comprising a substrate and a color material layer formed on the substrate using the above-mentioned photosensitive coloring composition.

The present invention also relates to a display device equipped with the above color filter.

The present invention also relates to a solid-state imaging device equipped with the above-mentioned color filter.

According to the present invention, it is possible to provide a photosensitive coloring composition that has good developability (developer solubility, development time) in the unexposed areas and can form a pattern having excellent shape, adhesion, heat resistance, and solvent resistance. The present invention can also provide an optical filter, an image display device, and a solid-state imaging device.

The following describes in detail the embodiment of the photosensitive composition of the present invention. Note that the present invention is not limited to the following embodiment, and can be modified within the scope of the problem that can be solved.

In the present invention, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless otherwise specified. In addition, "C.I." means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.
In addition, the molecular weight of the compound in the present invention is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry) for low molecular weight compounds whose molecular weight can be specified, and is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent for compounds having a molecular weight distribution.
A monomer is a compound that forms a resin by polymerization. The monomer is in a state before polymerization, and the monomer unit forms a resin and is derived from the monomer, that is, a partial structure based on the monomer. As described later, even if the monomer unit immediately after polymerization has a functional group and the functional group is modified, the partial structure that can be called the side chain of the monomer unit after modification and the corresponding partial structure of the raw material monomer from which it is derived are not the same, but are considered to be a monomer unit based on the raw material monomer.
The polymerizable compound (C) is a compound contained in the photosensitive coloring composition and forms a coating film by polymerization.

<Photosensitive Coloring Composition>
One embodiment of the present invention relates to a photosensitive coloring composition (hereinafter also referred to as photosensitive composition). The photosensitive composition of the present invention is a photosensitive coloring composition containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), characterized in that the alkali-soluble resin (B) contains an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by the following general formula (1), and the photopolymerization initiator (D) contains a compound (D1) represented by the following general formula (2).

General formula (1)

In general formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n is an integer of 1 to 15.

General formula (2)

In formula (2), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₆ represents a hydrogen atom or a monovalent substituent.

The mechanism by which the photosensitive composition having the above-mentioned structure can solve the problems of the present invention is not clear, but is speculated as follows.
It is speculated that the compound (D1) represented by the general formula (2) has a rigid, hydrophobic and heat-resistant fluorene skeleton compared to 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, which are photopolymerization initiators that have been widely used in the color filter field, and therefore a highly resistant cured film can be obtained. On the other hand, since it has a rigid fluorene skeleton, it takes time to dissolve in a developer. The general formula (1) has an alkylene oxide chain with moderate flexibility. In addition, since the general formula (1) contains a benzene ring, it is speculated that π-π interaction with the fluorene skeleton of the general formula (2) works, and the two compounds are close to each other. It is speculated that the dissolution time in a developer is significantly shortened by the general formula (2) being located in the vicinity of the alkali-soluble resin (B). It is also presumed that the use of a dispersant (E1) having an acidic group in combination further improves the developability while maintaining the curability of the coating film.

The components that are or can be included in the photosensitive composition of one embodiment are described in detail below.

The photosensitive composition of the present invention contains a colorant (A).

The colorant (A) may be either a pigment or a dye, and these may be used in combination.

(Pigment)
A pigment is a compound classified as a pigment in the Colour Index.
Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2 , 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 1 84, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260 , 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are preferred, and C.I. Pigment Red 177,254,291,295,296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are more preferred.

Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, and 73.

Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 1 27, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP-A-2012-226110 are exemplified. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A-2012-226110 are preferred.

Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Of these, C.I. Pigment Green 36, 58, 59, 62, and 63 are preferred.

Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

Examples of purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, C.I. Pigment Violet 19 and 23 are preferred.

Examples of black pigments include C.I. Pigment Black 1, 6, 7, 12, 20, and 31. In addition, at least two pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and purple pigments may be used as black colorants.

Among the pigments, examples of inorganic pigments include titanium oxide, barium sulfate, silica, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

(dye)
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are their derivatives and lake pigments obtained by converting dyes into lakes.

The acid dye preferably has an acid group such as sulfonic acid or carboxylic acid. In addition, a salt-forming compound which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. In addition, a salt-forming compound which is a salt of a resin component having such a functional group and an acid dye is also preferable. In addition, the salt-forming compound is easily modified into a sulfonamide compound to obtain a photosensitive composition having excellent resistance (light resistance, solvent resistance).
In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

Although basic dyes can be used as they are, salt-forming compounds that form salts with organic acids, perchloric acid, or metal salts thereof are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, in the salt-forming compounds of basic dyes, the anion component that acts as a counter ion is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. In addition, the resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

The chemical structure of dyes includes, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine Examples of the dye structure include dyes derived from dyes selected from the group consisting of polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

The colorant (A) may be used alone or in combination of two or more types.

The content of colorant (A) is preferably 5 to 70 mass %, and more preferably 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

(Micronization of pigments)
The pigment is preferably micronized before use. The method of micronization is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while being heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. From the viewpoint of cost, sodium chloride (table salt) is preferred as the water-soluble inorganic salt. From the viewpoints of both processing efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of pigment.

The water-soluble organic solvent functions to moisten the pigment and the water-soluble inorganic salt, and is a solvent that dissolves (is miscible with) water, but does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, from the viewpoint of safety, a high-boiling point solvent with a boiling point of 120°C or higher is preferred. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

In the salt milling treatment, a resin may be added as necessary. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in the organic solvent. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[Alkali-soluble resin (B)]
The alkali-soluble resin (B) may be any resin that dissolves in an alkali developer, and may be any known resin. The alkali-soluble resin (B) preferably has an alkali-soluble group such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, or a phenolic hydroxyl group. Among these, the carboxyl group is preferred.
Specific examples include acrylic resins having an acidic group, α-olefin/maleic acid (anhydride) copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, isobutylene/maleic acid (anhydride) copolymers, etc. The alkali-soluble resin (A) can contain a polymerizable unsaturated group such as a vinyl group, a (meth)allyl group, or a (meth)acryloyl group, or a thermosetting group such as an epoxy group or an oxetanyl group.

(Alkali-soluble resin (B1) containing monomer unit (b1) based on monomer represented by general formula (1))
The photosensitive composition of the present invention contains, as the alkali-soluble resin (B), an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by the following general formula (1).

General formula (1)

In general formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n is an integer of 1 to 15.

Examples of monomer units (b1) based on the monomer represented by general formula (1) include ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

It is preferable that the alkali-soluble resin (B1) further contains a polymerizable unsaturated group-containing monomer unit (b2).

[Polymerizable unsaturated group-containing monomer unit (b2)]
Methods for incorporating the polymerizable unsaturated group-containing monomer unit (b2) into the alkali-soluble resin (B1) include, for example, the following methods (i) to (iii).

<Method (i)>
In the method (i), for example, a polymer (precursor) of a monomer containing an epoxy group-containing monomer is first synthesized, and then a carboxyl group of a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Of these, acrylic acid and methacrylic acid are preferred.

From the viewpoint of developability, a monomer unit in which a carboxyl group of a carboxyl group-containing monomer is added to an epoxy group of an epoxy group-containing monomer unit, and then reacted with an acid anhydride is also useful as the polymerizable unsaturated group-containing monomer unit (b2).

Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc.

<Method (ii)>
In the method (ii), for example, a polymer (precursor) of a monomer containing a carboxyl group-containing monomer is first synthesized, and then an epoxy group of an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

<Method (iii)>
In the method (iii), for example, a polymer (precursor) of monomers including a hydroxyl group-containing monomer and a carboxyl group-containing monomer is first synthesized, and then the hydroxyl group of the precursor is reacted with an isocyanate group of an isocyanate group-containing monomer (modifying compound).

Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate.

Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

From the viewpoint of heat resistance and solvent resistance, the content of the polymerizable unsaturated group-containing monomer unit (b2) is preferably 5 to 80 mol %, and more preferably 10 to 80 mol %, of all the constituent units of the alkali-soluble resin (B1).

From the viewpoints of adhesion, heat resistance, and solvent resistance, it is preferable that the alkali-soluble resin (B) contains an alkali-soluble resin (B2) containing an alicyclic hydrocarbon-containing monomer unit (b3). It is presumed that the alicyclic hydrocarbon structure, which is highly hydrophobic and has both flexibility and rigidity, can form a tough film. It is also presumed that the inclusion of a polymerizable unsaturated group allows the resins to crosslink with each other upon exposure to form a tougher cured film, resulting in a pattern with good heat resistance and solvent resistance.

The alkali-soluble resin (B2) is not particularly limited as long as it is a resin containing an alicyclic hydrocarbon-containing monomer unit (b3), and known resins can be used. For example, there are copolymers of a monomer forming a polymerizable unsaturated group-containing monomer unit (b2) and a monomer forming an alicyclic hydrocarbon-containing monomer unit (b3), copolymers in which a compound having a polymerizable unsaturated group is reacted with a copolymer of a monomer forming an alicyclic hydrocarbon-containing monomer unit (b3) and another monomer copolymerizable therewith to introduce a polymerizable unsaturated group-containing monomer unit (b2), and copolymers obtained by the method described in JP-A-2008-165059.

[Alicyclic Hydrocarbon-Containing Monomer Unit (b3)]
Examples of monomers forming the alicyclic hydrocarbon-containing monomer unit (b3) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, from the viewpoints of suppressing water spots and pattern shape, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

From the viewpoints of adhesion, heat resistance, and solvent resistance, the content of the alicyclic hydrocarbon-containing monomer unit (b3) is preferably 1 to 60 mol %, and more preferably 1 to 40 mol %, of all the constituent units of the alkali-soluble resin (B2).

From the viewpoint of heat resistance and solvent resistance, the content of the polymerizable unsaturated group-containing monomer unit (b2) is preferably 5 to 80 mol %, and more preferably 10 to 80 mol %, of all the constituent units of the alkali-soluble resin (B2).

[Monomer unit (b4) having a homopolymer glass transition temperature of 0° C. or lower]
From the viewpoint of pattern shape, the alkali-soluble resin (B2) preferably contains a monomer unit (b4) having a homopolymer glass transition temperature of 0° C. or lower. More preferably, the monomer unit (b4) has a homopolymer glass transition temperature of −10° C. or lower, and particularly preferably, the monomer unit (b4) has a homopolymer glass transition temperature of −30° C. or lower. Note that the homopolymer refers to a homopolymer of each monomer, and the glass transition temperature value is the value shown in Brandrup, J. Immergut, E. H. (eds.), “Polymer Handbook, Third Edition, John Wiley & Sons, 1989”.

Examples of monomers forming monomer units (b4) whose homopolymer has a glass transition temperature of 0°C or less include phenoxyethyl acrylate (-22°C), lauryl acrylate (-3°C), 2-ethylhexyl acrylate (-50°C), n-hexyl acrylate (-57°C), n-butyl acrylate (-48°C), isobutyl acrylate (-40°C), ethyl acrylate (-24°C), lauryl methacrylate (-65°C), n-hexyl methacrylate (-5°C), 2-ethylhexyl methacrylate (-10°C), 2-methoxyethyl acrylate (-50°C), and tetrahydrofurfuryl acrylate (-12°C). Among these, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferred.

From the viewpoint of the cross-sectional shape, the content of the monomer unit (b4) having a homopolymer glass transition temperature of 0°C or less is preferably 1 to 50 mol %, and more preferably 5 to 40 mol %, of all the constituent units of the alkali-soluble resin (B2).

[Other monomer units (b5)]
The alkali-soluble resin (B1) can contain monomer units other than (b1) and (b2).
The alkali-soluble resin (B2) may contain monomer units other than (b3) and (b4).
Examples of monomer units other than (b1) to (b4) (also referred to as other monomer units (b5)) are shown below.

Examples of the monomer forming the other monomer unit (b5) include (meth)acrylates such as methyl (meth)acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, and benzyl (meth)acrylate;
Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl methacrylate, and glycerin monomethacrylate;
Epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate;
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid;
(meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
vinyl acetate, vinyl propionate, or other vinyl fatty acids;
Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine;
2-(meth)acryloyloxyethyl acid phosphate, phosphate group-containing (meth)acrylates such as compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid, and the like;
Isocyanates such as 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate;
Examples of such monomers include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. These monomers may be used alone or in combination of two or more.

The monomer having an isocyanate group may be a blocked isocyanate group-containing monomer in which the isocyanate group is protected with a compound (blocking agent) that is released by heat.

Blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is preferred.
Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam.
Examples of the phenol compound include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol.
Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole.
Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred.
Examples of the pyrazole compound include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred.
Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan.
Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole.
Examples of the imide compound include succinimide, maleimide, maleimide, and phthalimide.
Examples of the urea compound include urea, thiourea, and ethyleneurea.
Examples of the imine compound include ethyleneimine and polyethyleneimine.
Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

Blocking agents can be used alone or in combination of two or more types.

The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and from the viewpoint of protection reactions and deprotection reactions, it is more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

Examples of blocked isocyanate group-containing monomers include the following compounds. Note that the present invention is not limited to these.

Commercially available blocked isocyanate group-containing monomers include Showa Denko's Karenz MOI-DEM (blocking agent desorption temperature: 85-95°C), MOI-BP (blocking agent desorption temperature: 105-115°C), and MOI-BM (blocking agent desorption temperature: 125-135°C). These monomers can be used alone or in combination of two or more.

The alkali-soluble resin (B2) can be used alone or in combination of two or more types.

From the viewpoints of developability, heat resistance, and solvent resistance, the content of the alkali-soluble resin (B2) is preferably 10 to 90 mass%, and more preferably 20 to 60 mass%, of 100 mass% of the alkali-soluble resin (B).

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 25,000.

From the viewpoint of developability, the acid value of the alkali-soluble resin (B) is preferably 30 to 200 mgKOH/g, and more preferably 40 to 180 mgKOH/g.

The content of the alkali-soluble resin (B) is preferably 1 to 80 mass %, and more preferably 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

The photosensitive composition of the present invention contains a polymerizable compound (C).

The polymerizable compound (C) may be a monomer or oligomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group having an ethylenically unsaturated double bond. The weight average molecular weight or formula weight of the polymerizable compound (C) is preferably less than 2000.

Examples of the polymerizable compound (C) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, urethane (meth)acrylate, and various other acrylic acid esters and methacrylic acid esters, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

Commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, and D-330 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, and M-405 manufactured by Toagosei Co., Ltd. M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Co., Ltd., AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., Miwon Specialty Chemical Co., Ltd. Miramer HR6060, 6100, 6200 manufactured by Daicel Allnex Co., Ltd., EBECRYL40, 130, 140, 145 manufactured by Daicel Allnex Co., Ltd., and OGSOL EA-0200, 0300 manufactured by Osaka Gas Chemicals Co., Ltd.

The polymerizable compound (C) may be used alone or in combination of two or more.

The content of the polymerizable compound (C) is preferably 5 to 70 mass %, and more preferably 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

(Lactone-modified polymerizable compound (C1))
From the viewpoint of suppressing heat resistance and solvent resistance, the polymerizable compound (C) preferably contains a lactone-modified polymerizable compound (C1).

The lactone-modified polymerizable compound (C1) is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound (C1) is obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound. The lactone-modified polymerizable compound (C1) is preferably a compound represented by the following general formula (4).

General formula (4)

In general formula (4), all six R are groups represented by the following general formula (5), or one to five of the six R are groups represented by the following general formula (5) and the remaining are groups represented by the following general formula (6).

General formula (5)

In formula (5), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and * represents a bond bonded to the oxygen atom of formula (4).

General formula (6)

In formula (6), R ¹ represents a hydrogen atom or a methyl group, and * represents a bond to the oxygen atom of formula (4).

The lactone-modified polymerizable compound (C1) is commercially available as, for example, the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. Examples thereof include DPCA-20 (a compound in which, in the above general formulas (4) to (6), m=1, the number of groups represented in general formula (5)=2, and all R ^1s are hydrogen atoms), DPCA-30 (a compound in which, in the above general formulas (4) to (6), m=1, the number of groups represented in general formula (5)=3, and all R ^1s are hydrogen atoms), DPCA-60 (a compound in which, in the above general formulas (4) to (6), m=1, the number of groups represented in general formula (5)=6, and all R ^1s are hydrogen atoms), and DPCA-120 (a compound in which, in the above general formulas (4) to (6), m=2, the number of groups represented in general formula (5)=6, and all R ^1s are hydrogen atoms).

From the viewpoint of heat resistance and solvent resistance, the lactone-modified polymerizable compound (C1) is preferably a compound in which, in the above general formulas (4) to (6), m=1, the number of groups represented by general formula (5)=2 to 6, and all of R ¹ 's are hydrogen atoms, and more preferably a compound in which, in the above general formulas (4) to (6), m=1, the number of groups represented by general formula (5)=2 or 3, and all of R ¹ 's are hydrogen atoms.

The lactone-modified polymerizable compound (C1) can be used alone or in combination of two or more types.

From the viewpoint of developability and heat resistance, the content of the lactone-modified polymerizable compound (C1) is preferably 5 to 90 mass% and more preferably 10 to 85 mass% in 100 mass% of the polymerizable compound (C).

(Polymerizable compound (C2) having an acidic group)
From the viewpoint of developability, the polymerizable compound (C) preferably contains a polymerizable compound (C2) having an acidic group. Examples of the acidic group of the polymerizable compound (C2) having an acidic group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, a carboxyl group is preferred.

Examples of the polymerizable compound (C2) having an acidic group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like.
Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.
Examples of polyvalent carboxylic acids include trimellitic acid and pyromellitic acid.
Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

Commercially available products of the polymerizable compound (C2) having an acidic group include Viscoat #2500P manufactured by Osaka Organic Industries, and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd.

The polymerizable compound (C2) having an acidic group can be used alone or in combination of two or more types.

From the viewpoint of developability and pattern shape, the content of the polymerizable compound (C2) having an acidic group is preferably 5 to 90 mass %, and more preferably 10 to 85 mass %, based on 100 mass % of the polymerizable compound (C).

(Polymerizable compound (C3) having a urethane group bond)
From the viewpoint of adhesion, the polymerizable compound (C) preferably contains a polymerizable compound (C3) having a urethane bond. Examples of the polymerizable compound (C3) having a urethane bond include a urethane (meth)acrylate obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and a urethane (meth)acrylate obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the polyhydric alcohol with a hydroxyl group-containing (meth)acrylate.

Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanates such as isophorone diisocyanate, as well as their biuret forms, isocyanate nurate forms, and trimethylolpropane adducts.

The polymerizable compound (C3) having a urethane bond can further contain an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, the carboxyl group is preferred.

The method for introducing an acidic group into a polymerizable compound having a urethane bond can be, for example, to first react the above-mentioned hydroxyl group-containing (meth)acrylate with the above-mentioned polyfunctional isocyanate. Then, the product can be synthesized by adding a mercapto compound having a carboxyl group to the product.

Examples of mercapto compounds having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

Commercially available polymerizable compounds (C3) having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

(Polymerizable compound having a hydroxyl group (C4))
From the viewpoints of developability and adhesion, the polymerizable compound (C) preferably contains a polymerizable compound (C4) having a hydroxyl group.

Examples of the polymerizable compound (C4) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric acid EO, or Examples of the acrylic acid esters include PO-modified (meth)acrylates, isocyanuric acid EO or PO-modified di(meth)acrylates, pentaerythritol tri(meth)acrylates, dipentaerythritol penta(meth)acrylates, polypentaerythritol penta(meth)acrylates, dipentaerythritol EO or PO-modified penta(meth)acrylates, dipentaerythritol caprolactone-modified penta(meth)acrylates, and epoxy (meth)acrylates in which the epoxy group of an epoxy compound reacts with the carboxyl group of (meth)acrylic acid. Among these, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred.

Commercially available polymerizable compounds (C4) having a hydroxyl group include, for example, KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd., Blenmar GLM, GLM-R, GMR-M, GMR-R, GAM, GAM-R, and G-FA80 manufactured by NOF Corp., Aronix M-5700 and M-920 manufactured by Toagosei Co., Ltd., NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), G-201P, Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL manufactured by Osaka Gas Chemical Co., Ltd. Examples include GA-5060P and GA-2800.

The polymerizable compound (C) may include a polymerizable compound having a tertiary amine structure or a polymerizable compound having a dendrimer structure or a hyperbranched structure.

(Polymerizable compound having a tertiary amine structure)
Examples of the polymerizable compound having a tertiary amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and diglycerol tri(meth)acrylate. Examples of the alkylene oxide-modified tetra(meth)acrylate include phosphorus tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerol alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate.
Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide.
The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

The (meth)acrylate compound (X) may be used alone or in combination of two or more types.

Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol;
Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

The amine compound (Y) can be used alone or in combination of two or more types.

There are no particular limitations on the method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y), and any known method can be used. For example, the methods described in International Publication No. 2006/075754, JP-T-2008-545859, JP-A-2017-066347, etc. can be mentioned.

The polymerizable compound having a tertiary amine structure may have an acidic group and/or a hydroxyl group. Examples of methods for introducing an acidic group and/or a hydroxyl group include a method of using a compound having an acidic group and/or a hydroxyl group in a (meth)acrylate compound (X) or an amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

Commercially available polymerizable compounds having a tertiary amine structure include, for example, Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd.

(Polymerizable compound having a dendrimer structure or a hyperbranched structure)
A polymerizable compound having a dendrimer structure has a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, and a polymerizable unsaturated group is bonded to the end of the branch, and has a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of the dendrimer structure.

Commercially available polymerizable compounds having a dendrimer structure or hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and Miramer SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18), and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials.

(Other polymerizable compounds (C5))
The photosensitive composition of the present invention can contain, as the polymerizable compound (C), a lactone-modified polymerizable compound (C1), a polymerizable compound having an acidic group (C2), a polymerizable compound having a urethane bond (C3), a polymerizable compound having a hydroxyl group (C4), a polymerizable compound having a tertiary amine structure, and a polymerizable compound having a dendrimer structure or a hyperbranched structure (hereinafter also referred to as other polymerizable compounds (C5)).

(Other polymerizable compounds (C5))
Examples of the other polymerizable compound (C5) include methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified or PO-modified tri(meth)acrylate, and the like. Examples of the acrylic acid ester include various acrylic acid esters and methacrylic acid esters such as isocyanuric acid EO- or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, and (meth)acrylic acid esters of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

Other commercially available polymerizable compounds (C5) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-211B manufactured by Toagosei Co., Ltd. M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, M-930, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., OGSOL EA-0200, EA-0300 manufactured by Osaka Gas Chemical Co., Ltd., Miwon Specialty Chemical Co., Ltd. Miramer HR6060, 6100, 6200 manufactured by Epson Corporation, and NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

Other polymerizable compounds (C5) can be used alone or in combination of two or more types.

The polymerizable compound (C) preferably contains one or more polymerizable compounds selected from the group consisting of lactone-modified polymerizable compounds (C1), polymerizable compounds having an acidic group (C2), polymerizable compounds having a urethane bond (C3), and polymerizable compounds having a hydroxyl group (C4).

[Photopolymerization initiator (D)]
(Compound (D1) represented by general formula (2))
The photosensitive composition of the present invention contains a compound (D1) represented by general formula (2) as a photopolymerization initiator (D).

General formula (2)
(In general formula (2), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₆ represents a hydrogen atom or a monovalent substituent.)

R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, cyclohexylmethyl, etc. Among these, from the viewpoints of suppressing water spots and pattern shape, linear alkyl groups having 3 to 8 carbon atoms are preferred, and linear alkyl groups having 4 to 6 carbon atoms are more preferred.

_R6 represents a hydrogen atom or any monovalent substituent.
Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; benzoyl groups which may have a substituent; and thenoyl groups which may have a substituent. Examples of the substituents that the benzoyl group or thenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, hydrogen atoms and nitro groups are preferred, and hydrogen atoms are more preferred.

Examples of the method for producing compound (D1) represented by general formula (2) include those described in JP-T-2019-507108 and JP-T-2019-528331.

Specific examples of compound (D1) represented by general formula (2) are shown below. Note that the present invention is not limited to these.

Among the compounds of chemical formulas (7) to (9), the compound of chemical formula (7) is preferred from the viewpoints of developability, pattern shape, adhesion, heat resistance, and solvent resistance.

The compound (D1) represented by general formula (2) can be used alone or in combination of two or more types.

(Oxime-based photopolymerization initiator (D2))
The photosensitive composition of the present invention may contain an oxime-based photopolymerization initiator (D2) as the photopolymerization initiator (D). Examples of the oxime-based photopolymerization initiator (D2) include a compound (D2a) containing one oxime group in one molecule and a compound (D2b) containing two oxime groups in one molecule.

[Compound (D2a) containing one oxime group per molecule]
Examples of commercially available compounds (D2a) containing one oxime group per molecule include IRGACURE OXE-01, 02, and 03 manufactured by BASF, ADEKA ARCLES N-1919, NCI-831, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou New Materials Co., Ltd., OMNIRAD1312, 1314, and 1316 manufactured by IGM Resins, SPI-02, 03, 04, 06, and 07 manufactured by Samyang Corporation, and DFI-020 and EOX-01 manufactured by Daito Chemistry Co., Ltd.

Specific examples of compounds (D2a) containing one oxime group per molecule include the following. Note that the present invention is not limited to these.

Methods for producing the compounds of chemical formulas (10) to (13) include, for example, those described in JP-T-2004-534797, JP-A-2008-80068, JP-T-2012-526185, WO-2015/036910, WO-2015/152153, JP-T-2016-504270, and JP-T-2017-512886.

From the viewpoints of pattern shape, heat resistance and thermal stability, it is preferable that the compound (D2a) containing one oxime group per molecule contains one or more compounds selected from the group consisting of the compounds of chemical formulas (10) to (13).

Compounds (D2a) containing one oxime group per molecule can be used alone or in combination of two or more types.

[Compound (D2b) containing two oxime groups in one molecule]
Examples of the compound (D2b) containing two oxime groups in one molecule include compounds described in JP-A-2005-215378, JP-A-2011-105713, JP-T-2017-523465, JP-A-2021-011486, etc. Among them, the compound represented by the following general formula (14) is preferred.

General formula (14)

In the general formula (14), _X1 and _X2 each independently represent a carbonyl bond (-CO-) or a single bond. _X3 represents a single bond or a sulfur atom. _R1 represents an alkyl group having 1 to 20 carbon atoms, and _R2 and _R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. _R4 and _R5 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.

In the general formula (14), _X1 and _X2 each independently represent a carbonyl bond (-CO-) or a single bond. From the viewpoint of solubility in an organic solvent, it is preferable that at least one of _X1 and _X2 is a carbonyl bond (-CO-), and it is more preferable that _X1 and _X2 are a carbonyl bond (-CO-).

In formula (14), _X3 is a single bond or a sulfur atom, and is preferably a single bond.

In the general formula (14), R ₁ represents an alkyl group having 1 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, or the like. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Among these, an ethyl group, a propyl group, and an isopropyl group are preferable.

In general formula (14), _R2 and _R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocycle having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, or the like. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Among these, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group are preferred.
Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, and a morpholinyl group.
Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, etc. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc.

Among these, from the viewpoint of solubility in organic solvents, it is preferable that at least one of _R2 and _R3 is a linear alkyl group having 1 to 20 carbon atoms, and from the viewpoint of solubility in organic solvents and suppression of water stains, it is more preferable that R2 and R3 are a linear alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms.

In formula (14), R ₄ and R ₅ each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, or the like. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclopentylmethyl group, and a cyclohexyl group. Among these, the methyl group, the ethyl group, the propyl group, and the isopropyl group are preferred from the viewpoint of reactivity.
Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, and a morpholinyl group.
Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and an anthryl group. The aryl group may also be a group substituted with a halogen atom, an amino group, a nitro group, or the like. Among these, a phenyl group is preferred from the viewpoint of reactivity.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, etc. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc.

Among these, from the viewpoint of reactivity, R ₄ and R ₅ are preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or an ethyl group.

The method for producing the compound represented by general formula (14) is not particularly limited, and any known method can be used. For example, the methods described in JP-T-2017-523465, JP-A-2021-011486, etc. can be used.

Specific examples of compounds (D2b) containing two oxime groups in one molecule are shown below. Note that the present invention is not limited to these.

Among the compounds represented by formulas (15) to (18), the compound represented by formula (15) is preferred from the viewpoint of suppressing heat resistance and solvent resistance.

Compounds (D2b) containing two oxime groups in one molecule can be used alone or in combination of two or more types.

The content of the oxime-based photopolymerization initiator (D2) is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the photopolymerization initiator (D), from the viewpoints of developability, cross-sectional shape, adhesion, heat resistance, and solvent resistance.

(Other Photopolymerization Initiators (D3))
The photosensitive composition of the present invention can contain a compound (D1) represented by general formula (2) and a photopolymerization initiator (D3) other than the oxime-based photopolymerization initiator (D2) (hereinafter also referred to as other photopolymerization initiator (D3)).

Other photopolymerization initiators (D3) are not particularly limited as long as they are compounds capable of initiating polymerization of the polymerizable compound (C) by light, and known photopolymerization initiators can be used. For example, acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone;
Triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;
Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.

Other photopolymerization initiators (D3) can be used alone or in combination of two or more types.

From the viewpoint of photocurability, the content of the photopolymerization initiator (D) is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 15 to 30 parts by mass, per 100 parts by mass of the polymerizable compound (C).

[Dispersant (E)]
The photosensitive composition of the present invention contains a dispersant (E), except in the case where the dispersant (E) is an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by general formula (1).

(Dispersant having an acidic group (E1))
The dispersant (E) is preferably a resin having an adsorptive group having high affinity for the colorant (A). The adsorptive group preferably has at least one of a basic group and an acidic group, and from the viewpoint of developability, a dispersant (E1) having an acidic group is preferable.

Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups. Among these, carboxyl groups and phosphate groups are preferred from the viewpoints of adsorption to pigments and developability.

Polyester Dispersant (E1a)
Among the dispersants (E1) having an acidic group, a polyester dispersant (E1a) is preferred, which has a main chain containing an aromatic carboxylic acid ester moiety having an ester bond obtained by esterification reaction of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety, wherein the amount of the acid anhydride groups per mole of the hydroxyl groups is 0.9 to 1.5 moles, and the main chain containing the aromatic carboxylic acid ester moiety has a blocking moiety derived from a monoalcohol.

The polyester dispersant (E1a) is produced by a ring-opening reaction between a precursor aromatic compound having two or more acid anhydride groups and a precursor compound having two or more hydroxyl groups, to generate an ester bond and at the same time an aromatic carboxylic acid.
The vinyl polymer moiety of the polyester dispersant (E1a) can be polymerized, for example, by the following two methods. The first method is a method of polymerizing an ethylenically unsaturated monomer in the presence of a compound having a thiol group and two or more hydroxyl groups. The compound having a thiol group and two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule.
The second method is a method of polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and a hydroxyl group of a compound having a thiol group and two or more hydroxyl groups. Among them, a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a hydroxyl group of a compound having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of an aromatic tetracarboxylic dianhydride is preferred.
The difference between the above two methods is whether the polymer moiety obtained by polymerizing an ethylenically unsaturated monomer is introduced first or later. Although the molecular weight and other properties may differ slightly depending on various conditions, the same product can theoretically be produced if the raw materials and reaction conditions are the same.

Of the main chains containing aromatic carboxylate moieties, the aromatic carboxylic acid acts as a pigment adsorption group. An aromatic carboxylic acid is a structure in which a carboxyl group and an aromatic ring are directly bonded. In addition, the side chains containing vinyl polymer moieties act as pigment carrier affinity moieties. This suppresses pigment aggregation and provides excellent dispersion stability.
The main chain containing an aromatic carboxylate moiety is produced by an esterification reaction of 1 mole of a compound having two or more hydroxyl groups and 0.9 to 1.5 moles of an aromatic compound having two or more acid anhydride groups. Furthermore, at least one of the acid anhydride groups at the ends of the main chain containing an aromatic carboxylate moiety has a blocking moiety derived from a monoalcohol. That is, the acid anhydride group is ring-opened with the monoalcohol to produce an alcohol ester and a carboxyl group. This improves the filterability of the colored composition, suppresses foreign matter on the coating film formed by coating the colored composition, and further improves the resolubility in PGMAc of the solidified material derived from the colored composition formed in the coating device when the colored composition is coated. Note that, in the esterification reaction, the amount of the aromatic compound having two or more acid anhydride groups used is preferably 1.0 to 1.3 moles.

[Aromatic Compound Having Two or More Acid Anhydride Groups]
The anhydride groups of the aromatic compound having two or more acid anhydride groups used in the present invention can undergo a ring-opening reaction with a precursor compound having two or more hydroxyl groups to regularly arrange carboxyl groups, which serve as pigment adsorption groups, in the main chain of the polyester dispersant (E1a), thereby contributing to pigment dispersibility.

Examples of aromatic compounds having two or more acid anhydride groups include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

Aromatic compounds having two or more acid anhydride groups include aromatic tetracarboxylic dianhydrides represented by the following general formula (19) or (20).

General formula (19):

[In the general formula (19), k is 1 or 2.]

General formula (20):
[In general formula (20), Q1 is a direct bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, a group represented by the following general formula (21), or a group represented by the following general formula (22)]

General formula (21):

General formula (22):

From the viewpoint of adsorption to pigments, the aromatic compound having two or more acid anhydride groups is preferably an aromatic tetracarboxylic acid dianhydride, and more preferably pyromellitic dianhydride.

Aromatic compounds having two or more acid anhydride groups can be used in combination with aliphatic compounds having two or more acid anhydride groups.

[Compounds having two or more hydroxyl groups]
As described above, the compound having two or more hydroxyl groups is preferably a compound having a hydroxyl group and a thiol group in the molecule, and more preferably a compound having two hydroxyl groups and one thiol group in the molecule.

Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

Examples of the ethylenically unsaturated monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and the like. linear or branched alkyl (meth)acrylates such as methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, or methoxypolyethylene glycol polypropylene glycol (meth)acrylate;
cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tertiary butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, or isobornyl (meth)acrylate;
Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate;
(Meth)acryloxy-modified polydimethylsiloxanes (silicone macromers);
(meth)acrylates having a heterocycle, such as tetrahydrofurfuryl (meth)acrylate or 3-methyl-3-oxetanyl (meth)acrylate;
(meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, and nonylphenoxypolyethylene glycol (meth)acrylate;
(meth)acrylates having a carboxyl group, such as (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, and allyl (meth)acrylate;
N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine;
Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate;
nitriles such as (meth)acrylonitrile; or mixtures thereof.

Moreover, examples of monomers that can be used in combination with the above (meth)acrylic monomers include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and vinyl fatty acids such as vinyl acetate and vinyl propionate.

It is also possible to use a carboxyl group-containing ethylenically unsaturated monomer in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. can be selected.

The vinyl polymer moiety can be formed from a vinyl polymer having two hydroxyl groups at one end region. Its synthesis can be achieved by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, as well as by the following methods.

[1] A method of Michael addition of a resin having one (meth)acrylic group at one terminal region to a compound having one amine and two hydroxyl groups; [2] A method of epoxy addition of a resin having one carboxylic acid group at one terminal region to a compound having one epoxy group and one hydroxyl group; [3] A method of adding a resin having one vinyl ether group at one terminal region to a compound having one carboxylic acid group and two hydroxyl groups; and [4] A method of performing radical polymerization or atom transfer radical polymerization (living radical polymerization) using a polymerization initiator having two hydroxyl groups as the polymerization initiator.
By using these methods, it is possible to synthesize a resin having two hydroxyl groups at one terminal region, but it often results in a multi-step reaction and it is often difficult to control the molecular weight. From the viewpoint of productivity, too, the most preferred method is to radically polymerize an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group.

The vinyl polymer moiety can be synthesized by polymerizing a compound having two hydroxyl groups and one thiol group in the molecule with an ethylenically unsaturated monomer. The compound having two hydroxyl groups and one thiol group is used in an amount of 1 to 10% by mass, more preferably 2 to 9% by mass, and even more preferably 3 to 8% by mass, based on the total monomer mass of the ethylenically unsaturated monomer. When it is 1% by mass or more, the molecular weight of the vinyl polymer moiety is not too high, and the absolute amount of the vinyl polymer moiety as an affinity moiety for the pigment carrier and solvent can be suppressed, and the pigment dispersibility is further improved. When it is 10% by mass or less, the molecular weight of the vinyl polymer moiety is not too low, and the steric repulsion effect of the vinyl polymer moiety as an affinity moiety for the pigment carrier and solvent can be fully obtained, and the pigment dispersibility is further improved.

The polymerization temperature is 40 to 150°C, preferably 50 to 110°C. If it is 40°C or higher, the polymerization proceeds easily, and if it is 150°C or lower, it is easy to control the molecular weight.

When polymerizing, 0.001 to 5% by mass of a polymerization initiator can be used based on the total monomer mass of the ethylenically unsaturated monomer. Examples of polymerization initiators include azo compounds and organic peroxides.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

Polymerization initiators can be used alone or in combination of two or more types.

The synthesis of vinyl polymers is preferably carried out by bulk polymerization or solution polymerization. Examples of polymerization solvents for solution polymerization include, but are not limited to, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. Two or more of these polymerization solvents may be mixed together.

The side chains of the polyester dispersant (E1a) may have other polyol-based moieties in addition to the vinyl polymer moiety.

[Other polyols]
During polymerization, the density of the carboxylic acid group and the proportion of the solvent-soluble portion can be easily adjusted by using other polyols in combination.

Other polyols include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, and hexanetriol;
Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;
Modified polyether polyols obtained by ring-opening polymerization of the above-mentioned various polyhydric alcohols with various (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether;
Polyester polyols obtained by co-condensation of one or more of the above-mentioned various polyhydric alcohols with polyvalent carboxylic acids, in which the polyvalent carboxylic acids are particularly represented by succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, or 2,5,7-naphthalenetricarboxylic acid;
lactone-based polyester polyols obtained by polycondensation reaction of one or more of the above-mentioned various polyhydric alcohols with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone, or lactone-modified polyester polyols obtained by polycondensation reaction of the above-mentioned various polyhydric alcohols with polycarboxylic acids or various lactones;
Epoxy-modified polyester polyols obtained by using one or more of various epoxy compounds, such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and/or polyhydric alcohols, or glycidyl esters of monobasic and/or polybasic acids, in combination during the synthesis of polyester polyol; or
Examples of the polyol include polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, hydroxyl group-containing acrylic copolymers, hydroxyl group-containing fluorine-containing compounds, and hydroxyl group-containing silicone resins.

Other polyols may of course be used alone or in combination of two or more kinds, but from the viewpoint of compatibility and dispersion stability, the weight average molecular weight is preferably 40 to 10,000, more preferably 100 to 2,000, and even more preferably 100 to 1,000. When the weight average molecular weight is 40 or more, the density of the carboxylic acid group can be adjusted. When the weight average molecular weight is 10,000 or less, compatibility with other raw materials is good.

As other polyols, diols are preferred. In particular, by reacting with aromatic compounds having two or more acid anhydride groups, carboxyl groups that act as pigment adsorption groups can be arranged regularly in the main chain, which is advantageous for pigment dispersion. If a large amount of polyols with more than two hydroxyl groups are used, the main chain of the polyester becomes branched and complex and tall, making it difficult to obtain a dispersion effect. From a design perspective, such as adjusting the molecular weight of the polyester dispersant and adjusting the viscosity of the dispersion, it should be kept to a minimum. The amount to be used will be described later.

[Synthesis of polyester]
The polyester synthesis process for the polyester dispersant (E1a) used in the present invention will be described using as an example the reaction of a compound having two hydroxyl groups with a tetracarboxylic dianhydride, which are preferred compounds for a compound having two or more hydroxyl groups and an aromatic compound having two or more acid anhydride groups.

The tetracarboxylic dianhydride used in the present invention can react with hydroxyl groups to form ester bonds and leave pendant carboxyl groups on the resulting polyester backbone. The reactions of tetracarboxylic dianhydride with compounds having two hydroxyl groups when the molar amount of the compound having two hydroxyl groups is a and the molar amount of the tetracarboxylic dianhydride is b, i) a>b, ii) a=b, and iii) a<b, are shown in the following general formulas (23), (24), and (25). If the acid anhydride groups remaining in the products of the following general formulas (23) to (25) are hydrolyzed or the acid anhydride is ring-opened with an alcohol, the products of this reaction have two or three carboxyl groups in the X1 portion of the structural formula, and these multiple carboxyl groups are effective as adsorption sites for the pigment.

i) a>b

General formula (23):

ii) a = b

General formula (24):

iii) a<b

General formula (25):

R represents a hydrogen atom when an acid anhydride group is hydrolyzed, and represents the structure of a monoalcohol described below when an acid anhydride is ring-opened with a monoalcohol.

In the present invention, _X1 is a reaction residue after a tetracarboxylic dianhydride reacts with a hydroxyl group, and Y is a reaction residue after a compound having two hydroxyl groups reacts with an acid anhydride group. The preferred form of _X1 is a reaction residue after a tetracarboxylic dianhydride represented by the general formula (10) or (11) reacts with a compound having two hydroxyl groups.

[Synthesis of polyester dispersant (E1a)]
The polyester dispersant (E1a) is preferably prepared by introducing a vinyl polymer into Y in a compound having two hydroxyl groups via an S atom as described above for the synthesis of the polyesters represented by the general formulas (23) to (25). Two preferred synthesis patterns are shown below.

Composite pattern 1)
In the following general formula (26), an ethylenically unsaturated monomer is radically polymerized in the presence of a compound (a1) having two hydroxyl groups and one thiol group at one end to produce a vinyl polymer (a2) having two hydroxyl groups at one end, and this is reacted with a tetracarboxylic dianhydride (b1).

General formula (26):

When the molar ratio of (a1) is a (integer) and the molar ratio of (b) is b (integer), the molar ratio of the present invention is preferably 2b/2a = b/a = 0.9 to 1.5. Even if the molar ratio is less than 1, unreacted acid anhydride may remain, and the main chain end is blocked with a monoalcohol. If the molar ratio b/a is 0.9 or more, the proportion of sites adsorbed to the pigment in one molecule is sufficient, suppressing the generation of foreign matter, and if it is 1.5 or less, no acid anhydride group remains, resulting in good storage stability, and even if the acid anhydride is ring-opened, the acidic groups do not become excessive, resulting in good compatibility with pigment carriers and solvents. From the viewpoint of pigment dispersibility and stability, c/a = 1.0 to 1.3 is more preferable.

Composite pattern 2)
In the following general formulas (27) and (28), a compound having two hydroxyl groups and one thiol group at one end is reacted with a tetracarboxylic dianhydride to first produce a compound not containing a vinyl polymer moiety, and then the remaining thiol group is radically polymerized as a chain transfer agent to introduce a vinyl polymer moiety.

General formula (27):

General formula (28):

When the molar ratio of (a1) is a (integer) and the molar ratio of (b) is b (integer), the molar ratio of the present invention is preferably 2b/2a = b/a = 0.9 to 1.5. Even if the molar ratio is less than 1, unreacted acid anhydride may remain, and the acid anhydride is ring-opened with a monoalcohol. The ring-opening reaction of the acid anhydride with a monoalcohol may be performed either before radical polymerization as in general formula (27) or after radical polymerization as in general formula (28). If the molar ratio b/a is 0.9 or more, the proportion of sites adsorbed to the pigment in one molecule is sufficient, and the generation of foreign matter is suppressed. If the molar ratio is 1.5 or less, no acid anhydride group remains, and storage stability is good. Even if the acid anhydride is ring-opened, the acid group does not become excessive, and compatibility with the pigment carrier and solvent is good. From the viewpoint of pigment dispersibility and stability, b/a = 1.0 to 1.3 is more preferable.

[Reaction catalyst]
The catalyst used in the synthesis of the polyester dispersant (E1a) is preferably a tertiary amine compound, such as triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene.

[Reaction Solvent]
A solvent can be used in the synthesis of the polyester dispersant (E1a), such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate.

The main chain containing the aromatic carboxylic acid ester moiety in the polyester dispersant (E1a) has a capping moiety derived from a monoalcohol obtained by reacting an acid anhydride group with a monoalcohol.
Examples of monoalcohols include monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, and methylcyclohexanol;
monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether;
Examples of the monoalcohol include monoalcohols having a carbonyl group such as methyl lactate, ethyl lactate, diacetone alcohol, etc. These may be used alone or in combination of two or more.

The monoalcohol is preferably a compound having an ether group or a carbonyl group. The polyester dispersant (E1a) can have an ether group or a carbonyl group at the end of the main chain, which improves the PGMAc resolubility of the dispersant. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

The main chain containing the aromatic carboxylic acid ester moiety may have a blocking moiety that is reacted with water in addition to a blocking moiety derived from a monoalcohol.

When synthesizing the blocking portion, the amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 equivalents, more preferably 1.5 to 20 equivalents, per equivalent of the acid anhydride group remaining in the main chain. If there is 1 equivalent or more, no acid anhydride group remains and storage stability is good, while if there is 30 equivalents or less, ester exchange reaction due to the ester bond between the monoalcohol and the dispersant is unlikely to occur, and molecular weight reduction is unlikely to occur.

[Reaction conditions]
The ring-opening reaction temperature for polyester synthesis is in the range of 50° C. to 180° C., preferably 80° C. to 140° C. If the reaction temperature is 50° C. or higher, the reaction proceeds, whereas if the reaction temperature is 180° C. or lower, the carboxyl group and the hydroxyl group do not undergo an esterification reaction, and a decrease in acid value and gelation are unlikely to occur.

[Molecular weight]
The weight average molecular weight of the polyester dispersant (E1a) is preferably 2,000 to 35,000, more preferably 4,000 to 30,000, and even more preferably 4,000 to 25,000. When the molecular weight is 2,000 or more, pigment aggregation can be suppressed due to the steric repulsion effect of the solvent affinity moiety, and pigment dispersibility is further improved. When the molecular weight is 35,000 or less, solvent solubility is ensured, a sufficient steric repulsion effect can be maintained, and pigment dispersibility is further improved. When it is within the above range, the pigment aggregation suppression effect due to the steric repulsion effect becomes better.

[Acid value]
The acid value of the polyester dispersant (E1a) is preferably 5 to 200 mgKOH/g, more preferably 20 to 180 mgKOH/g, and even more preferably 30 to 150 mgKOH/g. When the acid value is 5 mgKOH/g or more, the pigment adsorption ability is improved and the pigment dispersibility is further improved. On the other hand, when the acid value is 200 mgKOH/g or less, there is no interaction between resins, and the viscosity of the pigment dispersion composition can be kept low.

The content of the polyester dispersant (E1a) in the coloring composition is preferably 0.01 to 100% by mass, more preferably 0.01 to 60% by mass, and even more preferably 5 to 40% by mass, based on the mass of the pigment. When the content of the polyester dispersant (E1a) is 0.01% by mass or more, a good dispersion effect is obtained, and when it is 100% by mass or less, there is no interaction between the resins and the viscosity of the pigment dispersion composition can be kept low.

The photosensitive composition of the present invention may use, as the dispersant (E), an acidic dispersant (E1b) of a polymerizable compound other than the polyester dispersant (E1a) or a dispersant having a basic group (E2).

Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and groups containing nitrogen atoms such as nitrogen-containing heterocycles.

Examples of resin types of acidic dispersants (E1b) of polymerizable compounds other than polyester dispersants (E1a) and dispersants having basic groups (E2) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphate esters.

The molecular structure of the acidic dispersant (E1b) of the polymerizable compound other than the polyester dispersant (E1a) and the dispersant having a basic group (E2) may be, for example, a random structure, a block structure, a graft structure, a comb structure, or a star structure. Among these, the block structure or the comb structure is preferred from the viewpoint of dispersion stability.

Commercially available products of acidic dispersants (E1b) of polymerizable compounds other than polyester dispersants (E1a) and dispersants having basic groups (E2) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 manufactured by BYK Japan Co., Ltd. , or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4404, 4405, 4406, 4407, 4408, 4409, 4410, 4411, 4412, 4413, 4414, 4415, 4416, 4417, 4418, 4419, 4420, 4421, 4422, 4423, 4424, 4425, 4426, 4427, 4428, 4429, 4430, 4431, 4432, 4433, 4434, 4435, 4436, 4437, 4438, 4439, 4440, 4441, 4442, 44439, 4444, 4450, 4452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4450, 4452, 4453, 4454, 4455, 4460, 4461, 4462, 4463, 4464, 446 06, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fiber Examples include Ajisuper PA111, PB711, PB821, PB822, and PB824 manufactured by NEC Corporation, and resins described in JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, WO 2008/007776 A, JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, JP 2009-251481 A, JP 2007-23195 A, and JP 1996-143651 A.

The dispersing resin (E) can be used alone or in combination of two or more types.

From the viewpoint of dispersion stability, the content of the dispersing resin (E) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the colorant (A).

[Dye derivative (F)]
The photosensitive composition of the present invention may contain a dye derivative (F).

The dye derivative (F) is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative (F) include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009/081930 A, WO 2011/052617 A, WO 2012/102399 A, and WO 2017-156397 A, phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016/163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are described in JP 63-264 A. 674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009/025325, quinacridone dye derivatives are shown in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383, dioxazine dye derivatives are shown in JP-A-2011-162662, thiazineindigo dye derivatives are shown in JP-A-2007-314785, and triazine Examples of benzoisoindole-based dye derivatives include those in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681. Examples of quinophthalone-based dye derivatives include those in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-226 110, naphthol dye derivatives are described in JP-A-2012-208329 and JP-A-2014-5439, azo dye derivatives are described in JP-A-2001-172520 and JP-A-2012-172092, acidic substituents are described in JP-A-2004-307854, and basic substituents are described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc. These documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but the compounds having substituents such as acidic groups, basic groups, and neutral groups in the organic dye residues are synonymous with dye derivatives.

The dye derivative (F) can be used alone or in combination of two or more types.

The content of the dye derivative (F) is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the colorant (A).

[Sensitizer (G)]
From the viewpoint of pattern shape, the photosensitive composition of the present invention preferably contains a sensitizer (G).

Examples of the sensitizer (G) include chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, as well as polymethine dyes, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples of the compounds include compounds having a fluorine-containing compound, ...

(Thioxanthone Compound (G1))
Examples of the thioxanthone compound (G1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferred.

(Benzophenone-based compound (G2))
Examples of the benzophenone compound (G2) include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

The sensitizer (G) can be used alone or in combination of two or more types.

From the viewpoint of pattern shape, the content of the sensitizer (G) is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 15 to 60 parts by mass, per 100 parts by mass of the compound (D1) represented by general formula (2).

[Thermosetting compound (H)]
From the viewpoint of heat resistance, the photosensitive composition of the present invention preferably contains a thermosetting compound (H), which reacts in a heating step to increase the crosslink density and improve the heat resistance.

The thermosetting compound (H) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy compound (H1))
Examples of the epoxy compound (H1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). Examples of the epoxy resins that can be used include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celoxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., etc.

The content of the epoxy compound (H1) is preferably 0.5 to 50 mass%, and more preferably 1 to 40 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition.

(Oxetane Compound (H2))
The oxetane compound (H2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

Commercially available products include, for example, OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Examples of bifunctional oxetane compounds include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc.

Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei.

Examples of trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

The content of the oxetane compound (H2) is preferably 0.5 to 50 mass %, and more preferably 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

A melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol type or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and/or ether groups per melamine ring. Having an appropriate number of methylol groups or ether groups makes it easier to obtain just the right amount of heat resistance.

Commercially available products include, for example, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 manufactured by Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and/or ether groups per melamine ring, are preferred in terms of increasing crosslink density.

The thermosetting compound (H) may be used alone or in combination of two or more types.

[Curing agent (curing accelerator)]
In the photosensitive composition of the present invention, a curing agent (curing accelerator) can be used in combination to assist the curing of the thermosetting compound (H). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

The hardeners can be used alone or in combination of two or more types.

The content of the curing agent is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound (H).

[Thiol-based chain transfer agent (I)]
The photosensitive composition of the present invention may contain a thiol-based chain transfer agent (I). When the thiol-based chain transfer agent (I) is used in combination with a photopolymerization initiator (D), a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, thereby improving the photosensitivity of the photosensitive composition.

The thiol chain transfer agent (I) is preferably a multifunctional thiol having two or more thiol groups (SH groups), more preferably a multifunctional thiol having four or more thiol groups. As the number of functional groups increases, the film becomes easier to photocure from the surface to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include thritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, and the like.

The thiol chain transfer agent (I) can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent (I) is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[Polymerization inhibitor (J)]
The photosensitive composition of the present invention may contain a polymerization inhibitor (J).

The polymerization inhibitor (J) is, for example, an alkyl catechol compound such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, or 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, or 2-n- Examples of such compounds include alkyl resorcinol compounds such as butyl resorcinol, 4-n-butyl resorcinol, 2-t-butyl resorcinol, and 4-t-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, t-butyl hydroquinone, and 2,5-di-t-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucin.

The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4 mass% based on 100 mass% of the nonvolatile content of the photosensitive composition.

[Ultraviolet absorber (K)]
The photosensitive composition of the present invention may contain an ultraviolet absorber (K).

The ultraviolet absorber (K) is an organic compound having an ultraviolet absorbing function, and examples of such compounds include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and straight chain alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl These include octyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan, ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA, KEMISORB 71, 73, 74, 79, and 279 manufactured by Chemipro Chemicals, and RUVA-93 manufactured by Otsuka Chemical.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adeka STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3-water, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adeka STAB 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (K).

[Antioxidant (L)]
The photosensitive composition of the present invention may contain an antioxidant (L).

The antioxidant (L) prevents the photopolymerization initiator (D) and thermosetting compound (H) contained in the photosensitive composition from yellowing due to oxidation during the thermal process of heat curing or ITO annealing. In particular, when the concentration of the colorant (A) in the photosensitive composition is high, the content of the polymerizable compound (C) decreases relatively, and the cured film is likely to yellow if the amount of the photopolymerization initiator (D) is increased or the thermosetting compound (H) is added to address this. Therefore, the inclusion of an antioxidant prevents the cured film from yellowing due to oxidation during the heating process.

Examples of the antioxidant (L) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl) N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediolbis[3-(3,5-di -t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc.

Commercially available products include, for example, Adeka STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by ChemiPro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan, and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2 ,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis(tetramethyl-4-piperidyl)imino, Bis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridylsebake ester, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

Commercially available products include, for example, Adeka STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals, Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan, and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical.

Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1 , 1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc.

Commercially available products include, for example, Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan, and Hostanox P-EPQ manufactured by Clariant Chemicals.

Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

Commercially available products include, for example, Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOX PLS manufactured by Chemipro Chemicals Co., Ltd.

The antioxidant (L) can be used alone or in combination of two or more types.

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[Leveling Agent (M)]
The photosensitive composition of the present invention may contain a leveling agent (M), which improves the wettability to a substrate during application and the drying property.

Examples of the leveling agent (M) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

Silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.

More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002, 2110 manufactured by Dow Corning Toray Co., Ltd. , 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Fluorosurfactants include surfactants or leveling agents that have a fluorocarbon chain.

More specifically, examples include Surflon S-242, S-243, S-420, S-611, S-651, and S-386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A manufactured by NEOS Corporation.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, Examples of such sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, etc.

More specifically, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS manufactured by Kao Corporation. -106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW -L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-6 0(K), Amito 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA CORPORATION, (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd., etc.

Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

More specifically, examples include Acetamine 24, Cortamine 24P, 60W, and 86P Conc., manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

More specifically, examples include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethylaminoacetate betaine, and alkyl amine oxides such as lauryl dimethylamine oxide.

More specifically, examples include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

The leveling agent (M) can be used alone or in combination of two or more types.

The content of the leveling agent (M) is preferably 0.001 to 2.0 mass %, and more preferably 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition. Within this range, the balance between the coatability and adhesion of the photosensitive composition is further improved.

[Storage stabilizer (N)]
The photosensitive composition of the present invention may contain a storage stabilizer (N), which stabilizes the viscosity of the photosensitive composition over time.

Examples of storage stabilizers (N) include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

Storage stabilizers (N) can be used alone or in combination of two or more types.

The content of the storage stabilizer (N) is preferably 0.1 to 10 mass% based on 100 mass% of the nonvolatile content of the photosensitive composition.

[Adhesion improver (O)]
The photosensitive composition of the present invention may contain an adhesion improver (O). This improves the adhesion between the coating and the substrate. It also makes it easier to form narrow patterns by photolithography.

Examples of the adhesion improver (O) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and other aminosilanes, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane, etc. silane coupling agents.

The adhesion improver (O) can be used alone or in combination of two or more types.

The content of the adhesion improver (O) is preferably 0.01 to 10 mass %, and more preferably 0.05 to 5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[Organic solvent (P)]
The photosensitive composition of the present invention may contain an organic solvent (P).

The organic solvent (P) may be, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Examples of the diglycerol monomethyl ether include diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

From an environmental perspective, the coloring composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). "Substantially not contained" preferably means that the amount of such organic solvent in the coloring composition is 50 ppm by mass or less, more preferably 30 ppm by mass or less, and even more preferably 10 ppm by mass or less.

The organic solvent (P) can be used alone or in combination of two or more types.

[Content of specific metal elements]
In the coloring composition of the present invention, from the viewpoint of electrical characteristics and light resistance under a low-oxygen environment, the total amount of metals Li, Na, K, Mg, Ca, Fe and Cr (hereinafter, also simply referred to as specific metal elements) contained in the coloring composition is preferably 300 mass ppm or less.

When the total amount of the specific metal elements in the coloring composition is within the above range, a color filter with excellent electrical properties and little loss in brightness in a low-oxygen environment can be formed.

The total amount of the specific metal elements contained in the coloring composition is preferably 200 ppm by mass or less, and particularly preferably 100 ppm by mass or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more.

The amount of each specific metal element contained in the coloring composition is preferably 40 ppm by mass or less, and more preferably 20 ppm by mass or less.

The method for reducing the specific metal element contained in the coloring composition is not particularly limited, but since the specific metal element is contained in large amounts in the coloring agent (A), it is preferable to remove the specific metal element from the coloring agent (A). In addition, since the specific metal element is also mixed in from the equipment used to manufacture the coloring composition, it is also preferable to suppress mixing from the equipment.

The method for reducing and removing the specific metal element contained in the colorant (A) is not particularly limited, and known methods can be used. For example, methods for preventing contamination from equipment during the manufacturing process include the methods described in JP-A-2010-83997 and JP-A-2018-36521. Furthermore, for example, methods for removing the specific metal element from the colorant (A) include the methods described in JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, and JP-A-2010-83997. Among these, a method of washing the colorant (A) with water containing a low content of the specific metal element, such as ion-exchanged water, is preferred.

There are no particular limitations on the method for washing the colorant (A), and any known method can be used. For example, the colorant (A) after synthesis is placed in a container containing ion-exchanged water and stirred. After stirring for a certain period of time, the mixture is filtered using a filter press to separate the colorant (A) from the ion-exchanged water. This process is repeated until the amount of the specific metal element reaches the desired value. It is preferable to wash the mixture while heating it. The colorant (A) is then dried with hot air and pulverized.

The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

It is preferable that the coloring composition of the present invention also reduces the content of metal elements other than the specific metal elements. Examples of metals other than the specific metal elements include Mn, Cs, Ti, Co, Si, Pd, etc.

[Water content]
The colored composition of the present invention preferably has a water content of 2.0% by mass or less.

The content of water in the coloring composition is more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less. There is no particular lower limit for the water content.

There are no particular limitations on the method for controlling the water content, and known methods can be used. For example, each of the above-mentioned components is thoroughly dried, etc., to reduce the amount of water contained in the components. Other examples include a method of producing a colored composition while blowing in dry air, an inert gas, or a mixed gas of these, and a method of dehydrating the colored composition by adding a molecular sieve after production.

The water content can be measured by known methods such as the Karl Fischer method.

[Method of producing photosensitive composition]
The photosensitive composition of the present invention is produced by, for example, adding a colorant (A), a dispersing resin (E), a dye derivative (F), an organic solvent (P), etc., and carrying out a dispersion treatment. The composition can then be produced by blending and mixing an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), etc., into the dispersion. The materials to be blended and the timing of blending are optional. The dispersion process can also be carried out multiple times.

Examples of dispersing machines used for dispersion processing include two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, and attritors.

The average dispersed particle size (secondary particle size) of the colorant in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A moderate particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape aspheric, and the average diameter being the D50 particle size. The organic solvent used for dispersion is used as the dilution solvent for measurement, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to give results with less variation.

It is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more, and contaminated dust from the photosensitive composition by means of centrifugation, filtration with a sintered filter or membrane filter, etc. It is preferable that the photosensitive composition of the present invention does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<Optical filter>
The optical filter of the present invention comprises a substrate and a filter segment formed from the photosensitive composition of the present invention. The optical filter can be used for various purposes. The optical filter herein is preferably a color filter.
In the case of a color filter, the filter segment has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (A) used. Instead of or in addition to the above filter segments, the filter segment may have a magenta filter segment, a cyan filter segment, a yellow filter segment, a white filter segment, a gray filter segment, and a black filter segment. Also, a clear filter may be included.
The substrate may be a transparent substrate or a reflective substrate. The transparent substrate may be a glass substrate. The reflective substrate may be a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[Method of manufacturing optical filters]
An optical filter can be produced by, for example, carrying out the steps of: (1) applying a photosensitive composition onto a substrate to form a layer (coating) of the composition; (2) exposing the layer to light in a pattern through a mask; (3) developing the unexposed parts with an alkali to form a patterned cured film; and (4) heat-treating (post-baking) the pattern.

The method for producing the optical filter will now be described in detail.
(Step (1))
In the step (1) of forming a composition layer, the photosensitive composition is applied onto a substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (prebaked) at a temperature of 50 to 120° C. for 10 to 120 seconds using an oven, a hot plate, or the like as necessary.
Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an image sensor such as a CCD or a CMOS formed on the surface. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with an upper layer, prevent diffusion of substances, and flatten the substrate surface.
The thickness of the layer is preferably from 0.05 to 10.0 μm, and more preferably from 0.3 to 5 μm.

(Step (2))
In the exposure step, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. Examples of the active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF (wavelength 193 nm).
In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure).

(Step (3))
The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is dissolved in an aqueous alkali solution, leaving only the cured areas to give a patterned cured film.
Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the developer is preferably from 0.001 to 10% by mass, and more preferably from 0.01 to 1% by mass.
The pH of the alkaline developer is preferably from 11 to 13, more preferably from 11.5 to 12.5. When used at an appropriate pH, roughening and peeling of the pattern is suppressed, and the remaining film rate after development is improved.

Examples of development methods include the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

(Step (4))
In the heat treatment (post-bake), the patterned cured film obtained in step (3) is heated to sufficiently cure. The temperature is preferably 80 to 300°C. The time is preferably about 2 minutes to 1 hour. When a material with low heat resistance is used for the substrate or when an organic electroluminescence element is used as the light source, the temperature is preferably 150°C or less, and more preferably 130°C or less.

(When forming a pattern by dry etching)
When forming a pattern by dry etching, for example, the resin composition of the present invention is applied onto a substrate, and the layer formed is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then dry etching is performed on the cured film using the patterned photoresist layer as a mask and an etching gas. For pattern formation by dry etching, the method described in JP2013-064993A can be referred to.

<Image display device>
The image display device of the present invention includes the optical filter of the present invention. Examples of the image display device include a liquid crystal display and an organic EL display.
The form of the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned.
The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

<Solid-state imaging element>
The film of the present invention can be used in a solid-state imaging device. The form used in the solid-state imaging device is not particularly limited, but for example, a substrate has a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon, a light-shielding film having an opening only for the light receiving part of the photodiode on the photodiode and the transfer electrode, a device protection film made of silicon nitride, etc. formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving part of the photodiode, and a filter on the device protection film. Furthermore, the device protection film may have a configuration having a light-collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the filter (the side closer to the substrate), or a configuration having a light-collecting means on the filter. The filter may also have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape, by partition walls. In this case, the partition wall preferably has a low refractive index with respect to each colored pixel.
An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), vehicle-mounted cameras, surveillance cameras, and optical sensors.

<Infrared sensor>
The film of the present invention can be used in an infrared sensor. The form in which it is used in an infrared sensor is not particularly limited. Fig. 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor including the film of the present invention. The infrared sensor shown in Fig. 1 includes a solid-state image sensor 110 as a sensor 100.

The imaging area provided on the solid-state imaging element 110 is composed of a combination of an infrared cut filter 111 and a color filter 112.

The infrared cut filter 111 can be formed using the resin composition of the present invention, and transmits light in the visible light range (e.g., light with a wavelength of 400 to 700 nm) and blocks light in the infrared range.

The color filter 112 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range, and for example, a color filter formed with red (R), green (G), and blue (B) pixels is used.

A resin film 114 capable of transmitting light of a wavelength transmitted through the infrared transmission filter 113 is disposed between the infrared transmission filter 113 and the solid-state imaging element 110. The infrared transmission filter 313 is a filter that blocks light in the visible light region and transmits infrared light of a specific wavelength, and can be formed using the resin composition of the present invention.

A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

In the embodiment shown in FIG. 1, a resin film 114 is disposed, but an infrared transmission filter 113 may be formed instead of the resin film 114.

This infrared sensor can simultaneously capture image information, making it possible to perform motion sensing that recognizes the object whose movement is to be detected. In addition, this infrared sensor can obtain distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass".
In the present invention, the non-volatile content or the concentration of the non-volatile content refers to the mass remaining after standing in an oven at 230° C. for 30 minutes.

Before describing the examples, each measurement method will be described.
The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mg KOH/g), and amine value (mg KOH/g) of the resin are as follows.

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and two "TSK-GEL SUPER HZM-N" packings were used as both packings connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The average molecular weight is a polystyrene equivalent value.

(Acid value of resin)
80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly, and titrated with an automatic titrator ("COM-555", Hiranuma Sangyo Co., Ltd.) using a 0.1 mol/L KOH aqueous solution as a titrant to measure the acid value (mg KOH/g). The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

(Amine value of resin)
The amine value of the resin is the total amine value (mg KOH/g) measured in accordance with the method of ASTM D 2074 and converted into non-volatile content.

<Production of colorant (A)>

(Finely divided red pigment (A-1))
100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60° C. Next, the kneaded mixture was poured into warm water, heated to about 80° C. and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80° C. overnight and pulverized to obtain a finely divided red pigment (A-1).

(Finely divided red pigment (A-2))
100 parts of C.I. Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60° C. Next, the kneaded mixture was poured into warm water, heated to about 80° C. and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80° C. overnight and pulverized to obtain a finely divided red pigment (A-2).

(Finely divided blue pigment (A-3))
100 parts of C.I. Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was added to 3,000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80° C. for 24 hours and pulverized to obtain a finely divided blue pigment (A-3).

(Micronized purple pigment (A-4))
100 parts of C.I. Pigment Violet 23, 1,200 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded product was charged into 8,000 parts of warm water, heated to 80° C. and stirred with a high-speed mixer for 2 hours to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 85° C. for 24 hours and pulverized to obtain a finely divided purple pigment (A-4).

(Finely divided green pigment (A-5))
100 parts of C.I. Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded product was added to 3,000 parts of warm water, heated to 70° C. and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80° C. for one day and pulverized to obtain a finely divided green pigment (A-5).

(Finely divided green pigment (A-6)
According to the examples of JP 2017-111398 A, a green pigment (A-6) of the following chemical formula (29) was obtained. 100 parts of the green pigment (A-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3000 parts of warm water, heated to 70 ° C. and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80 ° C. overnight and pulverized to obtain a finely divided green pigment (A-6).

Chemical formula (29)

(Finely divided yellow pigment (A-7))
100 parts of C.I. Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 80° C. This mixture was added to 2,000 parts of warm water, heated to 80° C. and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80° C. overnight and pulverized to obtain a finely divided yellow pigment (A-7).

(Finely divided yellow pigment (A-8))
100 parts of C.I. Pigment Yellow 139 ("Novoperm Yellow P-M3R" manufactured by Clariant), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 70° C. This mixture was added to 3000 parts of hot water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80° C. overnight and pulverized to obtain a finely divided yellow pigment (A-8).

(Finely divided yellow pigment (A-9))
100 parts of C.I. Pigment Yellow 185 (BASF Japan "Palitol Yellow D1155"), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80 ° C. Next, this kneaded product was put into 8 liters of warm water, heated to 80 ° C. and stirred with a high-speed mixer for 2 hours to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, then dried at 85 ° C. overnight and pulverized to obtain a finely divided yellow pigment (A-9).

(Finely divided yellow pigment (A-10)
According to the examples of JP 2012-226110 A, a yellow pigment (A-10) of the following chemical formula (30) was obtained. 100 parts of the yellow pigment (A-10), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded product was added to 8 liters of warm water, heated to 80° C. and stirred with a high-speed mixer for 2 hours to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, then dried at 85° C. overnight and pulverized to obtain a finely divided yellow pigment (A-10).

The average primary particle size of the above finely divided pigment was in the range of 5 to 120 nm.

(Dye (A-11))
A dye (A-11), which is a salt-forming compound consisting of CI Acid Red 52 and Resin 1 having a cationic group on the side chain, was produced by the following procedure.
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized, then charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the end of the dropwise addition, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6,830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, resin 1 having cationic groups on the side chains having ammonium groups and a resin component of 47% by mass was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.
Next, 30 parts of resin 1 having a cationic group on the side chain in terms of non-volatile content was added to 2,000 parts of water, thoroughly stirred and mixed, and then heated to 60 ° C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of C.I. Acid Red 52 in 90 parts of water, and the solution was gradually dropped into the resin solution. After dropping, the solution was stirred at 60 ° C for 120 minutes and reacted thoroughly. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when the bleeding disappeared, and the salt-forming compound was obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer to obtain dye (A-11), which is a salt-forming compound of 32 parts of C.I. Acid Red 52 and resin 1 having a cationic group on the side chain. At this time, the content of the component derived from C.I. Acid Red 52 in dye (A-11) was 25% by mass.

<Production of alkali-soluble resin (B)>
(Alkali-soluble resin (B1-1) solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 65.0 parts of cyclohexanone, heated to 80°C and substituted with nitrogen in the flask, and then a mixture of 57.0 parts of glycerol methacrylate (GLM), 8.6 parts of methacrylic acid, 15.0 parts of paracumylphenol EO-modified (1 mol) acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 19.4 parts of benzyl methacrylate (BzMA) and 0.9 parts of 2,2'-azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour while stirring the entire amount of the obtained copolymer solution, and then the solution was cooled to room temperature, and a mixture of 10.0 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.03 parts of dibutyltin laurate, and 5 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour to obtain a desired alkali-soluble resin (B1-1) solution with a non-volatile content of 20% by mass. The weight average molecular weight of this alkali-soluble resin (B1-1) was 42,000 and the acid value was 56 mgKOH/g.

(Preparation of alkali-soluble resin (B1-2) solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 70.0 parts of cyclohexanone, and the temperature was raised to 80°C. The flask was replaced with nitrogen, and then a mixture of 23.0 parts of n-butyl methacrylate, 14.0 parts of 2-hydroxyethyl methacrylate, 13.0 parts of methacrylic acid, 25.0 parts of paracumylphenol EO-modified (1 mole) acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 25.0 parts of benzyl methacrylate and 0.9 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours from the dropping tube. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain the desired alkali-soluble resin (B1-2) solution with a non-volatile content of 20% by mass. The weight average molecular weight of this alkali-soluble resin (B1-2) was 39,000 and the acid value was 85 mgKOH/g.

(Alkali-soluble resin (B1-3) solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 65.0 parts of cyclohexanone, the temperature was raised to 80°C, and the atmosphere in the flask was replaced with nitrogen, and then a mixture of 13.0 parts of n-butyl methacrylate, 44.0 parts of 2-hydroxyethyl methacrylate, 21.0 parts of methacrylic acid, 22.0 parts of paracumylphenol EO-modified (1 mol) acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), and 0.9 parts of 2,2'-azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected into the entire amount of the obtained copolymer solution for 1 hour while stirring, and then the solution was cooled to room temperature, and a mixture of 10.0 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.03 parts of dibutyltin laurate, and 5 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour to obtain a desired alkali-soluble resin (B1-3) solution with a non-volatile content of 20 mass%. The weight average molecular weight of this alkali-soluble resin (B1-3) was 14,000 and the acid value was 137 mgKOH/g.

(Preparation of alkali-soluble resin (B1-4) solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 70.0 parts of cyclohexanone, and the temperature was raised to 80°C. The flask was replaced with nitrogen, and then a mixture of 23.0 parts of n-butyl methacrylate, 14.0 parts of 2-hydroxyethyl methacrylate, 13.0 parts of methacrylic acid, 50.0 parts of nonylphenol EO-modified (1 mol) acrylate (Aronix M111 manufactured by Toa Gosei Co., Ltd.) and 0.9 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours from the dropping tube. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain the desired alkali-soluble resin (B1-4) solution with a non-volatile content of 20% by mass. The weight average molecular weight of this alkali-soluble resin (B1-4) was 33,000 and the acid value was 79 mgKOH/g.

(Preparation of alkali-soluble resin (B2-1) solution)
A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer, was charged with 100 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc), and heated to 120° C. while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 56.86 parts of glycidyl methacrylate, 66.09 parts of dicyclopentanyl methacrylate, and 31.25 parts of styrene, and a polymerization initiator dissolved in 5.0 parts of azobisisobutyronitrile in PGMAc were added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction.
After the dropwise addition, the mixture was stirred at 120° C. for another 2 hours to obtain a precursor. Next, the atmosphere in the flask was replaced with air, and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 28.82 parts of acrylic acid as modified compounds, and the mixture was reacted at 120° C. for 5 hours. This caused the epoxy group of glycidyl methacrylate to react with the carboxyl group of acrylic acid, and the epoxy group of glycidyl methacrylate was cleaved to generate a hydroxyl group, while simultaneously introducing a polymerizable unsaturated group.
Next, 48.68 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added as modified compounds and reacted at 120°C for 4 hours. As a result, some of the hydroxyl groups generated by cleavage of the epoxy groups of glycidyl methacrylate were reacted with tetrahydrophthalic anhydride to introduce carboxyl groups. Thereafter, PGMAc was added so that the non-volatile content was 20% by mass, to prepare an alkali-soluble resin (B2-1) solution. The alkali-soluble resin (B2-1) had a weight average molecular weight (Mw) of 10,000 and an acid value of 77 mgKOH/g.

(Preparation of alkali-soluble resin (B2-2) solution)
262.0 parts of PGMAc was placed in a reaction vessel equipped with a separable four-neck flask thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer, and the vessel was heated to 120°C while injecting nitrogen gas into the vessel, and a mixture of 49.7 parts of 2-ethylhexyl acrylate, 99.4 parts of glycidyl methacrylate, 6.6 parts of dicyclopentanyl methacrylate, 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise from the dropping tube at the same temperature over 2.5 hours.
After the dropwise addition, the mixture was stirred at 120° C. for another 2 hours to obtain a precursor. The flask was then replaced with air, and 50.4 parts of acrylic acid as a modified compound, 0.6 parts of triphenylphosphine as a catalyst, and 0.2 parts of methylhydroquinone were added, and the mixture was reacted at 110° C. for 10 hours. As a result, the epoxy group of glycidyl methacrylate was reacted with the carboxyl group of acrylic acid, and a hydroxyl group was generated by cleavage of the epoxy group of glycidyl methacrylate, while a polymerizable unsaturated group was introduced.
Next, 21.3 parts of tetrahydrophthalic anhydride was added as a modified compound and reacted at 110°C for 4 hours. As a result, some of the hydroxyl groups generated by cleavage of the epoxy groups of glycidyl methacrylate were reacted with tetrahydrophthalic anhydride to introduce carboxyl groups. Thereafter, PGMAc was added so that the non-volatile content was 20 mass%, to prepare an alkali-soluble resin (B2-2) solution. The alkali-soluble resin (B2-2) had an acid value of 38 mgKOH/g and a weight average molecular weight of 12,000.

(Preparation of alkali-soluble resin (B2-3) solution)
182 parts of PGMAc was placed in a reaction vessel equipped with a separable four-neck flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer, and the vessel was heated to 100° C. while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 70.5 parts of benzyl methacrylate, 43.0 parts of methacrylic acid, 22.0 parts of dicyclopentanyl methacrylate, 3.6 parts of azobisisobutyronitrile as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours.
After the dropwise addition, the mixture was stirred at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate (50 mol% relative to the carboxyl group of the methacrylic acid used in this reaction), 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask, and the reaction was continued at 110°C for 6 hours. As a result, the carboxyl group of the methacrylic acid was reacted with the epoxy group of the glycidyl methacrylate, and a hydroxyl group was generated by cleavage of the epoxy group of the glycidyl methacrylate, and a polymerizable unsaturated group was introduced at the same time. Then, PGMAc was added so that the nonvolatile content was 20% by mass, and an alkali-soluble resin (B2-3) solution was prepared. The alkali-soluble resin (B2-3) had an acid value of 79 mgKOH/g and a weight average molecular weight of 13,000.

(Preparation of alkali-soluble resin (B2-4) solution)
160 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable four-neck flask, and heated to 120° C. while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 109.25 parts of benzyl methacrylate, 24.1 parts of methacrylic acid, 22.03 parts of dicyclopentanyl methacrylate, 1.0 part of azobisisobutyronitrile as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours.
After the dropwise addition, the mixture was stirred at 120° C. for another 2 hours. Then, PGMAc was added so that the non-volatile content was 20% by mass, to prepare an alkali-soluble resin (B2-4) solution. The alkali-soluble resin (B2-4) had a weight average molecular weight of 17,500 and an acid value of 98 mgKOH/g.

<Production of polymerizable compound (C)>
(Polymerizable compound having a urethane bond (C3-1))
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was dropped from the dropping tube over 2 hours. After dropping, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 cm ^-1 was confirmed by IR. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60°C for 6 hours. The nonvolatile content was adjusted to 50% by mass, and a polymerizable compound (C3-1) having an average number of polymerizable unsaturated groups of 9, an acidic group, and a urethane bond was obtained.

<Production of Dispersant (E)>
(Dispersant (E1a-1) Solution)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 50.0 parts of tert-butyl acrylate (t-BA), 45.0 parts of methyl methacrylate (MMA), 5.0 parts of methacrylic acid (MAA), and 25.0 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol (thioglycerol) were added. The temperature was raised to 90°C, and a solution in which 0.1 parts of 2,2'-azobisisobutyronitrile (AIBN) was dissolved in 45.7 parts of PGMAc was added, and the reaction was carried out for 10 hours. It was confirmed that 95% had reacted by measuring the non-volatile content.
Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, PMA), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU) as a catalyst were added and reacted at 120 ° C. for 5 hours. Then, 12.1 g of 3-methoxybutanol (3MB) was added and reacted at 120 ° C. for 3 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was completed, PGMAc was added to prepare a non-volatile content of 50% by mass, and a solution of dispersant (E1a-1) with an acid value of 110 mg KOH / g and a weight average molecular weight of 9000 was obtained.

(Production Examples of Dispersants (E1a-2) and (E1a-3))
Synthesis was carried out in the same manner as in the production example of dispersant (E1a-1) except that the raw materials and the amounts charged were used as shown in Table 1, to obtain solutions of dispersant (E1a-2) and dispersant (E1a-3).

(Dispersant (E1b-1) Solution)
A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the solution was diluted with PGMAc so that the non-volatile content was 30% by measuring the non-volatile content, thereby obtaining a dispersant (E1b-1) solution having an acid value of 70 mgKOH/g and a weight average molecular weight of 8,500.

(Dispersant (E1b-2) Solution)
A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 80 parts of methyl methacrylate, 120 parts of ethyl acrylate, and 40 parts of methoxypropyl acetate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 80°C, and 4.4 parts of 3-mercapto-1,2-propanediol was added, followed by adding 0.2 parts of 2,2'-azobisisobutyronitrile in 20 batches every 30 minutes, and reacting for 12 hours at 80°C. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120°C for 2 hours and at 80°C for 5 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a dispersant (E1b-2) with an acid value of 44 mg KOH/g per non-volatile content was obtained. Furthermore, a dispersant (E1b-2) solution with a non-volatile content of 30% was obtained by adjusting the non-volatile content with PGMAc.

(Dispersant (E1b-3) Solution)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst, and then substituted with nitrogen gas, and reacted at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, the compound obtained in the first step was charged with 160 parts in terms of non-volatile content, 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc, and the inside of the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% had reacted by measuring the nonvolatile content. Finally, 500 parts of a PGMAc diluted solution with a nonvolatile content of 50% of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm ⁻¹ due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the nonvolatile content was adjusted with PGMAc to obtain a dispersant (E1b-3) solution with a nonvolatile content of 30%. The acid value of the obtained dispersant (E1b-3) was 68 mgKOH/g, the unsaturated double bond equivalent was 1,593, and the weight average molecular weight was 13,000.

(Dispersant (E1b-4) Solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6.5 parts of pyromellitic anhydride, 4 parts of 3-mercapto-1,2-propanediol, 0.01 parts of monobutyltin oxide as a catalyst, and 59.6 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, 25 parts of methyl methacrylate, 25 parts of n-butyl methacrylate, 5 parts of methacrylic acid, 10 parts of t-butyl acrylate, 15 parts of (3-ethyloxetan-3-yl)methyl methacrylate, 20 parts of cyclohexyl methacrylate (CHMA), and 51.1 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., 0.12 parts of AIBN were added, and the reaction was continued for 10 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. PGMAc was added to obtain a dispersant (E1b-4) solution with a non-volatile content of 30%. The resulting dispersant (E1b-4) had an acid value of 59.7 mg KOH/g and a weight average molecular weight of 13,000.

(Dispersant (E2-1) Solution)
In a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to this reaction apparatus, and the mixture was stirred while maintaining 110° C. under a nitrogen atmosphere to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was taken to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more calculated from the nonvolatile content. The reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added so that the nonvolatile content was 30% in the nonvolatile content measurement, and a dispersant (E2-1) solution was obtained. The obtained dispersant (E2-1) had an amine value of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn).

<Preparation of Dispersion>
(Dispersion 1)
Using zirconia beads with a diameter of 0.5 mm, the mixture was dispersed for 3 hours in an Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1 having the following composition: The organic solvent (P-1) was PGMAc.
Finely divided blue pigment (A-3): 9.05 parts by weight Finely divided purple pigment (A-4): 0.31 parts by weight Dye (A-11): 4.16 parts by weight Dye derivative (F-1): 1.04 parts by weight Dispersant (E1a-1) solution: 3.47 parts by weight Alkali-soluble resin (B1-2) solution: 10.00 parts by weight Organic solvent (P-1): 71.97 parts by weight

Dye derivative (F-1): Structure shown below
pc represents a phthalocyanine skeleton.

(Dispersions 2 to 17)
Dispersions 2 to 17 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts thereof shown in Tables 2-1 and 2-2 were changed.

Dye derivative (F-2) in Tables 2-1 and 2-2: the following structure

Dye derivative (F-3) in Tables 2-1 and 2-2: the following structure

<Preparation of Photosensitive Composition>
[Example 1]
(Photosensitive Composition 1)
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain Photosensitive Composition 1.
Dispersion 1: 14.43 parts by weight Alkali-soluble resin (B1-2) solution: 20.23 parts by weight Alkali-soluble resin (B2-1) solution: 30.00 parts by weight Polymerizable compound (C1-1): 1.0 part by weight Polymerizable compound (C2-1): 1.0 part by weight Polymerizable compound (C3-1): 2.0 parts by weight Polymerizable compound (C4-1): 1.0 part by weight Polymerizable compound (C5-1): 2.0 parts by weight Compound (D1-1) represented by general formula (2): 1.20 parts by weight Sensitizer (G1-1): 0.80 parts by weight Thermosetting compound (H1-1): 0.06 parts by weight Antioxidant (L): 0.02 parts by weight Leveling agent (M): 1.00 parts by weight Adhesion improver (O): 0.02 parts by weight Organic solvent (P): 25.27 parts by weight

[Examples 2 to 53, Comparative Examples 1 to 3]
(Photosensitive Compositions 2 to 56)
Photosensitive compositions 2 to 56 were prepared in the same manner as in Example 1, except that the photosensitive composition 1 in Example 1 was changed to the raw materials and amounts shown in Tables 3-1 to 3-6.

The details of each ingredient listed in Tables 3-1 to 3-6 are as follows:

[Polymerizable compound (C)]
(Lactone-modified polymerizable compound (C1))
C1-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)
C1-2: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)

(Polymerizable compound (C2) having an acid group)
C2-1: Aronix M-520 (manufactured by Toagosei Co., Ltd.)

(Polymerizable compound having a urethane bond (C3))
C3-1: Polymerizable compound having a urethane bond (C3-1)

(Polymerizable compound having a hydroxyl group (C4))
C4-1: Aronix M-306 (manufactured by Toagosei Co., Ltd.)

(Other polymerizable compounds (C5))
C5-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

[Photopolymerization initiator (D)]
(Compound (D1) represented by general formula (2))
D1-1: Compound of the above-mentioned chemical formula (7) D1-2: Compound of the above-mentioned chemical formula (8) D1-3: Compound of the above-mentioned chemical formula (9)

(Oxime-based photopolymerization initiator (D2))
D2a-1: TRONLY TR-PBG-3057 (manufactured by Changzhou Strong New Materials Co., Ltd., a compound containing one oxime group per molecule)
D2a-2: Compound of the above-mentioned chemical formula (10) D2a-3: Compound of the above-mentioned chemical formula (11) D2a-4: Compound of the above-mentioned chemical formula (12) D2a-5: Compound of the above-mentioned chemical formula (13) D2b-1: Compound of the above-mentioned chemical formula (15)

(Other Photopolymerization Initiators (D3))
D3-1: Omnirad 907 (manufactured by IGM Resins, acetophenone-based compound)
D3-2: Omnirad 369 (manufactured by IGM Resins, acetophenone-based compound)

[Sensitizer (G)]
(Thioxanthone Compound (G1))
G1-1: 2,4-diethylthioxanthone (benzophenone compound (G2))
G2-1: 4,4'-bis(diethylamino)benzophenone

[Thermosetting compound (H)]
(Epoxy compound (H1))
H1-1: EHPE-3150 (manufactured by Daicel Corporation)

[Antioxidant (L)]
L-1: IRGANOX 1010 (manufactured by BASF Japan)
L-2: Adeka STAB LA-52 (manufactured by ADEKA Corporation)
The above (L-1) and (L-2) were mixed in equal amounts to prepare an antioxidant (L).

[Leveling Agent (M)]
M-1: BYK-330 (manufactured by BYK-Chemie)
M-2: Megafac F-551 (DIC)
One part each of (M-1) and (M-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution as a leveling agent (M).

[Adhesion improver (O)]
O-1: 3-glycidoxypropyltrimethoxysilane O-2: X-12-1048 (manufactured by Shin-Etsu Silicone Co., Ltd.)
The above (O-1) and (O-2) were mixed in equal amounts to prepare an adhesion improver (O).

[Organic solvent (P)]
P-1: Propylene glycol monomethyl ether acetate 30 parts P-2: Cyclohexanone 30 parts P-3: Ethyl 3-ethoxypropionate 10 parts P-4: Propylene glycol monomethyl ether 10 parts P-5: Cyclohexanol acetate 10 parts P-6: Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above parts by mass to obtain organic solvent (P).

<Evaluation of Photosensitive Composition>
The obtained photosensitive compositions 1 to 56 (Examples 1 to 53 and Comparative Examples 1 to 3) were evaluated for developability (solubility in the developer, development time), cross-sectional shape, adhesion, heat resistance, and solvent resistance by the following methods. The evaluation results are shown in Table 4.

[Developer solubility]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm, so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 ° C. for 1 minute. Then, the substrate was placed in a petri dish, and 20 g of an aqueous developer containing 0.12 mass % of a nonionic surfactant and 0.04 mass % of potassium hydroxide at 23 ° C. was poured in. The state in which the coating of the photosensitive composition dissolved from the substrate was visually observed. The evaluation criteria are as follows, with 3 or more being considered practical.
5: The coating of the photosensitive composition is dissolved in the developer without cracking.
4: The coating of the photosensitive composition is dissolved in the developer, but slight cracks are generated in the coating, and the powdery coating quickly dissolves.
3: The photosensitive composition film is slightly dissolved in the developer, but cracks occur in the film and small pieces of the film peeled off from the substrate are dissolved.
2: After the photosensitive composition coating cracks, a large portion of the coating peeled off from the substrate dissolves little by little.
1: After the photosensitive composition coating cracked, a large portion of the coating peeled off from the substrate did not dissolve at all.

[Developing time]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm, so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 ° C. for 1 minute. Then, the substrate was placed in a petri dish, and 20 g of an aqueous developer containing 0.12 mass % of a nonionic surfactant and 0.04 mass % of potassium hydroxide at 23 ° C. was poured in. The time when the developer was poured in was set as 0 seconds, and the time until the coating of the photosensitive composition was completely dissolved was measured. The evaluation criteria are as follows, and 3 or more is considered to be practical.
5: Less than 100 seconds.
4: Between 100 and 150 seconds.
3: Between 150 and 200 seconds.
2: More than 200 seconds but less than 300 seconds.
1: More than 300 seconds.

[Cross-sectional shape]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 ° C. for 1 minute. Next, after cooling the substrate to room temperature, it was exposed to light at an illuminance of 30 mW / cm ² and 50 mJ / cm ² through a photomask with a stripe pattern of 100 μm width using a high-pressure mercury lamp. Thereafter, the substrate was spray-developed using an aqueous developer containing 0.12 mass % of a nonionic surfactant and 0.04 mass % of potassium hydroxide at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 30 minutes. The spray development was performed for each coating of the photosensitive composition in the shortest time possible to form a pattern without remaining development residue.
The cross-sectional shape of the pattern was confirmed using a scanning electron microscope (Hitachi High-Tech Corporation's "S-3000H"). The cross-sectional shape was evaluated by capturing an SEM image of the cross section of a 100 μm wide stripe pattern and measuring the taper angle between the substrate and the end of the pattern cross section. The evaluation criteria are as follows, with 3 or more being considered practical.
5: Taper angle 40 degrees or more and less than 50 degrees 4: Taper angle 50 degrees or more and less than 60 degrees 3: Taper angle 30 degrees or more and less than 40 degrees, or 60 degrees or more and less than 70 degrees 2: Taper angle 20 degrees or more and less than 30 degrees, or 70 degrees or more and less than 90 degrees 1: Taper angle less than 20 degrees, or 90 degrees or more

[Adhesion]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 ° C. for 1 minute. Next, after cooling the substrate to room temperature, the substrate was exposed to light at an illuminance of 30 mW/cm ² and 50 mJ/cm ² through a photomask having a stripe pattern with a width of 5 to 25 μm and an interval of 5 μm. Thereafter, the substrate was spray-developed using an aqueous developer containing 0.12 mass % of a nonionic surfactant and 0.04 mass % of potassium hydroxide at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 30 minutes. The spray development was performed for each coating of the photosensitive composition in the shortest time possible to form a pattern without residual development.
The obtained patterns of widths of 5, 10, 15, 20, and 25 μm on the substrate were observed with an optical microscope to confirm the minimum line width of the remaining pattern. The evaluation criteria are as follows, with a score of 3 or higher being considered practical.
5: Fine lines of 10 μm or less remain.
4: A thin line of 15 μm remains.
3: A thin line of 20 μm remains.
2: 25 μm fine lines remain.
1: No fine lines remain.

[Heat resistance evaluation]
The obtained photosensitive composition was applied by spin coating onto a glass substrate (Corning Eagle 2000) measuring 100 mm long x 100 mm wide x 0.7 mm long, so that the film thickness after drying was 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Next, the substrate was cooled to room temperature, and then exposed to light at an illuminance of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp. Thereafter, the substrate was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 40 seconds, followed by washing with ion-exchanged water, air drying, and heating in a clean oven at 230° C. for 30 minutes.
The chromaticity ([L*(1), a*(1), b*(1)]) of the resulting coating film under Illuminant C was measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optical Co., Ltd.). Thereafter, the coating film was heated at 230°C for 1 hour to evaluate heat resistance, and the chromaticity ([L*(2), a*(2), b*(2)]) under Illuminant C was measured, and the color difference ΔEab* was calculated using the following formula. The evaluation criteria were as follows, with a score of 3 or higher being considered practical.
ΔEab* = ((L*(2) - L*(1)) ^² + (a*(2) - a*(1)) ^² + (b*(2) - b*(1)) ^² ) ^1/2
5: ΔEab* is less than 1 4: ΔEab* is 1 or more and less than 2 3: ΔEab* is 2 or more and less than 3 2: ΔEab* is 3 or more and less than 5 1: ΔEab* is 5 or more

[Solvent resistance evaluation]
The obtained photosensitive composition was applied by spin coating onto a glass substrate (Corning Eagle 2000) measuring 100 mm long x 100 mm wide x 0.7 mm long, so that the film thickness after drying was 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Next, the substrate was cooled to room temperature, and then exposed to light at an illuminance of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp. Thereafter, the substrate was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 40 seconds, followed by washing with ion-exchanged water, air drying, and heating in a clean oven at 230° C. for 30 minutes.
The chromaticity ([L*(1), a*(1), b*(1)]) of the resulting coating film under Illuminant C was measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optical Co., Ltd.). Thereafter, to evaluate solvent resistance, the film was immersed in N-methyl-2-pyrrolidone at 23°C for 30 minutes, and the chromaticity ([L*(2), a*(2), b*(2)]) under Illuminant C was measured, and the color difference ΔEab* was calculated using the following formula. The evaluation criteria were as follows, with a score of 3 or higher being considered practical.
ΔEab* = ((L*(2) - L*(1)) ^² + (a*(2) - a*(1)) ^² + (b*(2) - b*(1)) ^² ) ^1/2
5: ΔEab* is less than 1 4: ΔEab* is 1 or more and less than 2 3: ΔEab* is 2 or more and less than 3 2: ΔEab* is 3 or more and less than 5 1: ΔEab* is 5 or more

Claims (8)

A photosensitive coloring composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a dispersant (E) (excluding the case of an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by the following general formula (1)),
The alkali-soluble resin (B) contains an alkali-soluble resin (B1) containing a monomer unit (b1) based on a monomer represented by the following general formula (1),
A photosensitive coloring composition, wherein the photopolymerization initiator (D) contains a compound (D1) represented by the following general formula (2):
General formula (1)
In general formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n is an integer of 1 to 15.
General formula (2)
(In general formula (2), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₆ represents a hydrogen atom or a monovalent substituent.) The photosensitive coloring composition according to claim 1, wherein the dispersant (E) includes a dispersant (E1) having an acidic group. the dispersant (E1) having an acidic group is a polyester dispersant (E1a),
The polyester dispersant (E1a) has a main chain containing an aromatic carboxylic acid ester moiety having an ester bond formed by esterification reaction of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety, the acid anhydride group is 0.9 to 1.5 moles per mole of the hydroxyl groups, and the main chain containing the aromatic carboxylic acid ester moiety has a blocking moiety derived from a monoalcohol, characterized in that the photosensitive coloring composition according to claim 2. The photosensitive coloring composition according to claim 1, wherein the content of the monomer units (b1) based on the monomer represented by general formula (1) is 10 to 70 mass % of the total monomer units of the alkali-soluble resin (B1). The photosensitive coloring composition according to claim 2, wherein the acid value of the dispersant (E1) having an acidic group is 40 to 140 mg KOH/g. A color filter having a substrate and filter segments formed from the photosensitive coloring composition according to any one of claims 1 to 4. An image display device having the color filter according to claim 6. A solid-state imaging device comprising the color filter according to claim 6 .