Pigment dispersion composition, photosensitive resin composition, resin cured film, and image display element

Abstract

Provided are: a pigment dispersion composition which has good pigment dispersibility; and a photosensitive resin composition from which a resin cured film having excellent developability, excellent solvent resistance and excellent pattern adhesion can be obtained. This pigment dispersion composition comprises a binder resin (A-1) comprising a resin (A-1a) or a resin (A-1b), a pigment (B), a polymeric dispersant (C), and a solvent (D). The resin (A-1a) has a structure such that an ethylenically unsaturated group-containing compound (m-4) that has a group having reactivity with a carboxyl group is added to some of carboxyl groups in a copolymer (P) of monomers (M), wherein the monomers (M) include: a polymerizable monomer (m-1) comprising a polymerizable monomer (m-1a) that has a bridged cyclic hydrocarbon group or a polymerizable monomer (m-1b) represented by formula (1); acrylic acid (m-2); and an aromatic ring-containing polymerizable monomer (m-3).

Description

Pigment dispersion composition, photosensitive resin composition, cured resin film, and image display element

[0001] The present disclosure relates to a pigment dispersion composition, a photosensitive resin composition, a cured resin film, a color filter, and an image display device. This application claims priority to Japanese Patent Application No. 2023-208642, filed on December 11, 2023, the contents of which are incorporated herein by reference.

[0002] Currently, from the viewpoint of resource and energy conservation, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in fields such as various coatings, printing, paints, and adhesives. Photosensitive resin compositions are used in the field of electronic materials such as printed wiring boards, such as solder resists and color filter resists. Color filters generally consist of a transparent substrate such as a glass substrate, red, green, and blue pixels formed on the transparent substrate, a black matrix formed at the boundaries between the pixels, and a protective film formed on the pixels and the black matrix. Color filters having such a configuration are typically manufactured by sequentially forming colored patterns such as the black matrix and pixels, and patterns such as the protective film, on the transparent substrate. Various methods have been proposed for forming various patterns. Among these, the pigment / dye dispersion method, which uses a photosensitive resin composition as a resist and is produced by a photolithography process that involves repeated coating, exposure, development, and baking, is currently mainstream because it provides colored patterns that are highly durable and have few defects such as pinholes.

[0003] Generally, photosensitive resin compositions used in photolithography contain an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a pigment / dye dispersion composition (also referred to as a colorant), and a solvent. While the pigment / dye dispersion method has the above advantages, it requires heat resistance capable of withstanding high baking temperatures and resistance to various solvents to which it is exposed during the manufacturing process, since black matrices and red, green, and blue patterns are repeatedly formed. Generally, photosensitive resin compositions used in photolithography are required to have negative resist properties. For example, Patent Document 1 discloses the use of a polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.

[0004] In recent years, there has been a demand for higher image quality and higher definition in displays such as liquid crystal displays and organic electroluminescence displays, and there is also a demand for designs that achieve higher brightness and an expanded color reproduction range for color filters. In order to achieve higher brightness and an expanded color reproduction range, there are examples of using only dyes instead of pigments as coloring materials for colorants, but dyes have inferior heat resistance and solvent resistance compared to pigments, and their usage ratios and types are limited, so in most cases pigments are included in the coloring materials.

[0005] When forming color filters using pigments, it is essential to uniformly refine the pigments. By refining the pigments, scattering of light passing through the color filter by the pigment particles is reduced, contributing to higher transmittance and achieving higher brightness. Furthermore, efforts are being made to increase the concentration of coloring materials in colorants in order to expand the color reproduction range.

[0006] JP 2019-112494 A

[0007] However, there is a problem that finely divided pigment particles are prone to aggregation and decrease in pigment dispersibility. Furthermore, as the concentration of colorant increases, the concentration of dispersant and binder resin decreases, so there is a need to achieve various resist properties such as pigment dispersibility, solvent resistance, and pattern adhesion with smaller amounts of dispersant, binder resin, and other components.

[0008] The present disclosure has been made to solve the above-mentioned problems, and aims to provide a pigment dispersion composition that can provide sufficient pigment dispersibility even when the concentrations of the dispersant and binder resin are reduced due to an increase in the pigment concentration. It also aims to provide a photosensitive resin composition that can provide a cured resin film that is excellent in developability, solvent resistance, and pattern adhesion, a color filter having the cured product thereof, and an image display element including the same.

[0009] The present invention includes the following aspects: [1] A pigment dispersion composition comprising a binder resin (A-1), a pigment (B), a polymer dispersant (C), and a solvent (D), wherein the binder resin (A-1) is a resin in which an ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is added to some of the carboxy groups of a copolymer (P) which comprises a structural unit derived from at least one polymerizable monomer (m-1) selected from the group consisting of a polymerizable monomer (m-1a) (excluding polymerizable monomer (m-1b)) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer (m-1b) represented by the following formula (1), a structural unit derived from acrylic acid (m-2), and a structural unit derived from an aromatic ring-containing polymerizable monomer (m-3), and wherein the unsaturated group equivalent of the resin (A-1) is 100 to 700 g / mol: (In formula (1), R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R １ and R ２ may be bonded to form a ring structure. ３ and R ４each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, which may be linear or branched.) [2] The pigment dispersion composition according to [1], wherein the weight average molecular weight of the binder resin (A-1) is 5,000 to 30,000 g / mol. [3] The pigment dispersion composition according to [1] or [2], wherein the group reactive with a carboxy group possessed by the ethylenically unsaturated group-containing compound (m-4) is an epoxy group or an oxetanyl group. [4] The pigment dispersion composition according to any one of [1] to [3], wherein, of all the structural units of the copolymer (P), the content of structural units derived from the polymerizable monomer (m-1) is 1 to 30 mol%, the content of structural units derived from the acrylic acid (m-2) is 55 to 95 mol%, and the content of structural units derived from the aromatic ring-containing polymerizable monomer (m-3) is 1 to 30 mol%. [5] The pigment dispersion composition according to any one of [1] to [4], wherein the content of the ethylenically unsaturated group-containing compound (m-4) is 20 to 80 mol per 100 mol of all structural units of the copolymer (P). [6] The pigment dispersion composition according to any one of [1] to [4], wherein the content of the ethylenically unsaturated group-containing compound (m-4) is 40 to 90 mol per 100 mol of structural units derived from the acrylic acid (m-2). [7] The pigment dispersion composition according to any one of [1] to [6], wherein the polymer dispersant (C) has at least one group selected from the group consisting of a tertiary amino group and a quaternary ammonium cation group. [8] The pigment dispersion composition according to [7], wherein the polymer dispersant (C) is a block polymer of at least one monomer selected from the group consisting of a monomer having a tertiary amino group and an ethylenically unsaturated group, and a monomer having a quaternary ammonium cation group and an ethylenically unsaturated group, and another monomer having an ethylenically unsaturated group. [9] The pigment dispersion composition according to any one of claims 1 to 8, comprising: 10 to 50 parts by mass of the binder resin (A-1); and 10 to 80 parts by mass of the polymer dispersant (C) relative to 100 parts by mass of the pigment (B).

[10] A photosensitive resin composition comprising: a binder resin (A); a pigment (B); a polymer dispersant (C); a solvent (D); a reactive diluent (E); and a photopolymerization initiator (F), wherein the binder resin (A) comprises a binder resin (A-1), and the binder resin (A-1) is a resin in which an ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is added to a portion of the carboxy groups of a copolymer (P) comprising a structural unit derived from at least one polymerizable monomer (m-1) selected from the group consisting of a polymerizable monomer (m-1a) (excluding the polymerizable monomer (m-1b)) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer (m-1b) represented by the following formula (1), a structural unit derived from acrylic acid (m-2), and a structural unit derived from an aromatic ring-containing polymerizable monomer (m-3): A photosensitive resin composition characterized in that the binder resin (A-1) has an unsaturated group equivalent weight of 100 to 700 g / mol. (In formula (1), R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R １ and R ２ may be bonded to form a ring structure. ３ and R ４each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, which may be linear or branched.)

[11] The photosensitive resin composition according to

[10] , wherein the binder resin (A) further contains a binder resin (A-2).

[12] The photosensitive resin composition according to

[11] , wherein the binder resin (A-2) is at least one resin selected from the group consisting of a (meth)acrylic resin, an epoxy (meth)acrylic resin, and a vinyl ester resin, and does not belong to the binder resin (A-1).

[13] The photosensitive resin composition according to

[10] , wherein, per 100 parts by mass of the pigment (B), the binder resins (A) are contained in an amount of 50 to 280 parts by mass in total, the polymer dispersant (C) is contained in an amount of 10 to 80 parts by mass, the reactive diluent (E) is contained in an amount of 40 to 200 parts by mass, and the photopolymerization initiator (F) is contained in an amount of 0.1 to 10 parts by mass.

[14] A cured resin film obtained by curing the photosensitive resin composition according to

[10] or

[11] .

[15] A color filter having a cured product of the photosensitive resin composition according to

[10] or

[11] .

[16] An image display element having the color filter according to

[15] .

[0010] According to the present disclosure, it is possible to provide a pigment dispersion composition with good pigment dispersibility. It is also possible to provide a photosensitive resin composition that can yield a cured resin film with excellent developability, solvent resistance, and pattern adhesion. Furthermore, it is also possible to provide a color filter having a cured product of the photosensitive resin composition, and an image display element including the color filter.

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below. In this specification, the term "(meth)acryloyloxy group" refers to one or more groups selected from methacryloyloxy groups and acryloyloxy groups. The same applies to "(meth)acrylic acid" and "(meth)acrylate."

[0012] <Photosensitive Resin Composition> The pigment dispersion composition of this embodiment contains a binder resin (A-1), a pigment (B), a polymer dispersant (C), and a solvent (D). The binder resin (A-1) is a resin in which an ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is added to a portion of the carboxy groups of a copolymer (P). The copolymer (P) contains a structural unit derived from a polymerizable monomer (m-1), a structural unit derived from acrylic acid (m-2), and a structural unit derived from an aromatic ring-containing polymerizable monomer (m-3). The polymerizable monomer (m-1) is at least one selected from the group consisting of a polymerizable monomer (m-1a) (excluding polymerizable monomer (m-1b)) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer (m-1b) represented by the following formula (1): The pigment dispersion composition, wherein the binder resin (A-1) has an unsaturated group equivalent weight of 100 to 700 g / mol. (In formula (1), R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R １ and R ２ may be bonded to form a ring structure. ３ and R ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, which may be linear or branched.

[0013] [Binder Resin (A-1)] The binder resin (A-1) is a resin in which an ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is added to a portion of the carboxy groups of the copolymer (P). The copolymer (P) contains a structural unit derived from a polymerizable monomer (m-1), a structural unit derived from acrylic acid (m-2), and a structural unit derived from an aromatic ring-containing polymerizable monomer (m-3). The polymerizable monomer (m-1) is at least one selected from the group consisting of a polymerizable monomer (m-1a) (excluding the polymerizable monomer (m-1b)) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer (m-1b) represented by the above formula (1). The inclusion of the binder resin (A-1) improves the dispersibility of the pigment dispersion composition or photosensitive resin composition described below. Furthermore, when the photosensitive resin composition is exposed to light through a photomask and developed, the developability and pattern adhesion are good, and the resulting cured film has good solvent resistance.

[0014] First, the copolymer (P), which is a precursor of the binder resin (A-1) of this embodiment, will be described. "Copolymer (P)" The copolymer (P) used in this embodiment contains, as constituent monomers (M), at least one polymerizable monomer (m-1) selected from the group consisting of polymerizable monomers (m-1a) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and polymerizable monomers (m-1b) represented by the above formula (1), acrylic acid (m-2), and an aromatic ring-containing polymerizable monomer (m-3). The terms "polymerizable monomer (m-1a) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms," "polymerizable monomer (m-1b) represented by the following formula (1)," "polymerizable monomer (m-1)," "acrylic acid (m-2)," and "aromatic ring-containing polymerizable monomer (m-3)" may be referred to as "monomer (m-1a)," "monomer (m-1b)," "monomer (m-1)," "monomer (m-2)," and "monomer (m-3)," respectively.

[0015] "Monomer (m-1)" Monomer (m-1) is at least one selected from monomer (m-1a) and monomer (m-1b). Monomer (m-1a) has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. Here, the bridged cyclic hydrocarbon preferably has a structure represented by the following formula (3) or (4). Examples of bridged cyclic hydrocarbons include adamantane and norbornane. The bridged cyclic hydrocarbon group refers to a group corresponding to the remaining portion of the structure after removing some of the hydrogen atoms. Furthermore, monomer (m-1a) does not include monomer (m-1b), which will be described later.

[0016]

[0017] In formula (3), A and B each independently represent a linear or branched alkylene group (including cyclic groups) having 1 to 10 carbon atoms. A and B may be the same or different. The branches of A and B may be bonded to each other to form a cyclic structure. R ５ represents a hydrogen atom or a methyl group.

[0018]

[0019] In formula (4), A', B', and D each independently represent a linear or branched alkylene group (including cyclic) having 1 to 10 carbon atoms. A', B', and D may be the same or different. The branches of A', B', and D may be bonded to each other to form a cyclic structure. R ６ represents a hydrogen atom or a methyl group.

[0020] As the monomer (m-1a), a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is preferred, and adamantyl (meth)acrylate or a (meth)acrylate having a structure represented by the following formula (5) is more preferred.

[0021]

[0022] In formula (5), R ７ ~R ９ R each independently represents a hydrogen atom or a methyl group. １０ and R １１represents a hydrogen atom or a methyl group, or may be bonded to form a saturated or unsaturated ring. The ring is preferably a 5- or 6-membered ring. * represents a bond connected to the (meth)acryloyloxy group.

[0023] Specific examples of the (meth)acrylate having the structure represented by the above formula (5) include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0024] The monomer (m-1b) is a polymerizable monomer represented by the above formula (1). １ and R ２ Examples of the substituent in the hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, represented by the formula (I) include an alkoxy group and an aryl group. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, include linear or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a t-amyl group, a stearyl group, a lauryl group, and a 2-ethylhexyl group; alicyclic groups such as a cyclohexyl group, a t-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group, and a 2-methyl-2-adamantyl group; alkyl groups substituted with an alkoxy group, such as a 1-methoxyethyl group and a 1-ethoxyethyl group; and alkyl groups substituted with an aryl group, such as a phenylaralkyl group. ３ and R ４ Specific examples of the hydrocarbon group having 1 to 4 carbon atoms, which may be linear or branched, represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

[0025] Specific examples of the monomer (m-1b) include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-ene, Examples include tricyclo[4.4.0.12,5]undec-3-ene, tricyclo[6.2.1.01,8]undec-9-ene, tetracyclo[4.4.0.12,5.17,10.01,6]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12]dodec-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadec-4-ene, etc. These may be used alone or in combination of two or more.

[0026] By including the monomer (m-1a) and / or the monomer (m-1b), good dispersibility can be obtained as a pigment dispersion composition or a photosensitive resin composition. Furthermore, the development rate of the photosensitive resin composition can be adjusted to a desired level. Furthermore, a color filter having high surface hardness and suppressing bleed-out of the colorant can be provided. At the same time, the color filter has high resistance to thermal decomposition and high resistance to thermal yellowing, thereby minimizing color change after baking. Either the monomer (m-1a) or the monomer (m-1b) may be used alone, or both may be used. In particular, from the viewpoint of hardness, adamantyl (meth)acrylate or a (meth)acrylate having a structure represented by the above formula (5) is preferred as the monomer (m-1), with dicyclopentanyl (meth)acrylate being more preferred.

[0027] "Monomer (m-2)" The copolymer (P) of this embodiment contains the monomer (m-2) as the constituent monomer (M). The monomer (m-2) is acrylic acid. The binder resin (A-1) contains a carboxy group derived from the monomer (m-2), which enhances its affinity with alkaline developers, resulting in a photosensitive resin composition with excellent developability and enabling the provision of high-resolution color filters with precise dimensional accuracy. In particular, the use of the monomer (m-2) as the copolymer (P) results in a pigment dispersion composition or photosensitive resin composition with excellent pigment dispersibility compared to other acid group-containing polymerizable monomers having a carboxy group, sulfo group, phospho group, or the like. Therefore, improved pigment dispersibility can be expected to result in improved color filter brightness and transmittance. Furthermore, improved pigment dispersibility can also reduce light scattering by pigment particles during exposure, thereby contributing to improved developability of the photosensitive resin composition. When methacrylic acid is used in place of the monomer (m-2), the viscosity of the resin tends to increase, which may result in insufficient stability during the synthesis of the copolymer (P), making it impossible to ensure the desired content. Furthermore, since the viscosity of the pigment dispersion composition or the photosensitive resin composition also tends to increase, there is a concern that it may be necessary to increase the amount of the solvent (D) or the reactive diluent (E) beyond the preferred range of content ratio in order to lower the viscosity. The copolymer (P) of this embodiment can use an acid group-containing polymerizable monomer other than the monomer (m-2) in combination as a constituent monomer within a range that does not impair the effects of the present invention, but for the reasons described above, it is preferable not to use such a monomer.

[0028] "Monomer (m-3)" Monomer (m-3) is not particularly limited as long as it is a polymerizable monomer containing an aromatic ring other than monomer (m-1a), monomer (m-1b), and monomer (m-2). By including monomer (m-3), affinity with pigment (B) is improved, and a pigment dispersion composition or photosensitive resin composition with excellent pigment dispersibility can be obtained. Accordingly, it is possible to provide a pigment dispersion composition or photosensitive resin composition that can obtain sufficient pigment dispersibility even when the concentrations of the dispersant and binder resin are reduced due to an increase in pigment concentration.

[0029] Specific examples of monomer (m-3) include benzyl (meth)acrylate, phenyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, rosin (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, styrene, α-, o-, m-, and p-alkyl, nitro, cyano, and amide derivatives of styrene, N-phenylmaleimide, and N-(4-hydroxyphenyl)maleimide. From the standpoints of ease of copolymerization and availability, the use of benzyl (meth)acrylate, phenyl (meth)acrylate, styrene, and α-, o-, m-, and p-alkyl derivatives of styrene is preferred, and the use of benzyl (meth)acrylate is more preferred. These compounds may be used alone or in combination of two or more.

[0030] "Ratio of Each Monomer in Copolymer (P)" There are no particular limitations on the ratio of each monomer (molar ratio of each monomer) in the copolymer (P) of this embodiment. Furthermore, the ratio of monomer (m-1), when the total of all constituent monomers of copolymer (P) is taken as 100 mol%, is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. When the total of all constituent monomers of copolymer (P) is taken as 100 mol%, the ratio of monomer (m-1) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less. Any combination of these lower and upper limits may be used. There are no limitations on the ratio of monomer (m-1a) and / or (m-1b) within monomer (m-1), and any ratio can be used. When the ratio of monomer (m-1) is 1 mol% or more, desired properties derived from monomer (m-1) can be obtained. When the blending ratio of the monomer (m-1) is 40 mol % or less, other polymerizable monomers can be blended sufficiently, and compatibility with other properties can be achieved.

[0031] The proportion of monomer (m-2), when the total of all constituent monomers of copolymer (P) is taken as 100 mol%, is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 55 mol% or more. The proportion of monomer (m-2), when the total of all constituent monomers of copolymer (P) is taken as 100 mol%, is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less. Any combination of these lower and upper limits may be used. When the blending proportion of monomer (m-2) is 40 mol% or more, good developability of the pigment dispersion composition can be obtained, and a sufficient amount of ethylenically unsaturated groups can be introduced into the side chains of copolymer (P). On the other hand, when this blending proportion is 95 mol% or less, other monomers can be blended in sufficiently, thereby achieving compatibility with other properties.

[0032] The proportion of monomer (m-3) is preferably 1 mol% or more, more preferably 4 mol% or more, and even more preferably 8 mol% or more, when the total of all constituent monomers of copolymer (P) is 100 mol%. The proportion of monomer (m-3) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total of all constituent monomers of copolymer (P) is 100 mol%. Any combination of these lower and upper limits may be used. When this blending proportion is 1 mol% or more, the desired properties derived from the aromatic monomer can be obtained, and when this blending proportion is 40 mol% or less, other monomers can be sufficiently blended, thereby achieving compatibility with other properties.

[0033] "Other Polymerizable Monomers" The copolymer (P) of this embodiment may contain structural units derived from other polymerizable monomers, as long as the desired properties derived from the monomers (m-1), (m-2), and (m-3) are not impaired. That is, other polymerizable monomers copolymerizable with the monomers (m-1a), (m-1b), (m-2), and (m-3) may be included. The other polymerizable monomers are generally radically polymerizable compounds having an ethylenically unsaturated group. Specific examples of the radically polymerizable compounds include dienes such as butadiene, non-reactive (meth)acrylic acid esters, reactive (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, maleimides, and unsaturated dicarboxylic acid diesters. Examples of the non-reactive (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, and hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, and the like.Examples of the reactive (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 6-hydroxypent ... cyclohexyl (meth)acrylate, 5-hydroxy-3-methyl-pentyl (meth)acrylate, cyclohexane-1,4-dimethanol-mono(meth)acrylate, 2-(2-hydroxyethyloxy)ethyl (meth)acrylate, 2,3-dihydroxy(meth)acrylate, butanetriol mono(meth)acrylate, pentanetriol mono(meth)acrylate, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, Examples of the isocyanato group-containing ethylenically unsaturated compound include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 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, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and compounds having a blocked isocyanato group obtained by blocking the isocyanato group of the above-mentioned isocyanato group-containing ethylenically unsaturated compound with a blocking agent. Examples of the (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, and (meth)acrylic acid anthracenylamide.Examples of the vinyl compounds include (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene. Examples of the maleimides include N-cyclohexylmaleimide and N-laurylmaleimide. Examples of the unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate. These may be used alone or in combination of two or more, as necessary.

[0034] "Proportion of other polymerizable monomers" The proportion of other polymerizable monomers in the copolymer (P) of this embodiment is preferably 10 mol % or less, more preferably 5 mol % or less, when the total of all constituent monomers of the copolymer (P) is 100 mol %.

[0035] "Compound added to copolymer (P)" Next, the binder resin (A-1) in which an ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is added to copolymer (P) will be described. The ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is sometimes referred to as "compound (m-4)."

[0036] "Compound (m-4)" Compound (m-4) has a group reactive with a carboxy group and an ethylenically unsaturated group. Examples of the group reactive with a carboxy group include an epoxy group, an oxetanyl group, an isocyanato group, a hydroxyl group, and an amino group. By adding a carboxy group derived from monomer (m-2) of copolymer (P) to a group reactive with a carboxy group possessed by compound (m-4), an ethylenically unsaturated group can be introduced into the side chain of copolymer (P). By having binder resin (A-1) have an ethylenically unsaturated group derived from compound (m-4), it is possible to provide a pigment dispersion composition or a photosensitive resin composition that suppresses bleeding out of pigment (B) and exhibits excellent resist properties such as heat resistance, solvent resistance, pattern adhesion, and developability.

[0037] Specific examples of compound (m-4) include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, 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, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, ) acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 5-hydroxy-3-methyl-pentyl (meth)acrylate, cyclohexane-1,4-dimethanol-mono(meth)acrylate, 2-(2-hydroxyethyloxy)ethyl (meth)acrylate, 2,3-dihydroxy (meth)acrylate, butanetriol mono(meth)acrylate, pentanetriol mono(meth)acrylate, aminoethyl (meth)acrylate, monomethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, etc. These may be used alone or in combination of two or more. Among these, from the viewpoints of availability and reactivity with the copolymer (P), those having an epoxy group or an oxetanyl group are preferred, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate are more preferred, and glycidyl (meth)acrylate is even more preferred.

[0038] "Incorporation ratio of compound (m-4)" The incorporation ratio of compound (m-4) relative to copolymer (P) is preferably 20 moles or more, more preferably 25 moles or more, and even more preferably 30 moles or more, based on 100 moles of the total of all constituent monomers of copolymer (P). The incorporation ratio of compound (m-4) relative to copolymer (P) is preferably 80 moles or less, more preferably 70 moles or less, and even more preferably 65 moles or less. Any combination of these lower and upper limits may be used. By keeping the compound (m-4) content within the above range, the effect of introducing an ethylenically unsaturated group can be exerted, and the amount of unreacted compound (m-4) remaining can also be reduced. The incorporation ratio of compound (m-4) relative to copolymer (P) is preferably 20 moles or more, more preferably 30 moles or more, and even more preferably 40 moles or more, based on 100 moles of the constituent units derived from acrylic acid (m-2) in copolymer (P). The ratio of compound (m-4) introduced to copolymer (P) is preferably 95 mol or less, more preferably 90 mol or less, and even more preferably 85 mol or less. Any combination of these lower and upper limits may be used.

[0039] "Physical Properties of Binder Resin (A-1)" The acid value of the binder resin (A-1) in this embodiment (a value measured in accordance with standards such as JIS K6901 5.3) is not particularly limited as long as it contains a carboxylic acid derived from acrylic acid (m-2) and is 0 mgKOH / g or greater. It is preferably 10 to 400 mgKOH / g, more preferably 20 to 200 mgKOH / g, even more preferably 30 to 125 mgKOH / g, and most preferably 35 to 110 mgKOH / g. When the acid value of the binder resin (A-1) is 10 mgKOH / g or greater, the developability of the binder resin (A-1) as a photosensitive resin composition is good. On the other hand, when the acid value of the binder resin (A-1) is 400 mgKOH / g or less, a uniform composition can be provided without impairing the affinity with other components contained in the pigment dispersion composition and the photosensitive resin composition.

[0040] The molecular weight (weight average molecular weight in terms of polystyrene) of the binder resin (A-1) in this embodiment is not particularly limited, but is preferably 5,000 g / mol or more, more preferably 10,000 g / mol or more, and even more preferably 12,000 g / mol or more. The molecular weight (weight average molecular weight in terms of polystyrene) of the binder resin (A-1) is preferably 30,000 g / mol or less, more preferably 20,000 g / mol or less, and even more preferably 18,000 g / mol or less. Any combination of these lower and upper limits may be used. When the molecular weight of the binder resin (A-1) is 5,000 or more, excellent heat resistance, solvent resistance, and pattern adhesion can be ensured. On the other hand, when the molecular weight of the binder resin (A-1) is 30,000 or less, the molecular weight and viscosity during production of the binder resin (A-1) can be controlled within appropriate ranges, and practical pigment dispersion compositions and photosensitive resin compositions can be provided.

[0041] The ethylenically unsaturated group equivalent of the binder resin (A-1) in this embodiment is 100 g / mol or more, preferably 150 g / mol or more, and more preferably 200 g / mol or more. The ethylenically unsaturated group equivalent of the binder resin (A-1) is 700 g / mol or less, preferably 600 g / mol or less, more preferably 550 g / mol or less, and most preferably 500 g / mol or less. Any combination of these lower limit values ​​and upper limit values ​​may be used. If the ethylenically unsaturated group equivalent of the binder resin (A-1) is greater than 700 g / mol, the adhesion and solvent resistance of the cured resin film obtained by curing the photosensitive resin composition will be insufficient. If the ethylenically unsaturated group equivalent of the binder resin (A-1) is less than 100 g / mol, the amount of ethylenically unsaturated groups introduced is too large, which causes problems such as difficulty in synthesizing the binder resin (A-1) and failure to obtain storage stability as a pigment dispersion composition or a photosensitive resin composition.

[0042] "Method for producing binder resin (A-1)" The copolymer (P), which is a precursor of the binder resin (A-1), can be obtained by carrying out a copolymerization reaction according to a radical polymerization method known in the art. For example, the monomers to be used for copolymerization may be dissolved in a solvent, and then a polymerization initiator may be added to the solution, followed by reaction at 50 to 130°C for 1 to 20 hours. Alternatively, the monomers to be used for copolymerization and the polymerization initiator may be added dropwise to a solvent adjusted to 50 to 130°C, and the reaction may be carried out.

[0043] The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inactive to radical polymerization, and commonly used organic solvents can be used. Specific examples include glycol ether-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; aromatic solvents such as toluene and xylene; and ester-based solvents such as ethyl acetate, isopropyl acetate, and ethyl lactate. These can be used alone or in combination of two or more. Among these, glycol ether-based solvents are particularly preferred.

[0044] The amount of solvent used in this copolymerization reaction is not particularly limited, but is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the total amount of monomers used in the copolymerization. In particular, by using 1,000 parts by mass or less of the solvent, it is possible to suppress a decrease in the molecular weight of the copolymer (P) due to chain transfer, and to control the viscosity of the copolymer (P) within an appropriate range. Furthermore, by using 30 parts by mass or more of the solvent, it is possible to prevent an abnormal polymerization reaction, to carry out the polymerization reaction stably, and to prevent discoloration and gelation of the copolymer (P).

[0045] The polymerization initiator that can be used in this copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compounds can be used. Specific examples include azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), azobis(2-methylpropionate)dimethyl, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. These can be used alone or in combination of two or more types, and it is desirable to select a radical polymerization initiator with an appropriate half-life depending on the polymerization temperature.

[0046] The amount of the polymerization initiator used in this copolymerization reaction is not particularly limited, but is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass, relative to 100 parts by mass of the total amount of the monomers used in the copolymerization.

[0047] A known addition reaction can be used as a method for adding compound (m-4) to a portion of the carboxy groups of copolymer (P). For example, a polymerization inhibitor and a catalyst are added to a solution of copolymer (P), followed by addition of compound (m-4), and the addition reaction is carried out at room temperature to 150°C, preferably 50 to 120°C. The polymerization inhibitor is added to prevent side reactions of the introduced unsaturated groups. Specific examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene. Specific examples of catalysts include tertiary amino groups such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and organometallic compounds such as chromium and tin.

[0048] [Pigment (B)] In this embodiment, the pigment (B) is not particularly limited as long as it can be uniformly dispersed in the composition to form the pixels of the color filter. Pigments of various colors can be used, including pigments of the three primary colors of light, such as red, green, and blue, as well as pigments of complementary colors, such as yellow, orange, and purple, and pigments such as black and brown used in black matrices. The chemical structure of the pigment (B) can include all organic pigments, such as isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, xanthene, diketopyrrolopyrrole, perylene, perinone, quinacridone, indigoid, dioxazine, indigoid, phthalocyanine, anthocyanin, and azo-based pigments, as well as inorganic pigments, such as carbon black, titanium black, and titanium dioxide.

[0049] In particular, the pigment (B) in this embodiment preferably contains a green pigment having a halogenated phthalocyanine skeleton represented by the following formula (6).

[0050]

[0051] In formula (6), M represents a divalent or tetravalent metal atom. From the viewpoint of color reproducibility, zinc or copper is preferred, and zinc is particularly preferred. X represents one of a hydrogen atom, a chlorine atom, and a bromine atom, and contains at least one chlorine atom or bromine atom. The ratio of chlorine atoms and bromine atoms added varies depending on brightness and color reproducibility; the more chlorine atoms and the fewer bromine atoms, the higher the brightness, and conversely, the more bromine atoms and the fewer chlorine atoms, the better the color reproducibility tends to be. The number of chlorine atoms is preferably 1 to 10, more preferably 1.5 to 8. The number of bromine atoms is preferably 5 to 15, more preferably 7 to 14.

[0052] By using the pigment (B) together with the binder resin (A-1) and the polymer dispersant (C) described below, a pigment dispersion composition having excellent pigment dispersibility and storage stability can be obtained, and a color filter having high brightness and a wide color reproduction range can be provided. At the same time, solvent resistance and pattern adhesion of the colored pattern can be imparted.

[0053] The halogenated phthalocyanine pigment may be a commercially available product or may be prepared by hand. Examples of commercially available products include C.I. Pigment Green 7, 36, 58, and 59. Among these, C.I. Pigment Green 58 and 59 are preferred due to their high brightness and excellent color reproducibility. When preparing the pigment by hand, a known production method is used. Examples of the known production method include (1) or (2) below. (1) A method in which a phthalocyanine skeleton is formed in the presence of a catalyst such as ammonium molybdate using phthalic acid or phthalonitrile, in which some or all of the hydrogen atoms in the aromatic ring have been substituted with halogen atoms, as a starting material. (2) A method in which phthalocyanine is halogenated with chlorine gas or bromine gas. The crude pigment obtained by these methods can be dry-ground in a grinder such as a ball mill or a vibration mill, and then treated by a known solvent salt milling method or the like to obtain the desired green pigment.

[0054] Other pigments may be used in combination as long as they contain at least a halogenated phthalocyanine skeleton and can be uniformly dispersed with other compositions to form color filter pixels. There are no particular limitations. Pigments of various colors can be used, including pigments of the three primary colors of light (red, green, and blue), pigments that can be used as complementary colors (yellow, orange, purple, etc.), and pigments such as black and brown used in black matrices. The chemical structures of these pigments include organic pigments such as isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, xanthene, diketopyrrolopyrrole, perylene, perinone, quinacridone, indigoid, dioxazine, indigoid, anthocyanin, and azo-based pigments, as well as inorganic pigments such as carbon black, titanium black, and titanium dioxide.

[0055] Specific examples of other pigments include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; Examples of suitable pigments include red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60; purple pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38; brown pigments such as C.I. Pigment Brown 23 and 25; and black pigments such as C.I. Pigment Black 1 and 7, carbon black, titanium black, and iron oxide. These pigments may be used alone or in combination of two or more depending on the color of the desired pixel.

[0056] Furthermore, as the colorant in this embodiment, not only the pigment (B) but also a dye may be used in combination. When a dye is used in combination, higher brightness, a wider color reproduction range, and better developability can be expected compared to when a pigment is used. On the other hand, when a pigment is used in combination, the heat resistance is superior to that of a dye, and there is less color change after forming a colored pattern. Depending on the required performance and the color of the target pixel, a dye and a pigment may be used in combination.

[0057] As the dye, it is preferable to use an acid dye having an acidic group such as a carboxy group, a salt of an acid dye with a nitrogen compound, a sulfonamide of an acid dye, or the like, from the viewpoints of solubility in the solvent (D) or an alkaline developer described below, interaction with other components in the resin composition, heat resistance, and the like. Specific examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 11 Acid violet 6B, 7, 9, 17, 19; acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more.

[0058] [Polymer Dispersant (C)] The polymer dispersant (C) is not particularly limited as long as it can disperse the pigment (B). From the viewpoint of pigment dispersibility, a polymer compound having at least one substituent selected from the group consisting of a tertiary amino group and a quaternary ammonium cation group is preferred. Examples of the polymer compound include any of the following (1) to (4): (1) Polyamines (or polyammonium cation salts) obtained by homopolymerizing or copolymerizing a monomer having a tertiary amino group and an ethylenically unsaturated group, or a monomer having a quaternary ammonium cation group and an ethylenically unsaturated group; (2) Polyamines (or polyammonium cation salts) obtained by copolymerizing a monomer having a tertiary amino group and an ethylenically unsaturated group, or a monomer having a quaternary ammonium cation group and an ethylenically unsaturated group, with another monomer having an ethylenically unsaturated group; (3) Compounds obtained by alkylating a polymer compound containing one or more primary and / or secondary amino groups to form a tertiary amino group; and (4) Compounds obtained by further treating a tertiary amino group with an acidic compound or an alkyl halide compound to form a quaternary ammonium cation salt. The polymer dispersant (C) is preferably a block polymer of at least one monomer selected from the group consisting of a monomer having a tertiary amino group and an ethylenically unsaturated group and a monomer having a quaternary ammonium cation group and an ethylenically unsaturated group, and a monomer having another ethylenically unsaturated group. Examples of the monomer having another ethylenically unsaturated group include (meth)acrylates having an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkylene glycol group, or the like.

[0059] In particular, a polyamine (or polyammonium cation salt) obtained by block polymerizing a monomer having a tertiary amino group and an ethylenically unsaturated group and / or a monomer having a quaternary ammonium cation group and an ethylenically unsaturated group with another monomer having an ethylenically unsaturated group is preferred as the polymer dispersant (C). By using a block-polymerized polyamine (or polyammonium cation salt) as the polymer dispersant (C), the tertiary amino group and / or the quaternary ammonium cation group is unevenly distributed in one terminal region, improving affinity with the pigment (B). Furthermore, the affinity of the other terminal region with other pigment dispersion compositions, specifically the binder resin (A-1) and the solvent (D) described below, is increased, thereby dramatically improving pigment dispersibility. Note that examples of monomers having other ethylenically unsaturated groups that can improve affinity with other pigment dispersion compositions include (meth)acrylates having an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkylene glycol group, or the like.

[0060] The amine content of the polymer dispersant (C) can be quantitatively determined by measuring the amine value (a value measured in accordance with standards such as JIS K7237). The amine content of the polymer dispersant (C) of this embodiment is not particularly limited, but is preferably 10 mgKOH / g to 200 mgKOH / g, and more preferably 30 mgKOH / g to 160 mgKOH / g. An amine value of 10 mgKOH / g or more enhances affinity with the pigment (B), resulting in sufficient pigment dispersibility. On the other hand, an amine value of 200 mgKOH / g or less can suppress yellowing of the colored pattern caused by amines.

[0061] The molecular weight (weight average molecular weight in terms of polystyrene) of the polymer dispersant (C) of this embodiment is not particularly limited, but is preferably 1,000 to 50,000, and more preferably 3,000 to 30,000. Furthermore, the molecular weight distribution of the polymer dispersant (C) (the value obtained by dividing the weight average molecular weight in terms of polystyrene by the number average molecular weight) is preferably within the range of 1.0 to 2.0, more preferably 1.0 to 1.7, and even more preferably 1.0 to 1.5. When the molecular weight and molecular weight distribution of the polymer dispersant (C) are within the above ranges, the viscosity of the pigment dispersion composition can be controlled within an appropriate range, and sufficient pigment dispersibility can be obtained. In particular, the narrower the molecular weight distribution, the more effective pigment dispersibility can be obtained with a smaller amount of dispersant.

[0062] The polymer dispersant (C) may be a commercially available product or may be prepared by the user. Alternatively, a commercially available product or a polyamine obtained by a known block polymer production method may be optionally modified and functionally modified. When a commercially available product is used, examples of suitable polymer compounds include the DISPERBYK series manufactured by BYK-Chemie, the Solsperse series manufactured by Lubrizol Corporation, and the EFKA-PX series manufactured by BASF. These polymer dispersants (C) may be used alone or in combination of two or more types, as necessary.

[0063] When preparing the polymer dispersant (C) by oneself, the polyamines shown above are synthesized using a known block polymer production method. Specific examples of monomers having a tertiary amino group and an ethylenically unsaturated group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, and (meth)acrylamides such as acryloylmorpholine. These monomers may be used alone, or two or more types may be used. Specific examples of monomers having a quaternary ammonium cation group and an ethylenically unsaturated group include organic halogen compound salts of monomers having a tertiary amino group. There are no particular limitations on the organic halogen compound salts; however, from the viewpoint of ease of availability, specific examples include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, benzyl chloride, ethyl alcohol chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, benzyl bromide, ethyl alcohol bromide, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzyl iodide, and ethyl alcohol iodide. The introduction of a quaternary ammonium cation group does not require the use of the above-mentioned monomers. For example, first, a monomer having a tertiary amino group and another monomer having an ethylenically unsaturated group are block polymerized. Then, the organic halogen compound salt is added to a tertiary amine at a given temperature in the presence of a catalyst, thereby replacing part or all of the tertiary amine with a quaternary ammonium cation group. On the other hand, examples of monomers having another ethylenically unsaturated group that can enhance the affinity with other pigment dispersion compositions include (meth)acrylates having an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, or a (poly)oxyalkylene skeleton.There are no particular limitations on the acrylate as long as it does not impair the affinity with other pigment dispersion compositions. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. Examples of the monomer include (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; 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 fatty acid vinyls such as vinyl acetate and vinyl propionate. These monomers may be used alone or in combination of two or more.

[0064] [Solvent (D)] The solvent (D) is not particularly limited as long as it does not react with the components contained in the pigment dispersion composition or photosensitive resin composition of this embodiment and can dissolve or disperse them. The solvent (D) can be the same as the solvent used in producing the binder resin (A-1) or the polymer dispersant (C), and the solvent contained after the reaction can be used as is or can be further added. Furthermore, when other components are added, the solvent may be one that is present in the other components.

[0065] Specific examples of the solvent (D) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate. These may be used alone or in combination of two or more. Among these, glycol ether-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are preferably used when producing color filters, are preferred.

[0066] [Composition of Pigment Dispersion Composition] The preferred amounts of each component in the pigment dispersion composition of this embodiment are as follows.

[0067] The content of the binder resin (A-1) is preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass, and even more preferably 20 to 30 parts by mass, relative to 100 parts by mass of the pigment (B). When the content of the binder resin (A-1) is 10 parts by mass or more, a photosensitive resin composition with good developability can be obtained, and a cured resin film with excellent solvent resistance and pattern adhesion can be obtained. When the content of the binder resin (A-1) is 50 parts by mass or less, the content of the pigment (B) can be sufficiently ensured, and a cured resin film with excellent color reproducibility can be obtained.

[0068] The content of the polymer dispersant (C) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the pigment (B). When the content of the polymer dispersant (C) is 5 parts by mass or more, a pigment dispersion composition with excellent pigment dispersibility can be obtained. When the content of the polymer dispersant (C) is 50 parts by mass or less, a sufficient content of the pigment (B) can be ensured, and a photosensitive resin composition with excellent color reproducibility can be obtained.

[0069] The blending amount of the solvent (D) is preferably 100 to 900 parts, more preferably 120 to 600 parts, and even more preferably 150 to 400 parts, when the total of the components of the pigment dispersion composition excluding the solvent (D) is 100 parts by mass. When the content of the solvent (D) is within the above range, the pigment dispersion composition has an appropriate viscosity.

[0070] [Method for Producing Pigment Dispersion Composition] The pigment dispersion composition of this embodiment is prepared by weighing out predetermined amounts of binder resin (A-1), pigment (B), polymeric dispersant (C), and solvent (D), and then micronizing and dispersing the pigment (B) using a known dispersion treatment process. In this dispersion treatment process, devices such as a paint shaker, bead mill, ball mill, roll mill, stone mill, jet mill, homogenizer, planetary mixer, and planetary mixer are often used. Furthermore, using beads with a diameter of 0.01 to 10 mm in this dispersion treatment process allows for efficient and uniform micronization of the pigment (B). While there are no restrictions on the material of the beads, the use of glass beads or zirconia beads is preferred in terms of hardness and contamination of the pigment dispersion composition. The appropriate conditions for the dispersion treatment, such as the time, temperature, bead diameter, and amount used, vary depending on the composition of the pigment dispersion composition and the size of the apparatus, and can be adjusted as appropriate. Finally, in order to remove fine dust particles, coarse particles and aggregates of the pigment (B) from the pigment dispersion composition, it is preferable to filter the pigment dispersion composition using a glass filter or the like.

[0071] <Photosensitive Resin Composition> The photosensitive resin composition of this embodiment may contain a binder resin (A), a pigment (B), a polymer dispersant (C), a solvent (D), a reactive diluent (E), and a photopolymerization initiator (F) as a final composition. The binder resin (A) may include a binder resin (A-1) and, if necessary, may further include a binder resin (A-2). The photosensitive resin composition of this embodiment may be, for example, a composition obtained by adding the binder resin (A-1), the reactive diluent (E), and the photopolymerization initiator (F) to a pigment dispersion composition, and, if necessary, adding a solvent (D). The photosensitive resin composition of this embodiment may be, for example, a composition obtained by adding the binder resin (A-1), the reactive diluent (E), and the photopolymerization initiator (F) to a pigment dispersion composition, and, if necessary, adding a binder resin (A-2). The pigment dispersion composition may contain a binder resin (A-1) or a binder resin (A-2), a pigment (B), a polymer dispersant (C), and a solvent (D). That is, the pigment dispersion composition may or may not contain a binder resin (A-1).

[0072] The photosensitive resin composition of this embodiment preferably contains 50 to 280 parts by mass of the total binder resin (A) consisting of the binder resin (A-1) and the binder resin (A-2), 40 to 200 parts by mass of the reactive diluent (E), and 0.1 to 10 parts by mass of the photopolymerization initiator (F) relative to 100 parts by mass of the pigment (B). The solvent (D) may be the same as the solvent (D) contained in the pigment dispersion composition, or a different solvent may be added.

[0073] [Binder Resin (A-1)] The binder resin (A-1) contained in the photosensitive resin composition of this embodiment has the same meaning as the binder resin (A-1) contained in the pigment dispersion composition of this embodiment. However, in the photosensitive resin composition of this embodiment, when a binder resin (A-1) is further added to a pigment dispersion composition containing the binder resin (A-1), the first binder resin (A-1) and the binder resin (A-1) added the second time may be resins of the same structure or different structures. It is preferable that the first binder resin (A-1) and the binder resin (A-1) added the second time are similar.

[0074] [Binder Resin (A-2)] The binder resin (A-2), an optional component of the photosensitive resin composition of this embodiment, is not particularly limited. Resins not belonging to the binder resin (A-1), such as (meth)acrylic resins, epoxy (meth)acrylic resins, and vinyl ester resins, which are commonly used in negative resists, are preferred. Specific preferred skeletons are resins containing an ethylenically unsaturated double bond, such as a vinyl group or a (meth)acryloyl group, and a substituent that contributes to alkali solubility, such as a carboxylic acid, phosphoric acid, or sulfonic acid. By using these resins, a photosensitive resin composition having excellent pattern adhesion and developability can be provided.

[0075] Among these resins, it is preferable to use a (meth)acrylic resin having a (meth)acryloyloxy group and a carboxy group, particularly from the viewpoint of being able to easily provide resins with a wide range of properties. This resin may be a commercially available product or may be prepared by the user. In addition, a solvent (D) may be added to appropriately control the molecular weight during synthesis and to appropriately adjust the viscosity after synthesis.

[0076] The physical properties of the binder resin (A-2) are not particularly limited. In addition, from the viewpoint of ease of production of the photosensitive resin composition and compatibility with other compositions, it is preferable that the weight average molecular weight is 1,000 to 50,000, the acid value of the solid content is 10 to 200 mg KOH / mg, the double bond equivalent is 100 to 3,000 g / mol, and the viscosity of the binder resin (A-2) solution is 0.1 to 1,000 dPa s.

[0077] The total content of the binder resin (A) including the binder resin (A-1) and the binder resin (A-2) is preferably 50 to 280 parts by mass, more preferably 75 to 230 parts by mass, and even more preferably 100 to 200 parts by mass, relative to 100 parts by mass of the pigment (B).

[0078] [Reactive Diluent (E)] The reactive diluent (E) is not particularly limited as long as it is a low molecular weight compound containing an ethylenically unsaturated double bond such as a vinyl group or a (meth)acryloyloxy group. Specific examples of the reactive diluent (E) include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di( Examples of the (meth)acrylic monomer include (meth)acrylic monomers such as tris(hydroxyethyl)isocyanurate, methylolpropane di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; triallyl cyanurate, etc. These may be used alone or in combination of two or more. Among these, compounds having a plurality of (meth)acryloyloxy groups are preferred, and compounds having three or more (meth)acryloyloxy groups, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate, are more preferred.

[0079] The content of the reactive diluent (E) is preferably 40 to 200 parts by mass, more preferably 60 to 180 parts by mass, and even more preferably 80 to 160 parts by mass, relative to 100 parts by mass of the pigment (B).

[0080] [Photopolymerization initiator (F)] The photopolymerization initiator (F) is preferably a photoradical generator, and specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. Examples of such thioxanthones include oxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acylphosphine oxides; and xanthones. These may be used alone or in combination of two or more.

[0081] The content of the photopolymerization initiator (F) is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the total amount of the binder resin (A-1), the binder resin (A-2), and the reactive diluent (E).

[0082] In addition to the above components, the photosensitive resin composition of the present embodiment may contain known additives such as a photoacid generator, a photobase generator, a coupling agent, a leveling agent, etc., in order to impart predetermined properties, as well as fillers, etc. The amounts of these components to be added are not particularly limited as long as they do not impair the effects of the present invention.

[0083] [Method for Producing Photosensitive Resin Composition] The photosensitive resin composition of this embodiment can be produced by mixing the above-mentioned components using a known mixing device. For example, the photosensitive resin composition can be produced by first preparing a pigment dispersion composition, and then sequentially mixing the binder resin (A-1), reactive diluent (E), photopolymerization initiator (F), and the like. If necessary, a binder resin (A-2) may be further added. Furthermore, if necessary, a solvent (D) may be further added in addition to the solvent (D) contained in the pigment dispersion composition. The solvent (D) added later may be the same as or different from the solvent (D) contained in the pigment dispersion composition.

[0084] The photosensitive resin composition obtained as described above has sufficient pigment dispersibility, can achieve high brightness, and can exhibit various resist properties such as solvent resistance, pattern adhesion, and developability, even when the colorant concentration of the colorant is increased and the concentrations of the dispersant and binder resin are reduced. As a result, a colored pattern with excellent reliability can be formed. In other words, by using the photosensitive resin composition, a color filter with excellent reliability can be provided.

[0085] <Color Filter> Next, a color filter having a colored pattern made of a cured product of the photosensitive resin composition of the present invention will be described. The color filter of the present invention has a colored pattern formed using the above-mentioned photosensitive resin composition. A color filter usually comprises a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries between each pixel, and a protective film formed on the pixels and the black matrix. In this configuration, except that the pixels and black matrix (colored pattern) are formed using the above-mentioned photosensitive resin composition, the other components can be known.

[0086] Next, one embodiment of a method for manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate, or the like can be used as appropriate.

[0087] The colored pattern can be formed by photolithography. Specifically, the photosensitive resin composition is applied to a substrate to form a coating film, and then the coating film is exposed to light through a photomask with a predetermined pattern to photocure the exposed portions. The unexposed portions are then developed with an alkaline aqueous solution and baked to form the desired colored pattern.

[0088] The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include screen printing, roll coating, curtain coating, spray coating, and spin coating. After application of the photosensitive resin composition, the solvent (D) may be evaporated by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate, as needed. The heating conditions are not particularly limited and may be appropriately set depending on the type of photosensitive resin composition used. Generally, heating at a temperature of 50°C to 120°C for 30 seconds to 30 minutes is sufficient.

[0089] The formed coating film is then partially exposed by irradiating it with active energy rays such as ultraviolet light or excimer laser light through a negative mask. The amount of energy radiation to be irradiated may be appropriately selected depending on the composition of the photosensitive resin composition, and is preferably, for example, 30 to 2000 mJ / cm. The light source used for exposure is not particularly limited, but examples thereof include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, and metal halide lamps.

[0090] The alkaline aqueous solution used for development is not particularly limited, and examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amino group-based compounds such as ethylamino group, diethylamino group, and dimethylethanolamino group; and aqueous solutions of p-phenylenediamino group-based compounds such as tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates thereof. These aqueous solutions may contain an antifoaming agent or a surfactant, as needed. After development with the alkaline aqueous solution, it is preferable to wash the resulting film with water and then dry it.

[0091] The baking conditions are not particularly limited, and the heat treatment may be carried out depending on the type of photosensitive resin composition used. Generally, the heating is carried out at 130 to 250° C. for 10 to 60 minutes.

[0092] The above-described coating, exposure, development, and baking processes can be sequentially repeated using a photosensitive resin composition for the black matrix and photosensitive resin compositions for the red, green, and blue pixels to form a desired colored pattern. Thereafter, a protective film is formed on the colored pattern (each of the RGB pixels and the black matrix). The protective film is not particularly limited, and any known protective film may be used.

[0093] The color filters manufactured in this way have excellent pigment dispersibility due to the uniform fineness of the pigment, achieve high brightness, and have various resist properties such as excellent solvent resistance, adhesion, and developability, and are high-definition.

[0094] <Image Display Element> The image display element of this embodiment is an image display element equipped with the above-described color filter, and specific examples thereof include a liquid crystal display element, an organic EL display element, and a solid-state imaging element such as a CCD element or a CMOS element. The image display element of this embodiment may be manufactured according to a conventional method, except for the use of the above-described color filter. For example, when manufacturing a liquid crystal display element, the above-described color filter is formed on a substrate, and then electrodes, spacers, and the like are formed in sequence. Then, electrodes, etc. are formed on another substrate, and the two are bonded together, after which a predetermined amount of liquid crystal is injected and sealed.

[0095] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In these examples, parts and percentages are all by mass unless otherwise specified.

[0096] <Method for measuring weight-average molecular weight> The weight-average molecular weight described below means a weight-average molecular weight calculated in terms of standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions: Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Resonac Co., Ltd.) Column temperature: 40°C Sample: 0.2% tetrahydrofuran solution of binder resin (A-1) Developing solvent: tetrahydrofuran Detector: differential refractometer (Shodex RI-71S) (manufactured by Showa Denko K.K.) Flow rate: 1 mL / min

[0097] <Method for measuring acid value> The number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the solid content of the binder resin (A-1) was measured according to JIS K6901 5.3.2. Measuring instrument: 776 Dosimat (Metrohm) Mixed indicator: mixed indicator of bromothymol blue and phenol red

[0098] <Method for Measuring Unsaturated Group Equivalent> This is the mass of the binder resin (A-1) per mole of ethylenically unsaturated groups, and is a calculated value calculated based on the amount of monomer used.

[0099] <Method for measuring amine value> This is the mass of polymer dispersant (C) per mole of tertiary amino group and quaternary ammonium cation group, and is a calculated value calculated based on the amount of monomer used. The calculation was performed in accordance with the definition of amine value (a value measured according to standards such as JIS K7237), and was expressed as the number of mg of potassium hydroxide required to neutralize the amine components contained in 1 g of solid content of polymer dispersant (C).

[0100] A synthesis example of the binder resin (A-1) and a comparative synthesis example are shown below.

[0101] Synthesis Example 1 24.6 g of propylene glycol monomethyl ether acetate and 184.3 g of propylene glycol monomethyl ether were placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was then stirred while purging with nitrogen gas and heated to 120°C. Next, a monomer mixture to which a polymerization initiator had been added was added dropwise from the dropping funnel to the flask. The monomer mixture consisted of 52.8 g of dicyclopentanyl methacrylate (m-1a), 121.0 g of acrylic acid (m-2), and 84.5 g of benzyl methacrylate (m-3). The polymerization initiator was 33.6 g of t-butylperoxy-2-ethylhexanoate (13.0 parts by mass relative to 100 parts by mass of the total of the monomers (m-1a), (m-2), and (m-3)). After the dropwise addition was completed, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction, thereby obtaining copolymer (P). Next, the atmosphere in the flask was replaced with dry air, and then 119.3 g of glycidyl methacrylate (m-4), 1.13 g of triphenylphosphine as a catalyst (0.3 parts by mass relative to 100 parts by mass of the total of the monomers (m-1a), (m-2), (m-3), and (m-4)), and 1.13 g of hydroquinone monomethyl ether as a polymerization inhibitor (0.2 parts by mass relative to 100 parts by mass of the total of the monomers (m-1a), (m-2), (m-3), and (m-4)) were added. The addition reaction to copolymer (P) was carried out at 120°C for 5 hours with stirring. Thereafter, propylene glycol monomethyl ether acetate was added as a solvent so that the solids content became 40.0%, and a solution of binder resin (A-1) having an ethylenically unsaturated double bond and a carboxy group as an alkali-soluble group was obtained as Sample No. 1. The blending ratio of each monomer when the total of monomers (m-1a), (m-2), and (m-3) is defined as 100 mol %, as well as the weight average molecular weight, acid value, and unsaturated group equivalent of binder resin (A-1) are shown in Table 1.

[0102] Synthesis Examples 2 to 11, Comparative Synthesis Examples 1 to 5 Samples No. 2 to 16 were obtained as binder resins (A-1) in the same manner as in Synthesis Example 1, except that the blending ratios of the monomers were as shown in Table 1. The blending ratios of the respective monomers, and the weight average molecular weight, acid value, and unsaturated group equivalent of the binder resins (A-1) are shown in Table 1.

[0103] Comparative Synthesis Example 6 202.6 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was then stirred while purging with nitrogen gas and heated to 120°C. Next, a monomer mixture to which a polymerization initiator had been added was added dropwise from the dropping funnel to the flask. The monomer mixture consisted of 41.6 g of dicyclopentanyl methacrylate, 187.9 g of glycidyl methacrylate, and 66.6 g of benzyl methacrylate (m-3). The polymerization initiator was 32.6 g of t-butylperoxy-2-ethylhexanoate (11.0 parts by mass relative to 100 parts by mass of the total of monomers (m-1a), (m-2), and (m-3)). After the dropwise addition was completed, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction, yielding copolymer (P). Next, the atmosphere in the flask was replaced with dry air, and then 88.5 g of acrylic acid, 1.16 g of triphenylphosphine as a catalyst (0.3 parts by mass relative to 100 parts by mass of the total of the monomers (m-1a), (m-2), (m-3), and (m-4)), and 1.16 g of hydroquinone monomethyl ether as a polymerization inhibitor (0.2 parts by mass relative to 100 parts by mass of the total of the monomers (m-1a), (m-2), (m-3), and (m-4)) were added. An addition reaction to the copolymer (P) was then carried out with stirring at 120°C for 10 hours. Thereafter, 75.6 g of succinic anhydride was added at 115°C, and the mixture was stirred for 1 hour. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solids content was 40.0%, and Sample No. 17 was obtained as a resin solution of Comparative Synthesis Example 6 having an ethylenically unsaturated double bond and a carboxy group as an alkali-soluble group. The blending ratio of each monomer when the total of the monomers (m-1a), (m-3), and (m-4) is defined as 100 mol %, as well as the weight average molecular weight, acid value, and unsaturated group equivalent of the resin are shown in Table 1.

[0104]

[0105] In Table 1, TCDMA: dicyclopentanyl methacrylate, AA: acrylic acid, MAA: methacrylic acid, BZMA: benzyl methacrylate, GMA: glycidyl methacrylate, 2-EHA: 2-ethylhexyl acrylate, SA: succinic anhydride, PGMEA: propylene glycol monomethyl ether acetate, PGME: propylene glycol monomethyl ether.

[0106] A production example of the polymer dispersant (C) is shown below.

[0107] Synthesis Example 12: 133 g of propylene glycol monomethyl ether acetate, 80.5 g of isobornyl methacrylate, and 13.2 g of tetramethylethylenediamine as a catalyst were placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was stirred at 50°C for 1 hour while the atmosphere in the flask was replaced with nitrogen. Subsequently, 9.3 g of ethyl bromoisobutyrate and 5.6 g of cuprous chloride were added as catalysts, and the flask was heated to 110°C, after which a polymerization reaction was carried out for 4 hours. After the reaction, the solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Subsequently, 61 g of propylene glycol monomethyl ether acetate and 19.5 g of dimethylaminoethyl methacrylate as a monomer having a tertiary amino group were added. The reaction was further carried out for 2 hours at 110°C. After the reaction, the solution was sampled again, the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Then, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent to adjust the solid content to 40.0%, to obtain Sample No. 18 (amine value 70 mg KOH / g, weight average molecular weight 5500) which was a solution of polymer dispersant (C) having a tertiary amino group.

[0108] Synthesis Example 13: 133 g of propylene glycol monomethyl ether acetate, 70.0 g of isobornyl methacrylate, and 13.2 g of tetramethylethylenediamine as a catalyst were placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was stirred at 50°C for 1 hour while the atmosphere in the flask was replaced with nitrogen. Subsequently, 9.3 g of ethyl bromoisobutyrate and 5.6 g of cuprous chloride were added as catalysts, and the flask was heated to 110°C, after which a polymerization reaction was carried out for 4 hours. After the reaction, the solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Subsequently, 61 g of propylene glycol monomethyl ether acetate and 30.0 g of methacryloyloxyethylbenzyldimethylammonium chloride as a monomer having a quaternary ammonium cation group were added, and the reaction was carried out for an additional 2 hours at 110°C. After the reaction, the solution was sampled again, the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or higher based on the nonvolatile content. The solution was then cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent to adjust the solid content to 40.0%, yielding Sample No. 19 (amine value 60 mg KOH / g, weight average molecular weight 5000). Sample No. 19 was a solution of polymeric dispersant (C) having a quaternary ammonium cation group.

[0109] A production example of a pigment dispersion composition is shown below.

[0110] Examples 1 to 12, Comparative Examples 1 to 6 The following ingredients (1) to (3) were mixed in the compositions shown in Table 2 into an SUS container (inner diameter 50 mm x height 100 mm) filled with 200 g of zirconia beads (YTZ balls manufactured by Nikkato Corporation) having a diameter of 0.1 mm. (1) C.I. Pigment Green 58 (Fastogen Green A110 manufactured by DIC Corporation) (7.5 g) as the pigment (B). (2) Sample No. 18 having a tertiary amino group or Sample No. 19 having a quaternary ammonium cation group as the polymer dispersant (C). (3) Any of Samples No. 1 to No. 17 as the binder resin (A-1). Then, propylene glycol monomethyl ether acetate was added as the solvent (D) so that the solids content excluding the zirconia beads was 24%. The mixture was mixed and dispersed for 2 hours at room temperature using a paint shaker (Red Devil 5400 manufactured by Red Devil Equipment). Thereafter, the contents were suction filtered through a glass filter to obtain pigment dispersion compositions No. 1 to 18.

[0111] <Evaluation of pigment dispersibility> The viscosity of the pigment dispersion composition immediately after preparation was measured and evaluated using an E-type viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd., measurement temperature 25°C, cone No. 3, rotation speed 20 rpm). In addition, the pigment dispersibility and storage stability of the pigment dispersion composition were evaluated on a 5-point scale from 1 to 5 according to the following criteria based on the viscosity increase / decrease rate calculated from the viscosity measurement results after 2 weeks, with 3 or higher being considered acceptable. The evaluation results are shown in Table 2. 5: ±105% or less 4: ±105% to 115% 3: ±115% to 130% 2: ±130% to 170% 1: ±170% or more

[0112]

[0113] A production example of the binder resin (A-2) is shown below.

[0114] Synthesis Example 14 Sample No. 20 (molecular weight 32,000, solid content acid value 104 mg KOH / g, ethylenically unsaturated group equivalent 1,100 g / mol) was obtained as a solution of binder resin (A-2) in the same manner as in Synthesis Example 1, except that the following (1) to (5) were used: (1) 11.9 g of dicyclopentanyl methacrylate instead of 16.2 g of dicyclopentanyl methacrylate (m-1a); (2) 42.7 g of benzyl methacrylate instead of 51.8 g of benzyl methacrylate (m-3); (3) 20.9 g of methacrylic acid instead of 26.5 g of acrylic acid (m-2); (4) 1.6 g of t-butylperoxy-2-ethylhexanoate instead of 8.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator; (5) 11.5 g of glycidyl methacrylate instead of 15.7 g of glycidyl methacrylate (m-4).

[0115] An example of the production of a photosensitive resin composition is shown below.

[0116] Examples 13 to 24, Comparative Examples 7 to 12: When the solid content of each of the pigment dispersion compositions Nos. 1 to 18 was taken as 100 parts by mass, 80 parts by mass of the binder resin (A-2) sample No. 20, 80 parts by mass of dipentaerythritol hexaacrylate as the reactive diluent (E), and 4 parts by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime) as the photopolymerization initiator (F) were mixed. Propylene glycol monomethyl ether acetate was then added as the solvent (D) to achieve a total solid content of 30%, thereby preparing photosensitive resin compositions Nos. 1 to 17. The blending amounts of each component per 100 parts by mass of the pigment (B) were the same as those of the photosensitive resin composition Nos. 1 to 17. In Nos. 1 to 18, the binder resin (A-2) is 120 parts by mass, the reactive diluent (E) is 120 parts by mass, and the photopolymerization initiator (F) is 6 parts by mass.

[0117] <Preparation of Green Color Resist (1)> "Preparation of Sample for Solvent Resistance Test" Photosensitive resin compositions No. 1 to 18 were spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) so that the final cured coating film had an average thickness of 2.0 μm, and then heated at 100°C for 3 minutes to volatilize the solvent. Next, the entire surface of the coating film was exposed to light (using a USH-250BY lamp manufactured by Ushio Inc., exposure dose 40 mJ / cm). ２ ), and then baked at 230° C. for 30 minutes to obtain a green color resist (1) which was a cured coating film.

[0118] <Preparation of Green Color Resist (2)> "Preparation of Samples for Development Speed ​​and Pattern Adhesion Test" Photosensitive resin compositions No. 1 to 18 were spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) so that the final cured coating film had an average thickness of 2.0 μm, and then heated at 100° C. for 3 minutes to volatilize the solvent. Next, a photomask with a line-and-space or dot pattern was placed on the substrate, and the coating film was exposed to light (Ushio Inc. USH-250BY lamp was used, exposure dose 40 mJ / cm). ２ ) and photocured. Thereafter, the resist was developed with a 0.2% by mass aqueous solution of potassium hydroxide. Further, the resist was baked at 230°C for 30 minutes to obtain a green color resist (2) as a cured coating film.

[0119] <Developability Test> Regarding the development speed, the time required for the pattern to become fully visible during development with a 0.2% by mass aqueous potassium hydroxide solution in the development step of the above green color resist (2) was measured, and the time was evaluated on a 5-point scale from 1 to 5 according to the following criteria, with 3 or higher being considered a pass. The evaluation results are shown in Table 3. 5: Less than 40 seconds 4: 40 to 60 seconds 3: 60 to 80 seconds 2: 80 to 100 seconds 1: 100 seconds or more

[0120] <Pattern Adhesion Test> For pattern adhesion, an immersion test was conducted using the resulting coating film after the above development rate test. The developed cured film was immersed in propylene glycol monomethyl ether (PGME) at room temperature for 3 minutes, the solvent was then dried, and the dot pattern was observed under a microscope and evaluated on a 5-point scale from 1 to 5 according to the following criteria, with 3 or higher being considered a pass. The evaluation results are shown in Table 3. 5: Number of remaining dots: 40 or more 4: Number of remaining dots: 30 to 39 3: Number of remaining dots: 20 to 29 2: Number of remaining dots: 10 to 19 1: Number of remaining dots: 9 or less

[0121] <Solvent Resistance Test> The entire surface of the green color resist coating film (1) was immersed in N-methylpyrrolidone at 60°C for 3 minutes. The coating film was then removed and air-dried. After drying, the film thickness of the coating film was measured, and the residual film rate was calculated from the film thickness before immersion. The resulting residual film rate was evaluated on a 5-point scale from 1 to 5, with 3 or higher being considered a pass. The evaluation results are shown in Table 3. 5: 95% or higher 4: 90% to 95% 3: 85% to 90% 2: 65% to 85% 1: 65% or lower

[0122]

[0123] As can be seen from the results in Tables 2 and 3, it was confirmed that the pigment dispersion compositions in Examples 1 to 24 exhibited excellent pigment dispersibility and storage stability. It was also confirmed that the photosensitive resin compositions exhibited excellent pattern adhesion and solvent resistance. Furthermore, it was confirmed that a pigment dispersion composition capable of suppressing bleed-out of the colorant with high brightness was provided. Furthermore, it was shown that it was possible to provide a color filter that exhibited an excellent development speed and excellent processability.

[0124] In particular, comparing Synthesis Examples 1 to 3 and 4 to 6, it can be seen that the greater the amount of double bonds imparted to the resin, the better the development rate, pattern adhesion, and solvent resistance. Comparing Synthesis Examples 7 to 9, a molecular weight of 14,000 provides the best solvent resistance. It is expected that a higher molecular weight reduces elution into solvents, while a lower molecular weight increases the flexibility of the double bonds contained in the resin, improving reactivity. In Comparative Synthesis Examples 1 and 2, the double bond equivalent was 800 g / mol or more, resulting in insufficient curing and a deterioration in pattern adhesion and solvent resistance.

[0125] Comparing Comparative Synthesis Example 3, which used methacrylic acid, with Synthesis Example 5, which used acrylic acid, Comparative Synthesis Example 3 showed a significant increase in viscosity during copolymerization, gelling during epoxy addition, and synthesis was not possible. When synthesizing a resin containing many double bonds, it is necessary to incorporate a large amount of carboxylic acid as a reaction partner, but when methacrylic acid was used, the viscosity increased significantly, making synthesis difficult.

[0126] In Comparative Synthesis Examples 4 and 5, resins were prepared using monomers different from those used in Synthesis Examples 1 to 11, but the dispersion stability of the resulting millbases was poor. It was found that the polymerizable monomer (m-1) and aromatic ring-containing polymerizable monomer (m-3) used in the Synthesis Examples were important for ensuring dispersion stability.

[0127] In Comparative Synthesis Example 6, acrylic acid was not used in the synthesis of copolymer (P) but glycidyl methacrylate was used instead. When acrylic acid was used instead of glycidyl methacrylate as the compound to be added to copolymer (P) and succinic anhydride was further added to introduce a carboxy group, the dispersion stability of the pigment dispersion composition was poor.

[0128] To summarize the above results, from the viewpoint of dispersion stability, a resin containing polymerizable monomer (m-1), acrylic acid, and aromatic ring-containing polymerizable monomer (m-3) as constituent monomers of copolymer (P) is preferable. Furthermore, from the viewpoint of the amount of double bonds introduced and stable synthesis, a resin containing acrylic acid as a constituent monomer of copolymer (P) is preferable. Furthermore, from the viewpoint of pattern adhesion and solvent resistance, a double bond equivalent of 700 g / mol or less is preferable.

[0129] As described above, the present disclosure provides a pigment dispersion composition that has sufficient pigment dispersibility, can achieve high brightness, suppresses colorant bleed-out, and has excellent solvent resistance and pattern adhesion, and is highly reliable. It also provides a photosensitive resin composition containing the pigment dispersion composition, and a color filter containing the photosensitive resin composition.

[0130] According to the present invention, it is possible to provide a pigment dispersion composition having good pigment dispersibility. Furthermore, it is possible to provide a photosensitive resin composition that, by using the pigment dispersion composition, gives a cured product having excellent solvent resistance. Furthermore, it is possible to provide a color filter having a cured product of the photosensitive resin composition, and an image display element including the color filter.

Claims

1. A pigment dispersion composition comprising: a binder resin (A-1); a pigment (B); a polymer dispersant (C); and a solvent (D); wherein the binder resin (A-1) is a resin in which an ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is added to a portion of the carboxy groups of a copolymer (P) which contains a structural unit derived from at least one polymerizable monomer (m-1) selected from the group consisting of a polymerizable monomer (m-1a) (excluding polymerizable monomer (m-1b)) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer (m-1b) represented by the following formula (1), a structural unit derived from acrylic acid (m-2), and a structural unit derived from an aromatic ring-containing polymerizable monomer (m-3); and the binder resin (A-1) has an unsaturated group equivalent of 100 to 700 g / mol. (In formula (1), R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R １ and R ２ may be bonded to form a cyclic structure. ３ and R ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched.

2. The pigment dispersion composition according to claim 1, wherein the binder resin (A-1) has a weight average molecular weight of 5,000 to 30,000 g / mol.

3. The pigment dispersion composition according to claim 1, wherein the group reactive with a carboxy group contained in the ethylenically unsaturated group-containing compound (m-4) is an epoxy group or an oxetanyl group.

4. The pigment dispersion composition according to claim 1, wherein, in all structural units of the copolymer (P), the content of structural units derived from the polymerizable monomer (m-1) is 1 to 40 mol %, the content of structural units derived from the acrylic acid (m-2) is 40 to 95 mol %, and the content of structural units derived from the aromatic ring-containing polymerizable monomer (m-3) is 1 to 40 mol %.

5. The pigment dispersion composition according to claim 1, wherein the content of the ethylenically unsaturated group-containing compound (m-4) is 20 to 80 mol per 100 mol of the total structural units of the copolymer (P).

6. The pigment dispersion composition according to claim 1, wherein the content of the ethylenically unsaturated group-containing compound (m-4) is 20 to 95 mol per 100 mol of the structural unit derived from the acrylic acid (m-2).

7. The pigment dispersion composition according to claim 1, wherein the polymer dispersant (C) has at least one group selected from the group consisting of a tertiary amino group and a quaternary ammonium cationic group.

8. The pigment dispersion composition according to claim 7, wherein the polymeric dispersant (C) is a block polymer of at least one monomer selected from the group consisting of a monomer having a tertiary amino group and an ethylenically unsaturated group, and a monomer having a quaternary ammonium cation group and an ethylenically unsaturated group, and another monomer having an ethylenically unsaturated group.

9. The pigment dispersion composition according to any one of claims 1 to 8, comprising: 10 to 50 parts by mass of the binder resin (A-1); and 5 to 50 parts by mass of the polymer dispersant (C) relative to 100 parts by mass of the pigment (B).

10. A photosensitive resin composition comprising a binder resin (A), a pigment (B), a polymer dispersant (C), a solvent (D), a reactive diluent (E), and a photopolymerization initiator (F), wherein the binder resin (A) comprises a binder resin (A-1), and the binder resin (A-1) is a resin in which an ethylenically unsaturated group-containing compound (m-4) having a group reactive with a carboxy group is added to a portion of the carboxy groups of a copolymer (P) comprising a structural unit derived from at least one polymerizable monomer (m-1) selected from the group consisting of a polymerizable monomer (m-1a) (excluding polymerizable monomer (m-1b)) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer (m-1b) represented by the following formula (1), a structural unit derived from acrylic acid (m-2), and a structural unit derived from an aromatic ring-containing polymerizable monomer (m-3), The photosensitive resin composition according to claim 1, wherein the binder resin (A-1) has an unsaturated group equivalent of 100 to 700 g / mol. (In formula (1), R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R １ and R ２ may be bonded to form a cyclic structure. ３ and R ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched.

11. The photosensitive resin composition according to claim 10, wherein the binder resin (A) further contains a binder resin (A-2).

12. The photosensitive resin composition according to claim 11, wherein the binder resin (A-2) is at least one resin selected from the group consisting of a (meth)acrylic resin, an epoxy (meth)acrylic resin, and a vinyl ester resin, which does not belong to the binder resin (A-1).

13. The photosensitive resin composition according to claim 10, comprising, relative to 100 parts by mass of the pigment (B), a total of 50 to 280 parts by mass of the binder resin (A), 5 to 50 parts by mass of the polymer dispersant (C), 40 to 200 parts by mass of the reactive diluent (E), and 0.1 to 15 parts by mass of the photopolymerization initiator (F).

14. A cured resin film obtained by curing the photosensitive resin composition according to claim 10 or 11.

15. A color filter comprising a cured product of the photosensitive resin composition according to claim 10 or 11.

16. An image display device comprising the color filter according to claim 15.

Images