JP7344106B2 - Colored compositions and color filters - Google Patents

Description

The present invention relates to a coloring composition containing a polyhalogenated metal phthalocyanine pigment and a block copolymer as a dispersant, and a color filter.

Conventionally, in the production of color filters for use in liquid crystal displays and the like, methods for applying colorants to base materials include pigment dispersion methods, dyeing methods, electrodeposition methods, printing methods, and the like. Among these, the pigment dispersion method is the mainstream from the viewpoints of spectral characteristics, durability, pattern shape, and precision. In this pigment dispersion method, a coating film made of a pigment dispersion composition mixed with a pigment, a dispersant, a dispersion medium (solvent), a binder resin, etc. is formed on a substrate, and radiation is applied through a photomask with a desired pattern shape. It is cured by irradiation and alkaline development is performed.

In recent years, color filters have been required to have higher transmittance, higher brightness, higher contrast, and a wider color gamut.This has led to higher concentrations of pigments in pigment dispersion compositions, and unique transmission and absorption spectra that are closer to visible light wavelengths. Various studies are being conducted in this area, including the development of pigments that match the spectrum of backlight phosphors.

Furthermore, in alkaline development, an alkali-soluble binder resin plays a major role. However, in the case of a colored composition with a high concentration of pigment, the proportion of the binder resin, which is a developing component, decreases, resulting in a decrease in alkaline developability. Since coloring compositions using conventional dispersants do not have sufficient alkali developability, Patent Document 1 describes an A block having a polylactone chain in the side chain as a dispersant that can impart excellent alkali developability. It has been proposed to use an AB block copolymer consisting of a B block having a tertiary amino group in the side chain as a dispersant (see Patent Document 1 (paragraphs 0023 to 0045)).

In addition, particularly with regard to increasing the brightness of green pixels, new polyhalogenated zinc phthalocyanine pigments having a specific hue have been proposed, for example, as described in Patent Document 2 and Patent Document 3. As a result, higher brightness than conventional polyhalogenated copper phthalocyanine pigments was achieved (see Patent Document 2 (paragraphs 0142-0147) and Patent Document 3 (paragraphs 0144-0149)).

Japanese Patent Application Publication No. 2013-119568 Japanese Patent Application Publication No. 2004-070342 Japanese Patent Application Publication No. 2004-070343

In recent years, technological innovation has accelerated, and colored compositions containing polyhalogenated metal phthalocyanine pigments have not only excellent alkaline developability after application, but also excellent brightness of the colored layer even after high-temperature processing of components equipped with the colored layer. It is required to be there. However, with conventional dispersants, the brightness of the coating film after high-temperature processing was not sufficient.

The present invention has been made in view of the above circumstances, and is a colored composition containing a polyhalogenated metal phthalocyanine pigment as a coloring agent, which forms a colored layer that can suppress a decrease in brightness even when exposed to high temperatures. The purpose of the present invention is to provide a coloring composition that can be used.

The colored composition of the present invention that can solve the above problems contains a coloring material, a dispersant, a binder resin, and a dispersion medium, the coloring material contains a polyhalogenated metal phthalocyanine pigment, and the dispersing agent contains a polyhalogenated metal phthalocyanine pigment. A block copolymer having an A block and a B block, the A block having a structural unit derived from a (meth)acrylic monomer, and the B block having a structural unit represented by general formula (3); and It has a structural unit represented by the general formula (4), and is characterized in that the content of the structural unit represented by the general formula (4) in the B block is 1% by mass to 23% by mass. .

［式（１）において、Ｒ³¹およびＲ³²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ³¹およびＲ³²が互いに結合して環状構造を形成していてもよい。Ｒ³³は水素原子またはメチル基を表す。Ｘ³¹はアミド基、エステル基、または、単結合を表す。Ｙ³¹は２価の炭化水素基を表す。］

[In formula (1), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may be bonded to each other to form a cyclic structure. R ³³ represents a hydrogen atom or a methyl group. X ³¹ represents an amide group, an ester group, or a single bond. Y ³¹ represents a divalent hydrocarbon group. ]

［式（２）において、ｎは１～５の整数を示す。Ｒ⁴¹は置換基を有してもよい鎖状の炭化水素基を示す。］

[In formula (2), n represents an integer from 1 to 5. R ⁴¹ represents a chain hydrocarbon group which may have a substituent. ]

The colored composition of the present invention contains a polyhalogenated metal phthalocyanine pigment as a coloring agent, and a block copolymer having a specific structural unit as a dispersant. Block copolymers used as dispersants include those having a structural unit represented by formula (3). The structural unit represented by formula (3) has an amino group, and when the block copolymer is heated, it tends to be easily separated from the polymer chain by depolymerization. The monomer containing the polyhalogenated metal phthalocyanine pigment is considered to be the cause of yellowing of the colored layer containing the polyhalogenated metal phthalocyanine pigment. Therefore, when a colored layer formed from a colored composition containing a block copolymer having a structural unit represented by formula (3) is used as a color filter, the brightness tends to decrease due to heat treatment.

On the other hand, in the colored composition of the present invention, since the block copolymer used as a dispersant has a structural unit represented by formula (4) as well as a structural unit represented by formula (3), It is thought that even when the block copolymer is heated, the presence of the structural unit represented by formula (4) suppresses the separation of the structural unit represented by formula (3) from the polymer chain. It will be done. Therefore, when the colored layer is used as a color filter, reduction in brightness can be suppressed even when the colored layer containing the polyhalogenated metal phthalocyanine pigment is exposed to high temperatures.

The present invention also includes a color filter including a colored layer formed using the colored composition.

By using the colored composition of the present invention, it is possible to form a colored layer that can suppress a decrease in brightness even when exposed to high temperatures.

An example of a preferred embodiment of the present invention will be described below. However, the following embodiments are merely illustrative. The present invention is not limited to the following embodiments.

<Colored composition>
The colored composition of the present invention contains a coloring material, a dispersant, a binder resin, and a dispersion medium.

(1. Coloring material)
The colorant contains a polyhalogenated metal phthalocyanine pigment. The polyhalogenated metal phthalocyanine pigment is a pigment obtained by halogenating a metal phthalocyanine, such as polychlorocopper phthalocyanine, polybromo copper phthalocyanine, polybromochlorocopper phthalocyanine, polychlorozinc phthalocyanine, polybromozinc phthalocyanine, polybromochlorozinc phthalocyanine, etc. can be mentioned. The polyhalogenated metal phthalocyanine pigments may be used alone or in combination of two or more.

When the number of chlorine atoms and/or bromine atoms in the molecule of polyhalogenated metal phthalocyanine increases, the hue changes from blue to green. In order to obtain a green colored composition, it is preferable to use a polyhalogenated metal phthalocyanine having a total of 8 or more chlorine atoms and/or bromine atoms in the molecule.

Specifically, as the polyhalogenated metal phthalocyanine, a pigment represented by general formula (1) can be used.

［式（１）中、Ｍは銅または亜鉛であり、Ｘ¹～Ｘ¹⁶は、いずれも独立して塩素原子、臭素原子または水素原子である。ただし、Ｘ¹～Ｘ¹⁶において塩素原子と臭素原子の合計は８～１５であり、残りは水素原子である。］

[In formula (1), M is copper or zinc, and each of X ¹ to X ¹⁶ is independently a chlorine atom, a bromine atom, or a hydrogen atom. However, the total number of chlorine atoms and bromine atoms in X ¹ to X ¹⁶ is 8 to 15, and the remainder are hydrogen atoms. ]

The polyhalogenated metal phthalocyanine has a total of 8 to 15 chlorine atoms and/or chlorine atoms in 4 benzene rings per polyhalogenated metal phthalocyanine molecule (structure) in order to obtain a yellowish and brighter green color. Alternatively, it is preferable to use a structure in which a bromine atom is bonded and a hydrogen atom is bonded to the remaining position of the benzene ring, and a total of 9 to 15 chlorine atoms and/or bromine atoms are bonded to the four benzene rings. It is more preferable to use a structure in which bromine atoms are bonded to each other and a hydrogen atom is bonded to the remaining position of the benzene ring, and 13 to 15 bromine atoms are bonded to the four benzene rings, and the benzene A structure in which hydrogen atoms are bonded to the remaining positions of the ring is particularly preferred.

In the present invention, any polyhalogenated metal phthalocyanine pigment that satisfies the above general formula (1) can be used without particular limitation, and a plurality of pigments that satisfy the above general formula (1) may be used in combination. Good too.

Specifically, C. I. Pigment Green 7 (compound in which M in general formula (1) is copper and X ¹ to X ¹⁶ are chlorine atoms or hydrogen atoms); C. I. Pigment Green 36 (compound in which M in general formula (1) is copper and X ¹ to X ¹⁶ are chlorine, bromine or hydrogen atoms); C. I. Pigment Green 58 (compound in which M in general formula (1) is zinc and X ¹ to X ¹⁶ are chlorine, bromine or hydrogen atoms); C. I. Pigment Green 59 (a compound in which M in the general formula (1) is zinc and X ¹ to X ¹⁶ are chlorine, bromine, or hydrogen atoms), and these can be used alone or in combination of two or more. can be used.

The number average particle diameter of the coloring material may be appropriately selected depending on its use, and is not particularly limited. The coloring composition preferably contains a coloring material having a number average particle diameter of 10 nm to 150 nm from the viewpoint of high transparency and high contrast.

The coloring agent may be used in combination with a pigment or dye other than the polyhalogenated metal phthalocyanine pigment for adjusting the hue, etc., as long as the preferred physical properties of the present invention are not impaired.

Other pigments may be either organic pigments or inorganic pigments, but organic pigments containing organic compounds as a main component are particularly preferred. Examples of the pigment include pigments of various colors such as red pigment, yellow pigment, orange pigment, blue pigment, green pigment, and violet pigment. The structures of pigments include monoazo pigments, diazo pigments, azo pigments such as condensed diazo pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo pigments, and thio Examples include polycyclic pigments such as indigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The coloring composition may contain only one type of pigment, or may contain multiple types of pigment.

Specific examples of pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 122, 123, 146, 149, 168, 177, Red pigments such as 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; C. I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as C.I. I. Pigment Orange 36, 38, 43 and other orange pigments; C.I. I. Pigment Blue 15, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, and other blue pigments; C.I. I. Examples include purple pigments such as Pigment Violet 23, 29, 32, and 50.

When a coloring agent other than a polyhalogenated metal phthalocyanine pigment is used as the coloring agent, the content of the polyhalogenated metal phthalocyanine pigment in the total coloring material is preferably 40% by mass or more, more preferably 60% by mass. The content is more preferably 80% by mass or more. Note that the polyhalogenated metal phthalocyanine pigment alone may be used as the coloring material.

Moreover, the coloring material may contain a pigment derivative as a dispersion aid. It is preferable that the dye derivative contains an acidic dye derivative having an acidic group in order to ionicly bond and adsorb the amino group in the block copolymer contained in the dispersant. This dye derivative has an acidic group introduced into the dye skeleton. The pigment skeleton is preferably the same or similar to the coloring material constituting the coloring composition, or the same or similar to the compound that is the raw material for the pigment. Specific examples of the pigment skeleton include an azo pigment skeleton, a phthalocyanine pigment skeleton, an anthraquinone pigment skeleton, a triazine pigment skeleton, an acridine pigment skeleton, a perylene pigment skeleton, and preferably a phthalocyanine pigment skeleton. It is. The acidic group introduced into the dye skeleton is preferably a carboxy group, a phosphoric acid group, or a sulfonic acid group. Note that sulfonic acid groups are preferred for convenience of synthesis and strong acidity. Further, the acidic group may be directly bonded to the dye skeleton, or may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond.

The amount of the dye derivative used is not particularly limited, but is preferably 4 to 17 parts by weight, for example, based on 100 parts by weight of the colorant.

From the viewpoint of brightness, the upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 70% by mass, and 60% by mass, based on the total solid content of the coloring composition. It is more preferable. In addition, the lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass, based on the total solid content of the coloring composition. preferable. Here, the solid content refers to components other than the dispersion medium described below.

The content of the dispersant for the coloring material in the coloring composition is preferably 5 parts by mass to 200 parts by mass, preferably 10 parts by mass to 100 parts by mass, and 10 parts by mass, based on 100 parts by mass of the coloring material. Parts to 80 parts by mass are more preferred.

(2. Dispersant)
The dispersant used in the present invention has an A block having a structural unit derived from a (meth)acrylic monomer, a structural unit represented by general formula (3), and a structural unit represented by general formula (4). Contains a block copolymer having B block. The content of the block copolymer in the dispersant is 50% by mass or more, preferably 75% by mass or more, and more preferably 90% by mass or more. The colored composition may contain only the block copolymer as a dispersant.

(2-1. Block copolymer)
The block copolymer used in the dispersant includes an A block having a structural unit derived from a (meth)acrylic monomer, a structural unit represented by general formula (3), and a structural unit represented by general formula (4). and B block. Various constituent components of the block copolymer will be explained below.

In the present invention, "A block" can be translated as "A segment", and "B block" can be translated as "B segment". In the present invention, "vinyl monomer" refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule. The term "structural unit derived from a vinyl monomer" refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to become a carbon-carbon single bond. "(Meth)acrylic" refers to "at least one of acrylic and methacrylic." "(Meth)acrylate" refers to "at least one of acrylate and methacrylate." "(Meth)acryloyl" refers to "at least one of acryloyl and methacryloyl."

(2-1-1.A block)
The A block is a polymer block containing a structural unit derived from a (meth)acrylic monomer. The number of structural units derived from the (meth)acrylic monomer in the A block may be one, or two or more. By having a structural unit derived from a (meth)acrylic monomer, high affinity with the dispersion medium (solvent) and the binder resin blended into the coloring composition can be maintained.

The content of the structural unit derived from the (meth)acrylic monomer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably is 100% by mass.

The (meth)acrylic monomers include (meth)acrylates having a chain alkyl group (straight chain alkyl group or branched alkyl group), (meth)acrylates having a cyclic alkyl group, and (meth)acrylates having a polycyclic structure. , (meth)acrylate having an aromatic group, (meth)acrylate having a polyalkylene glycol structural unit, (meth)acrylate having a hydroxy group, (meth)acrylate having a lactone-modified hydroxy group, (meth)acrylate having an alkoxy group Examples include acrylate, (meth)acrylate having an oxygen-containing heterocyclic group, (meth)acrylate having an acidic group, (meth)acrylic acid, etc. Among these, one type or a combination of two or more types can be used. I can do it.

The (meth)acrylate having a straight chain alkyl group is preferably a (meth)acrylate having a straight chain alkyl group in which the straight chain alkyl group has 1 to 20 carbon atoms; (meth)acrylates having a linear alkyl group of 10 are more preferred. As the (meth)acrylate having a linear alkyl group, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, Examples include n-octyl (meth)acrylate, n-nonyl (meth)acrylate, decyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

The (meth)acrylate having a branched-chain alkyl group is preferably a (meth)acrylate having a branched-chain alkyl group in which the branched-chain alkyl group has 3 to 20 carbon atoms; Preferred are (meth)acrylates with a branched alkyl group of 10. Examples of the (meth)acrylate having a branched chain alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2- Examples include ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and the like.

The (meth)acrylate having a cyclic alkyl group is preferably a (meth)acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Examples of the cyclic alkyl group include a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group). Specific examples of (meth)acrylates having a cyclic alkyl group with a monocyclic structure include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate.

The (meth)acrylate having a polycyclic structure is preferably a (meth)acrylate having a polycyclic structure having 6 to 12 carbon atoms. Examples of the polycyclic structure include cyclic alkyl groups having a bridged ring structure (eg, adamantyl group, norbornyl group, and isobornyl group). Specific examples of (meth)acrylates having a polycyclic structure include isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and 2-methyl-2-adamantyl. (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like.

The (meth)acrylate having an aromatic group is preferably a (meth)acrylate having an aromatic group having 6 to 12 carbon atoms. Examples of the aromatic group include an aryl group, and may have a chain moiety such as an alkylaryl group, an aralkyl group, an aryloxyalkyl group, and the like. Specific examples of (meth)acrylates having an aromatic group include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.

Examples of the (meth)acrylate having a polyalkylene glycol structural unit include polyethylene glycol (degree of polymerization = 2 to 10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth)acrylate, polyethylene Glycol (degree of polymerization = 2-10) (meth)acrylates having polyethylene glycol structural units such as propyl ether (meth)acrylate; polypropylene glycol (degree of polymerization = 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization Examples include (meth)acrylates having a polypropylene glycol structural unit such as ethyl ether (meth)acrylate (=2-10) and polypropylene glycol (degree of polymerization=2-10) propyl ether (meth)acrylate.

Examples of the (meth)acrylate having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxypropyl (meth)acrylate. Examples include hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate. Among these, (meth)acrylates having a hydroxyalkyl group having 1 to 5 carbon atoms are more preferred.

Examples of the (meth)acrylate having a lactone-modified hydroxy group include those obtained by adding a lactone to the (meth)acrylate having a hydroxy group, and those having caprolactone added are preferable. The amount of caprolactone added is preferably 1 mol to 10 mol. Examples of the caprolactone adduct of (meth)acrylate having a hydroxy group include 1 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 2 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate adduct of caprolactone 2 mol; ) 3 mol caprolactone adduct of acrylate, 4 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 5 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 10 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, etc. is preferred.

Examples of the (meth)acrylate having an alkoxy group include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and the like.

The (meth)acrylate having an oxygen-containing heterocyclic group is preferably a (meth)acrylate having a 4- to 6-membered oxygen-containing heterocyclic group. Specific examples of (meth)acrylates having an oxygen-containing heterocyclic group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (2- Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 2-[(2-tetrahydropyranyl)oxy]ethyl (meth)acrylate, Examples include 1,3-dioxane-(meth)acrylate.

Examples of the acidic group include a carboxy group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphinic acid group (- PO ₂ H ₂ ). Examples of the (meth)acrylate having an acidic group include (meth)acrylate having a carboxy group, (meth)acrylate having a phosphoric acid group, and (meth)acrylate having a sulfone group.

Examples of the (meth)acrylate having a carboxy group include 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, and 2-(meth)acryloyloxyethyl phthalate. Examples include monomers obtained by reacting meth)acrylate with acid anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate. Examples of the (meth)acrylate having a sulfonic acid group include ethyl sulfonate (meth)acrylate. Examples of the (meth)acrylate having a phosphoric acid group include 2-(phosphonooxy)ethyl (meth)acrylate.

The A block may have a structural unit other than the structural unit derived from the (meth)acrylic monomer. Other structural units that may be included in the A block are not particularly limited as long as they are formed from a vinyl monomer that can be copolymerized with both the (meth)acrylic monomer and the vinyl monomer forming the B block described below. Vinyl monomers that can form other structural units of the A block may be used alone, or two or more types may be used in combination.

Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, aromatic vinyl monomers, vinyl monomers containing heterocycles, vinylamides, vinyl carboxylates, dienes, and the like. These vinyl monomers may have a hydroxy group or an epoxy group.

Examples of the α-olefin include 1-hexene, 1-octene, and 1-decene.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene, and the like.
Vinyl monomers containing heterocycles include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-phenylmaleimide, N-benzyl Examples include maleimide and N-cyclohexylmaleimide.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam, and the like.
Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate, and the like.
Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

The A block preferably contains a structural unit represented by general formula (2), that is, a structural unit derived from the (meth)acrylate having the lactone-modified hydroxy group. The structural unit represented by general formula (2) has an ester bond moiety and a terminal hydroxyl group in the side chain, so it has high affinity with the dispersion medium and binder resin, and the block copolymer has alkali developability. Increase.

［式（２）において、ｎ１は１～１０の整数を表す。Ｒ²¹は水素原子またはメチル基を表す。Ｒ²²は炭素数が１～１０のアルキレン基を表す。Ｒ²³は炭素数が１～１０のアルキレン基を表す。］

[In formula (2), n1 represents an integer from 1 to 10. R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an alkylene group having 1 to 10 carbon atoms. R ²³ represents an alkylene group having 1 to 10 carbon atoms. ]

In the formula (2), n1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5.

The alkylene group having 1 to 10 carbon atoms represented by R ²² may be linear or branched, but linear is preferable. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ²² include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Examples include nonamethylene group, decamethylene group, and 1-methylethylene group. R ²² is preferably an alkylene group having 1 to 5 carbon atoms.

The alkylene group having 1 to 10 carbon atoms represented by R ²³ may be linear or branched, but linear is preferable. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ²³ include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Examples include nonamethylene group and decamethylene group. R ²³ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms.

When the A block contains a structural unit represented by general formula (2), the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably is 30% by mass or more, particularly preferably 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 88% by mass or less. By setting the content of the structural unit derived from the (meth)acrylate having a lactone-modified hydroxy group within the above range, the alkali developability of the colored composition containing the block copolymer can be improved.

The A block preferably has a structural unit derived from a vinyl monomer having an acidic group (preferably a (meth)acrylate or (meth)acrylic acid having an acidic group). By having a structural unit derived from a vinyl monomer having an acidic group, the solubility in an alkaline developer increases, and the alkali developability of the colored composition can be improved. However, if the proportion increases, there is a risk that the affinity with the dispersion medium (solvent) and binder resin may decrease. Therefore, the proportion of structural units derived from vinyl monomers having acidic groups is preferably such that the overall acid value of the block copolymer is lower than the amine value.

When containing a structural unit derived from a vinyl monomer having an acidic group, its content is preferably 2% by mass or more and preferably 20% by mass or less in 100% by mass of A block. If the content of structural units derived from vinyl monomers having acidic groups is 2% by mass or more, the dissolution rate when neutralized with an alkali will be faster in alkaline development, and if it is 20% by mass or less, hydrophilicity will be high. Therefore, it is possible to prevent the formed pixels from becoming disorderly.

The A block has a content of less than 10% by mass of a structural unit represented by general formula (3), a structural unit represented by general formula (4), and a structural unit represented by general formula (5), which will be described later. , preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, a structural unit represented by general formula (3), a structure represented by general formula (4) It is most preferable that it does not contain a unit or a structural unit represented by general formula (5). The lower the content of the structural unit represented by the general formula (3), the structural unit represented by the general formula (4), and the structural unit represented by the general formula (5) in the A block, the better the dispersion of the colorant. Improved performance.

Preferably, the A block does not have an amino group. That is, it is preferable that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group. If a large amount of amino groups are present in the A block, the colorant will be adsorbed to both the A block and the B block when used as a dispersant, resulting in a decrease in the dispersion performance of the colorant. The content of structural units derived from vinyl monomers having an amino group in the A block (including those in which the amino group is quaternized) is preferably 3% by mass or less, more preferably 1% by mass or less, More preferably, it is 0.1% by mass or less, and most preferably 0% by mass.

When two or more types of structural units are contained in the A block, the various structural units contained in the A block may be contained in any form such as random copolymerization or block copolymerization in the A block. , is preferably contained in a random copolymerized form from the viewpoint of uniformity. For example, the A block may be formed of a copolymer of a structural unit consisting of an a1 block and a structural unit consisting of an a2 block.

(2-1-2.B block)
The B block is a polymer block containing a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4).

There may be only one type of structural unit represented by general formula (3), or two or more types may be used. By having the structural unit represented by the general formula (3), adsorption with the coloring material can be increased.

［式（３）において、Ｒ³¹およびＲ³²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ³¹およびＲ³²が互いに結合して環状構造を形成していてもよい。Ｒ³³は水素原子またはメチル基を表す。Ｘ³¹はアミド基、エステル基、または、単結合を表す。Ｙ³¹は２価の炭化水素基を表す。］

[In formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may be bonded to each other to form a cyclic structure. R ³³ represents a hydrogen atom or a methyl group. X ³¹ represents an amide group, an ester group, or a single bond. Y ³¹ represents a divalent hydrocarbon group. ]

Examples of the chain hydrocarbon group represented by R ³¹ and R ³² include a linear alkyl group and a branched alkyl group. The number of carbon atoms in the linear alkyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, etc. can be mentioned. The number of carbon atoms in the branched alkyl group is preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, isooctyl group, and the like.

Examples of the substituent on the chain hydrocarbon group represented by R ³¹ and R ³² include a halogen group, an alkoxy group, a benzoyl group (-COC ₆ H ₅ ), and a hydroxy group.

Examples of the cyclic hydrocarbon group represented by R ³¹ and R ³² include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain moiety. The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The number of carbon atoms in the aromatic group is preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, tolyl group, xylyl group, mesityl group, and the like. Examples of the cyclic alkyl group having a chain moiety and the chain moiety of an aromatic group having a chain moiety include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Examples include 1 to 3 alkylene groups.

Examples of the substituent on the cyclic hydrocarbon group represented by R ³¹ and R ³² include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.

The cyclic structure formed by bonding R ³¹ and R ³² to each other includes, for example, a 5- to 7-membered nitrogen-containing heterocycle or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, and is more preferably a saturated ring. Specific examples include structures represented by the following formulas (3-1), (3-2), and (3-3).

［式（３－１）、（３－２）、（３－３）において、Ｒ³⁴は、炭素数１～６のアルキル基を示す。ｌは０～５の整数を表す。ｍは０～４の整数を表す。ｎは０～４の整数を表す。＊は結合手を表す。ｌが２～５、ｍが２～４、ｎが２～４の場合、複数存在するＲ³⁴は、それぞれ同一でも異なっていてもよい。］

[In formulas (3-1), (3-2), and (3-3), R ³⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ^34s may be the same or different. ]

The X ³¹ represents an amide group (-CO-NH-), an ester group (-CO-O-), or a single bond. Note that the bonding direction of the amide group and the ester group is not particularly limited. Examples of the bonding mode of the amide group include C-CO-NH-Y ³¹ or C-NH-CO-Y ³¹ . Examples of the bonding mode of the ester group include C-CO-O-Y ³¹ or C-O-CO-Y ³¹ .

Examples of the divalent hydrocarbon group represented by Y ³¹ include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, an arenediyl group having 6 to 10 carbon atoms, and the like. Among these, alkylene groups having 1 to 10 carbon atoms are preferred. The alkylene group may be either linear or branched, but preferably linear. Y ³¹ is preferably an alkylene group having 1 to 5 carbon atoms.

Specific examples of vinyl monomers forming the structural unit represented by general formula (3) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, and ethylaminoethyl (meth)acrylate. meth)acrylate, ethylaminopropyl(meth)acrylate, ethylaminobutyl(meth)acrylate, diethylaminoethyl(meth)acrylate, diethylaminopropyl(meth)acrylate, diethylaminobutyl(meth)acrylate, propylaminoethyl(meth)acrylate, propyl Aminopropyl (meth)acrylate, propylaminobutyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, dipropylaminopropyl (meth)acrylate, dipropylaminobutyl (meth)acrylate, tert-butylaminoethyl (meth) Examples include acrylate, dimethylaminopropyl (meth)acrylamide, and the like.

The content of the structural unit represented by general formula (3) is preferably 10% by mass or more in 100% by mass of B block, more preferably 20% by mass or more, still more preferably 40% by mass or more, particularly preferably 60% by mass or more. It is preferably at least 99% by mass, more preferably at most 90% by mass, even more preferably at most 85% by mass. It is considered that by setting the content of the structural unit represented by the general formula (3) within this range, it has a high affinity with the coloring material.

There may be only one type of structural unit represented by general formula (4), or two or more types may be used. By having the structural unit represented by general formula (4), even when the block copolymer is exposed to high temperatures, the structural unit represented by formula (3) can be separated from the polymer chain by depolymerization. It is thought that this will be suppressed. Therefore, it is possible to obtain a colored composition with excellent brightness even during high-temperature processing after application.

［式（４）において、ｎは１～５の整数を示す。Ｒ⁴¹は置換基を有してもよい鎖状の炭化水素基を示す。］

[In formula (4), n represents an integer of 1 to 5. R ⁴¹ represents a chain hydrocarbon group which may have a substituent. ]

Examples of the chain hydrocarbon group represented by R ⁴¹ include a straight chain alkyl group and a branched chain alkyl group.
The number of carbon atoms in the linear alkyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, etc. can be mentioned.
The number of carbon atoms in the branched alkyl group is preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, isooctyl group, and the like.
Examples of the substituent on the chain hydrocarbon group represented by R ⁴¹ include a halogen group, an alkoxy group, and a hydroxy group.

The n is preferably 4 or less, more preferably 2 or less, particularly preferably 1.

Specific examples of vinyl monomers forming the structural unit represented by general formula (4) include vinyltoluene, ethylstyrene, propylstyrene, butylstyrene, dimethylstyrene, trimethylstyrene, tetramethylstyrene, pentamethylstyrene, and isopropylstyrene. , isobutylstyrene, tert-butylstyrene, and the like.

The content of the structural unit represented by general formula (4) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and 23% by mass in 100% by mass of the B block. % or less, more preferably 20% by mass or less, still more preferably 15% by mass or less. By setting the content of the structural unit represented by general formula (4) within this range, a colored composition with excellent brightness can be obtained even during high-temperature processing after application.

The B block may have a structural unit represented by general formula (5). The number of structural units represented by the general formula (5) in the B block may be one type or two or more types. If the B block has the structural unit represented by the general formula (5), strong adsorption to the surface of the coloring material can be maintained over a long period of time, and storage stability is further improved.

［式（５）において、Ｒ⁵¹は、水素原子、置換基を有していてもよい鎖状もしくは環状の炭化水素基を表す。Ｒ⁵²およびＲ⁵³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を表す。Ｒ⁵²およびＲ⁵³が互いに結合して環状構造を形成していてもよい。Ｒ⁵⁴は水素原子またはメチル基を表す。Ｘ⁵¹はアミド基、エステル基、または、単結合を表す。Ｙ⁵¹は２価の炭化水素基を表す。Ｚ^-は、対イオンを示す。］

[In formula (5), R ⁵¹ represents a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent. R ⁵² and R ⁵³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure. R ⁵⁴ represents a hydrogen atom or a methyl group. X ⁵¹ represents an amide group, an ester group, or a single bond. Y ⁵¹ represents a divalent hydrocarbon group. Z ^- represents a counter ion. ]

Examples of the chain hydrocarbon group represented by R ⁵¹ to R ⁵³ include a linear alkyl group, a branched alkyl group, and the like. The number of carbon atoms in the linear alkyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, etc. can be mentioned. The number of carbon atoms in the branched alkyl group is preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, isooctyl group, and the like.

Examples of the substituents possessed by the chain hydrocarbon groups represented by R ⁵¹ to R ⁵³ include halogen groups, alkoxy groups, benzoyl groups (-COC ₆ H ₅ ), and hydroxy groups.

Examples of the cyclic hydrocarbon group represented by R ⁵¹ to R ⁵³ include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain moiety. The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The number of carbon atoms in the aromatic group is preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, tolyl group, xylyl group, mesityl group, and the like. Examples of the cyclic alkyl group having a chain moiety and the chain moiety of an aromatic group having a chain moiety include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Examples include 1 to 3 alkylene groups.

Examples of the substituent on the cyclic hydrocarbon group represented by R ⁵¹ to R ⁵³ include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.

Examples of the cyclic structure formed by bonding R ⁵² and R ⁵³ to each other include a 5- to 7-membered nitrogen-containing heterocycle or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, and is more preferably a saturated ring. Specific examples include structures represented by the following formulas (5-1), (5-2), and (5-3).

［一般式（５－１）、（５－２）、（５－３）において、Ｒ⁵⁵は、Ｒ⁵¹である。Ｒ⁵⁶は、炭素数１～６のアルキル基を示す。ｌは０～５の整数を表す。ｍは０～４の整数を表す。ｎは０～４の整数を表す。＊は結合手を表す。ｌが２～５、ｍが２～４、ｎが２～４の場合、複数存在するＲ⁵⁶は、それぞれ同一でも異なっていてもよい。］

[In general formulas (5-1), (5-2), and (5-3), R ⁵⁵ is R ⁵¹ . R ⁵⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ^56s may be the same or different. ]

The X ⁵¹ represents an amide group (-CO-NH-), an ester group (-CO-O-), or a single bond. Note that the bonding direction of the amide group and the ester group is not particularly limited. Examples of the bonding mode of the amide group include C-CO-NH-Y ⁵¹ or C-NH-CO-Y ⁵¹ . Examples of the bonding mode of the ester group include C-CO-O-Y ⁵¹ or C-O-CO-Y ⁵¹ .

Examples of the divalent hydrocarbon group represented by Y ⁵¹ include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, an arenediyl group having 6 to 10 carbon atoms, and the like. Among these, alkylene groups having 1 to 10 carbon atoms are preferred. The alkylene group may be either linear or branched, but preferably linear. Y ⁵¹ is preferably an alkylene group having 1 to 5 carbon atoms.

Examples of Z ^- include halogen anions, carboxylate anions, sulfate anions, sulfonate anions, phosphate anions, and nitroxide anions.

Examples of the halogen anion include a fluoro anion, a chloro anion, a bromo anion, and an iodo anion.
Examples of the carboxylate anions include alkyl carboxylate anions such as acetate anions and propionate anions; aromatic carboxylate anions such as benzoate anions.
Examples of the sulfate anions include alkyl sulfate anions such as methyl sulfate anions and ethyl sulfate anions; aromatic sulfate anions such as phenyl sulfate anions and benzyl sulfate anions.
Examples of the sulfonate anion include alkylsulfonate anions such as methanesulfonate anion and ethanesulfonate anion; aromatic sulfonate anions such as benzenesulfonate anion and toluenesulfonate anion.
Examples of the phosphate anions include alkyl phosphate anions such as methylphosphonate anion and ethylphosphonate anion; aromatic phosphate anions such as phenylphosphonate anion and benzylphosphonate anion.

Specific examples of vinyl monomers forming the structural unit represented by formula (5) include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxypropyltrimethylammonium chloride, and (meth)acryloyloxybutyltrimethylammonium chloride. , (meth)acryloyloxyethylbenzyldimethylammonium chloride, (meth)acryloyloxypropylbenzyldimethylammonium chloride, (meth)acryloyloxybutylbenzyldimethylammonium chloride, (meth)acryloyloxyethylbenzyldiethylammonium chloride, (meth)acryloyloxy Propylbenzyldiethylammonium chloride, (meth)acryloyloxybutylbenzyldiethylammonium chloride, (meth)acryloyloxyethylbenzyldiethylammonium bromide, (meth)acryloyloxypropylbenzyldiethylammonium bromide, (meth)acryloyloxybutylbenzyldiethylammonium bromide, (meth)acryloyloxyethylbenzyldiethylammonium iodide, (meth)acryloyloxypropylbenzyldiethylammonium iodide, (meth)acryloyloxybutylbenzyldiethylammonium iodide, (meth)acryloyloxyethylbenzyldiethylammonium fluoride, ) Acryloyloxypropylbenzyldiethylammonium fluoride, (meth)acryloyloxybutylbenzyldiethylammonium fluoride, (meth)acryloyloxyethyltrimethylammonium methylsulfate, (meth)acryloyloxypropyltrimethylammonium methylsulfate, (meth)acryloyloxypropyltrimethylammonium methylsulfate ) Acryloyloxybutyltrimethylammonium methylsulfate, (meth)acryloyloxyethyldimethylethylammonium ethylsulfate, (meth)acryloyloxypropyldimethylethylammonium ethylsulfate, (meth)acryloyloxybutyldimethylethylammonium ethyl Sulfate, (meth)acryloyloxyethyltrimethylammonium toluene-4-sulfonate, (meth)acryloyloxypropyltrimethylammonium toluene-4-sulfonate, (meth)acryloyloxybutyltrimethylammonium toluene-4-sulfonate, etc. It will be done.

When containing a structural unit represented by general formula (5), its content is preferably 1% by mass or more, more preferably 5% by mass or more, and 60% by mass or less in 100% by mass of B block. Preferably, it is more preferably 40% by mass or less. It is considered that by setting the content of the structural unit represented by the general formula (5) within this range, it has a high affinity with the coloring material.

The B block may include only the structural unit represented by the general formula (3), the structural unit represented by the general formula (4), and the structural unit represented by the general formula (5), or may include other structural units. May include units. From the viewpoint of maintaining affinity with the coloring material, the structural unit represented by the general formula (3), the structural unit represented by the general formula (4), and the structure represented by the general formula (5) in the B block. The total content with units is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more in 100% by mass of B block. Moreover, it is preferable that the B block does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less in 100% by mass of the B block.

The mass ratio of the structural unit represented by the general formula (4) to the total of the structural unit represented by the general formula (3) and the general formula (5) in the B block (formula ( 4)/(Formula (3) + Formula (5))) is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and preferably 0.30 or less, more It is preferably 0.20 or less, more preferably 0.10 or less.

Specific examples of vinyl monomers that can form other structural units of block B include the same ones as those exemplified as specific examples of vinyl monomers that can form other structural units of block A.

When two or more types of structural units are contained in the B block, the various structural units contained in the B block may be contained in any form such as random copolymerization or block copolymerization in the B block. , is preferably contained in a random copolymerized form from the viewpoint of uniformity. For example, the B block may be formed of a copolymer of a structural unit consisting of a b1 block and a structural unit consisting of a b2 block.

(2-1-3. Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. In addition, the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B. When expressed as, a group consisting of (A-B) _m type, (A-B) _m -A type, (B-A) _m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) A copolymer having at least one type of structure selected from the following is preferable. Among these, AB type diblock copolymers are preferred from the viewpoint of handling properties during processing and physical properties of the composition. By constructing the AB type diblock copolymer, the structural unit derived from the (meth)acrylic monomer in the A block, the structural unit represented by the general formula (3) and the general formula ( It is thought that the structural units represented by 4) are localized and can efficiently interact favorably with the colorant, the dispersion medium (solvent), and the binder resin (alkali-soluble resin). The block copolymer may have blocks other than the A block and B block.

The content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and preferably 85% by mass or less, based on 100% by mass of the entire block copolymer. It is more preferably 80% by mass or less, and still more preferably 75% by mass or less. The content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 65% by mass or less, based on 100% by mass of the entire block copolymer. The content is more preferably 60% by mass or less, and even more preferably 55% by mass or less. By adjusting the content of A block and B block within the above range, the dispersion performance when used as a dispersant is further improved.

The mass ratio of A block to B block (A block/B block) in the block copolymer is preferably 40/60 or more, more preferably 50/50 or more, still more preferably 60/40 or more, and 98 /2 or less is preferable, more preferably 90/10 or less, still more preferably 80/20 or less. When the mass ratio of the A block to the B block is within the above range, the dispersion performance when used as a dispersant is further improved.

When the block copolymer contains a structural unit having an acidic group, the content of the structural unit derived from a vinyl monomer having an acidic group in the block copolymer is preferably 1% by mass or more and 10% by mass or less. is preferred.

The total content of the structural unit represented by the general formula (3), the structural unit represented by the general formula (4), and the structural unit represented by the general formula (5) in the block copolymer is: The content is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less.

The molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter referred to as "GPC"). The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 5,000 or more, even more preferably 7,000 or more, particularly preferably 10,000 or more, and 40, 000 or less, more preferably 30,000 or less, still more preferably 25,000 or less, particularly preferably 20,000 or less. If the weight average molecular weight is within the above range, the dispersion performance will be better when used as a dispersant.

The molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer)/(number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the width of the molecular weight distribution, resulting in a copolymer with uniform molecular weight, and when the value is 1.0, the width of the molecular weight distribution is the narrowest. That is, the lower limit value of PDI is 1.0. If the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, it will include those with small molecular weights and those with large molecular weights.

The amine value of the block copolymer is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 65 mgKOH/g or more, particularly preferably from the viewpoint of adsorption to the colorant and colorant dispersibility. is at least 80 mgKOH/g, preferably at most 200 mgKOH/g, more preferably at most 150 mgKOH/g, even more preferably at most 120 mgKOH/g.

When the block copolymer contains a structural unit having an acidic group, the acid value of the block copolymer is preferably 5 mgKOH/g or more, and preferably 50 mgKOH/g or less. By setting the acid value within this range, the block copolymer can suitably interact with the binder resin (alkali-soluble resin) without impairing its affinity with the coloring material.

(2-2. Method for producing block copolymer)
The method for producing the block copolymer includes a method in which the A block is first produced by a polymerization reaction of vinyl monomers, and the monomer of the B block is polymerized onto the A block; A method of polymerizing block monomers; A method of manufacturing A block and B block separately and then coupling A block and B block; A method of manufacturing A block first, and adding formula (3) and formula Tertiary amine structure of a part of the structural unit represented by formula (3) in the polymer obtained by polymerizing a monomer composition containing a vinyl monomer capable of forming the structural unit represented by (4) Examples include a method of quaternizing.

The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer is preferably one polymerized by living radical polymerization. Living radical polymerization maintains the simplicity and versatility of conventional radical polymerization, while being less likely to cause termination reactions or chain transfer, and allows for growth without being hindered by side reactions that deactivate growing terminals, resulting in improved molecular weight distribution. This is preferable because it is easy to precisely control and produce a polymer with a uniform composition.

Depending on the method of stabilizing the polymer growth terminal, living radical polymerization methods include a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); and a method using an organic tellurium compound. There are methods such as the method used (TERP method). Among these methods, it is preferable to use the TERP method from the viewpoint of diversity of monomers that can be used, control of molecular weight in the polymer region, uniform composition, or coloring.

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. For example, WO 2004/14848, WO 2004/14962, WO This is the method described in No. 2004/072126 and International Publication No. 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(a) A vinyl monomer is polymerized using an organic tellurium compound represented by formula (6).
(b) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by formula (6) and an azo polymerization initiator.
(c) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by formula (6) and an organic ditelluride compound represented by formula (7).
(d) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by formula (6), an azo polymerization initiator, and an organic ditelluride compound represented by formula (7).

［式（６）において、Ｒ⁶¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を示す。Ｒ⁶²およびＲ⁶³は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示す。Ｒ⁶⁴は、炭素数１～８のアルキル基、アリール基、置換アリール基、芳香族ヘテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を示す。
式（７）において、Ｒ⁶¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を示す。］

[In formula (6), R ⁶¹ represents an alkyl group, an aryl group, or an aromatic heterocyclic group having 1 to 8 carbon atoms. R ⁶² and R ⁶³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁶⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group.
In formula (7), R ⁶¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. ]

The organic tellurium compound represented by formula (6) is specifically ethyl-2-methyl-2-n-butyltellanyl-propionate, ethyl-2-n-butyltellanyl-propionate, (2-hydroxyethyl)-2- Examples include organic tellurium compounds described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870, such as methyl-methyltellanyl-propionate. Specific examples of the organic ditelluride compound represented by formula (7) include dimethyl ditelluride, dibutyl ditelluride, and the like. The azo polymerization initiator can be used without any particular restriction as long as it is an azo polymerization initiator used in normal radical polymerization, such as 2,2'-azobis(isobutyronitrile) (AIBN), 2 , 2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), 2,2'-azobis(4-methoxy-2,4- dimethylvaleronitrile) (V-70), and the like.

The polymerization process is carried out in a container purged with an inert gas, in which the vinyl monomer and the organic tellurium compound of formula (6) are combined, depending on the type of vinyl monomer, for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc. A polymerization initiator and/or an organic ditelluride compound of formula (7) are mixed. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Preferably, argon or nitrogen is used. The amount of the vinyl monomer used in (a), (b), (c) and (d) may be adjusted as appropriate depending on the physical properties of the desired copolymer.

The polymerization reaction can be carried out without a solvent, but it may also be carried out using an aprotic or protic solvent commonly used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, and tetrahydrofuran (THF). Furthermore, examples of the protic solvent include water, methanol, 1-methoxy-2-propanol, and the like. The solvents may be used alone or in combination of two or more. The amount of solvent to be used may be adjusted as appropriate, and is preferably 0.01 ml to 50 ml per 1 g of vinyl monomer. Although the reaction temperature and reaction time may be adjusted as appropriate depending on the molecular weight or molecular weight distribution of the resulting copolymer, stirring is usually carried out at 0° C. to 150° C. for 1 minute to 100 hours. After the polymerization reaction is completed, the desired copolymer can be separated from the resulting reaction mixture by removing the solvent used, residual vinyl monomer, etc., by ordinary separation and purification means.

The growing end of the copolymer obtained by the polymerization reaction is in the form of -TeR ⁶¹ (in the formula, R ⁶¹ is the same as above) derived from a tellurium compound, and is deactivated by operation in air after the polymerization reaction is completed. However, tellurium atoms may remain. Since a copolymer with tellurium atoms remaining at the terminals is colored and has poor thermal stability, it is preferable to remove the tellurium atoms. Methods for removing tellurium atoms include a radical reduction method; a method of adsorption with activated carbon, etc.; a method of adsorbing metal with an ion exchange resin, etc.; and a combination of these methods can also be used. The other end of the copolymer obtained by the polymerization reaction (the end opposite to the growing end) is -CR ⁶² R ⁶³ R ⁶⁴ derived from a tellurium compound (wherein R ⁶² , R ⁶³ and R ⁶⁴ are of the formula The form is the same as R ⁶² , R ⁶³ and R ⁶⁴ in (6).

When quaternizing the tertiary amine group of the structural unit represented by formula (3), examples of quaternizing agents include alkyl halides such as methyl chloride; aralkyl halides such as benzyl chloride; sulfuric acids such as dimethyl sulfate. Examples include dialkyl. A method for quaternizing the tertiary amine structure of a part of the structural unit represented by formula (3) in the polymer includes a method of bringing the polymer into contact with a quaternizing agent. Specifically, a method may be mentioned in which a monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (3) is polymerized, and then a quaternizing agent is added to this reaction solution and stirred. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 55° C. to 65° C., and the stirring time is preferably 5 hours to 20 hours.

(3. Binder resin)
The colored composition contains a binder resin (excluding the block copolymer). As the binder resin, an alkali-soluble resin, a polymerizable compound (polymerizable resin, a monomer having one polymerizable unsaturated bond in the molecule, a monomer having two or more polymerizable unsaturated bonds in the molecule, an oligomer, etc.) , thermosetting resin, thermoplastic resin, etc. These can be used alone or in combination of two or more. Among these, preferred are alkali-soluble resins and/or polymerizable compounds.

The content of the binder resin in the coloring composition is the total amount of binder resin used, and is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass based on the total solid content of the coloring composition. The content is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.

(3-1. Alkali-soluble resin)
The alkali-soluble resin may act as a binder for the coloring material and be soluble in a developer used in the development process when producing a color filter, preferably an alkaline developer. For example, although not particularly limited, a resin having an acidic group such as a carboxy group or a phenolic hydroxy group is preferable.

The alkali-soluble resin may be, for example, a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, in which at least a portion of the epoxy groups in the copolymer are unsaturated. A resin obtained by adding a basic acid, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction; A linear resin containing a carboxyl group in the main chain; Examples include resins in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of a group-containing resin; (meth)acrylic resins; epoxy (meth)acrylate resins having a carboxyl group; these may be used singly or in combination. A mixture of two or more species can be used.

The alkali-soluble resin is a random copolymer containing a structural unit derived from a carboxyl group-containing vinyl monomer, a structural unit derived from (meth)acrylate, and styrene, or an epoxy resin in which a (meth)acrylic group is introduced. A random copolymer containing a structural unit derived from a synthetic resin or a carboxyl group-containing vinyl monomer and a structural unit derived from a (meth)acrylate is preferred. As the carboxy group-containing vinyl monomer, (meth)acrylic acid is preferable. The (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate. , isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-hydroxylethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol mono( Examples include meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

The alkali-soluble resin preferably has a total content of structural units derived from carboxyl group-containing vinyl monomers and structural units derived from (meth)acrylates of 50% by mass or more, more preferably 60% by mass or more, and even more preferably is 70% by mass or more. Further, the alkali-soluble resin preferably has a structure derived from a carboxyl group-containing vinyl monomer of 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 90% by mass. It is preferably at most 70% by mass, more preferably at most 70% by mass.

Among the alkali-soluble resins, a random copolymer of a carboxyl group-containing vinyl monomer and (meth)acrylate is preferred. Specific examples of such copolymers include random copolymers of (meth)acrylic acid and butyl (meth)acrylate, random copolymers of (meth)acrylic acid and benzyl (meth)acrylate, and random copolymers of (meth)acrylic acid and benzyl (meth)acrylate. ) A random copolymer of acrylic acid, butyl (meth)acrylate, and benzyl (meth)acrylate, and the like. From the viewpoint of affinity between the alkali-soluble resin and the colorant, the alkali-soluble resin is particularly preferably a random copolymer of (meth)acrylic acid and benzyl (meth)acrylate. In the copolymer of a carboxyl group-containing vinyl monomer and (meth)acrylate, the content of (meth)acrylic acid is usually 5% to 90% by mass, and 10% to 70% by mass based on the total monomer components. It is preferably 20% by mass to 70% by mass. The polymerization method for these random copolymers is not particularly limited, but living radical polymerization is preferred from the viewpoint of alkali solubility.

The alkali-soluble resin may have a radically polymerizable carbon-carbon double bond in its side chain. By having a double bond in the side chain, the photocurability of the colored composition according to the present invention increases, so that resolution and adhesion can be further improved. Examples of methods for introducing a radically polymerizable carbon-carbon double bond into the side chain include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-(or m-, or p- ) A method of reacting a compound such as vinylbenzyl glycidyl ether with the acidic group of the binder resin may be mentioned.

The Mw of the alkali-soluble resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 20,000. If the Mw of the alkali-soluble resin is 3,000 or more, the heat resistance, film strength, etc. of the colored layer formed from the colored composition will be good, and if the Mw is 100,000 or less, the alkali development of this coating film will be good. The properties will be even better.

The acid value of the alkali-soluble resin is preferably 20 mgKOH/g to 170 mgKOH/g, more preferably 50 mgKOH/g to 150 mgKOH/g, and even more preferably 90 mgKOH/g to 150 mgKOH/g. When the acid value of the alkali-soluble resin is 20 mgKOH/g or more, the alkali developability when the colored composition is used as a colored layer becomes even better, and when it is 170 mgKOH/g or less, the heat resistance becomes better.
The coloring composition may contain only one type of alkali-soluble resin, or may contain multiple types. In the coloring composition, the content of the alkali-soluble resin is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, and 20 parts by mass, based on 100 parts by mass of the colorant. More preferably, the amount is from parts by weight to 80 parts by weight.

(3-2. Polymerizable compound)
The polymerizable resin as the polymerizable compound (for example, a (meth) Acrylic compounds, resins with crosslinking groups such as cinnamic acid introduced), compounds having one polymerizable unsaturated bond in the molecule (e.g., monofunctional (meth)acrylic monomers (alkyl (meth)acrylates, aralkyl (meth) acrylate, etc.)), compounds having two or more polymerizable unsaturated bonds in the molecule (e.g., polyfunctional (meth)acrylic monomers (di(meth)acrylate of dihydric alcohol, poly(meth)acrylate of trivalent or higher polyhydric alcohol), (meth)acrylate etc.)), etc. Examples of the polymerizable unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond. These can be used alone or in combination of two or more. Among these, compounds having two or more polymerizable unsaturated bonds in the molecule are preferred.

Examples of monomers having two or more polymerizable unsaturated bonds in the molecule as the polymerizable compound include bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,3-butylene glycol di(meth)acrylate. (meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta Examples include (meth)acrylate.

The content of the polymerizable compound in the coloring composition is preferably 10 parts by mass to 1,000 parts by mass, particularly preferably 20 parts by mass to 500 parts by mass, based on 100 parts by mass of the colorant. If the content of the polymerizable compound is within the above range, sufficient curability will be obtained and the alkali developability will also be good. It is also preferable to use an alkali-soluble resin and a polymerizable compound together as the binder resin.

(3-3. Thermosetting resin, thermoplastic resin)
Examples of the thermosetting resin and thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyurethane resin, phenolic resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin etc.

(4. Dispersion medium)
The dispersion medium used in the present invention can be appropriately selected as long as it can disperse or dissolve the other components constituting the coloring composition, does not react with these components, and has appropriate volatility. Can be used. For example, conventionally known organic solvents can be used, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether, etc. Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, Glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether Glycol dialkyl ethers such as , ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono- n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, Glycol alkyl ethers such as diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate Acetates; glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, diacetate; Ethers such as propyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone Ketones such as , ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butane diol, diethylene glycol, dipropylene Monohydric or polyhydric alcohols such as glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane Aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, Ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl Chains such as benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone, etc. alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; acetonitrile and benzonitrile Examples include nitriles such as. The organic solvent should be glycol alkyl ether acetates, glycol monoalkyl ethers, monohydric or polyhydric alcohols from the viewpoint of dispersibility of coloring materials, solubility of dispersants, coatability of coloring compositions, etc. is preferred. The coloring composition may contain only one type of solvent, or may contain multiple types.

When forming pixels of a color filter by photolithography, the boiling point of the dispersion medium is preferably 100°C to 200°C (under a pressure of 1013.25 hPa; hereinafter, the same applies to all boiling points), and 120°C to 170°C. More preferred. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferred because they have a good balance in coating properties, surface tension, etc., and have relatively high solubility of the constituent components in the coloring composition. Glycol alkyl ether acetates may be used alone or in combination with other dispersion media. Further, it is also preferable to use a dispersion medium having a boiling point of 150° C. or higher. By using a dispersion medium with a high boiling point in combination, it is possible to suppress the destruction of the mutual relationship between the colored compositions due to rapid drying of the colored compositions. Note that the dispersion medium having a boiling point of 150° C. or higher may be a glycol alkyl ether acetate.

The content of the dispersion medium in the coloring composition is not particularly limited and can be adjusted as appropriate. The upper limit of the content of the dispersion medium in the colored composition is usually 99% by mass. Further, the lower limit of the content of the dispersion medium in the colored composition is usually 70% by mass, preferably 80% by mass, considering the viscosity suitable for application of the colored composition. The dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the colored composition.

(5. Photopolymerization initiator)
The colored composition of the present invention may contain a photopolymerization initiator, if necessary. Thereby, radiation sensitivity can be imparted to the colored composition. The photopolymerization initiator is a compound that generates active species that can initiate polymerization of a polymerizable compound upon exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron beams, and X-rays.

Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, and α-diketones. Examples thereof include polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, and the like. The photopolymerization initiators can be used alone or in combination of two or more.

In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass, particularly preferably 1 part by mass to 100 parts by mass, based on 100 parts by mass of the polymerizable compound. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure, whereas if it is too large, the formed colored layer tends to easily fall off from the substrate during development.

(6. Other compounded agents)
The coloring composition of the present invention may contain other compounding agents in addition to the above-mentioned compounding agents, as long as they do not impair the preferred physical properties of the present invention. Other compounding agents include dispersants other than the above block copolymers (urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic esters). system dispersant, aliphatic modified polyester dispersant, etc.), sensitizing dye, thermal polymerization inhibitor, plasticizer, organic carboxylic acid compound, organic carboxylic acid anhydride, pH adjuster, antioxidant, ultraviolet absorber, light Stabilizers, preservatives, antifungal agents, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants), anti-aggregation agents, adhesion improvers, development improvements agents, storage stabilizers, etc.

Sensitizing dyes include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 , 4-diaminobenzophenone, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-( p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzothiazole, -diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, ( p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. can be mentioned.

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, and β-naphthol.

Examples of nonionic surfactants include fluorine surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluoropropyl) Fluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol Di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.), silicone surfactants, polyoxyethylene surfactants agents (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin) fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, etc.) Can be mentioned.

Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, aliphatic Alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer surfactants agents, etc.
Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
Examples of amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, amino acids, and the like.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerin, and the like.

Examples of organic carboxylic acid compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid; Aliphatic tricarboxylic acids such as tricarballylic acid and aconitic acid; benzoic acid Aromatic carboxylic acids in which a carboxyl group is directly bonded to a phenyl group, such as , phthalic acid, trimesic acid, pilopete acid, and merophanic acid; phenyl groups such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, phenylsuccinic acid, and cinnamylindenacetic acid. Examples include aromatic carboxylic acids to which a carboxyl group is bonded via a carbon bond. By containing an organic carboxylic acid compound, alkali developability and scumming can be improved.

Examples of organic carboxylic anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- Examples include cyclohexenedicarboxylic acid, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like. By containing an organic carboxylic acid anhydride, alkali developability and scumming can be improved.

<Method for producing colored composition>
The colored composition can be prepared by mixing a coloring material, a dispersant, a binder resin, a dispersion medium, and if necessary, a photopolymerization initiator and other ingredients. For mixing, for example, a mixing and dispersing machine such as a paint shaker, bead mill, ball mill, dissolver, or kneader can be used. Preferably, the colored composition is filtered after mixing. Since the coloring composition has alkaline developability, it can be suitably used for color filters.

<Color filter>
The color filter of the present invention includes a colored layer formed using the colored composition.

Examples of methods for manufacturing color filters include the following method. First, thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin, and polymethyl methacrylate resin, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic resin, and various types of glass. For example, after a colored composition in which a red pigment is dispersed is applied onto a transparent substrate such as the above transparent substrate, prebaking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, this coating film is exposed to light through a photomask, and then developed using an alkaline developer (such as an organic solvent or an aqueous solution containing a surfactant and an alkaline compound) to dissolve and remove the unexposed areas of the coating film. do. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed. Next, using a green coloring composition (the coloring composition of the present invention) or a blue coloring composition, each coloring composition is applied, prebaked, exposed, developed, and postbaked in the same manner as described above to obtain a green color. A pixel array and a blue pixel array are sequentially formed on the same substrate. As a result, a color filter is obtained in which pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate. However, in the present invention, the order in which pixels of each color are formed is not limited to the above. Further, a black matrix may be provided on the transparent substrate used to form the pixel array of the three primary colors of red, green, and blue.

When applying the colored composition to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, etc. can be adopted. In particular, it is preferable to employ a spin coating method or a slit die coating method.

After forming a protective film as necessary on the pixel pattern thus obtained, a transparent conductive film (ITO or the like) is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter.

The color filter of the present invention has high brightness, dimensional accuracy, etc., and can be suitably used for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, etc.

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples in any way, and can be implemented with appropriate modifications within the scope of the gist. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value and acid value of the block copolymer and binder resin, and the viscosity and brightness of the colored composition were evaluated according to the following methods.

The meanings of the abbreviations are as follows.
BTEE: Ethyl-2-methyl-2-n-butyltellanyl-propionate DBDT: Dibutyl ditelluride AIBN: 2,2'-azobis(isobutyronitrile)
BMA: n-butyl methacrylate PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Co., Ltd., Plaxel (registered trademark) FM5)
DMAEMA: 2-(dimethylamino)ethyl methacrylate Vt: Vinyltoluene St: Styrene PMA: Propylene glycol monomethyl ether acetate

(Polymerization rate)
¹ H-NMR was measured using a nuclear magnetic resonance (NMR) measuring device (manufactured by Bruker Biospin, model: AVANCE 500 (frequency 500 MHz)) (solvent: CDCl ₃ , internal standard: TMS). Regarding the obtained NMR spectrum, the integral ratio of the peaks of the vinyl group derived from the monomer and the ester side chain derived from the polymer was determined, and the polymerization rate of the monomer was calculated.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It was determined by gel permeation chromatography (GPC) using a high performance liquid chromatograph (manufactured by Tosoh, Model HLC-8320). The column is one SHODEX KF-603 (φ6 mm x 150 mm) (manufactured by SHODEX), the mobile phase is 10 mmol/L lithium bromide/10 mmol/L acetic acid/N-methyl-2-pyrrolidone solution, and the detector is a differential refractometer. It was used. The measurement conditions were a column temperature of 40° C., a sample concentration of 20 mg/mL, a sample injection amount of 10 μm, and a flow rate of 0.2 mL/min. A calibration curve was created using polystyrene (molecular weight: 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard substance, and the weight average molecular weight ( Mw) and number average molecular weight (Mn) were measured. The molecular weight distribution (PDI=Mw/Mn) was calculated from this measured value.

(amine value)
The amine value represents the mass of potassium hydroxide (KOH) equivalent to the basic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was subjected to neutralization titration with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titration device (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated using the following formula, using the inflection point of the titration pH curve as the titration end point.
B=56.11×Vs×0.1×f/w
B: Amine value (mgKOH/g)
Vs: Amount of 0.1 mol/L hydrochloric acid/2-propanol solution required for titration (mL)
f: Titer of 0.1 mol/L hydrochloric acid (2-propanol) w: Mass of measurement sample (g) (solid content equivalent)

(Acid value)
The acid value represents the weight of potassium hydroxide required to neutralize acidic components per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, several drops of 1.0 w/v% phenolphthalein ethanol (90) solution was added as an indicator to the resulting solution, and neutralization titration was performed with 0.1 mol/L potassium hydroxide/ethanol solution. . The titration end point was when a little redness remained, and the acid value was calculated using the following formula.
A=56.11×Vs×0.1×f/w
A: Acid value (mgKOH/g)
Vs: Amount of 0.1 mol/L potassium hydroxide/ethanol solution used for titration (mL)
f: Potency of 0.1 mol/L potassium hydroxide/ethanol solution w: Measured sample weight (g) (solid content conversion)

(viscosity)
Viscosity was measured using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.) using a cone rotor (1°34'×R24) at 25° C. and a rotor rotation speed of 60 rpm. The measurements were performed on colored compositions that were stored at 25° C. for 1 hour after preparation. Those with a viscosity of 30 mPa·s or less were evaluated as “○”, and those with a viscosity exceeding 30 mPa·s were evaluated as “×”.

(Luminance)
On a glass plate (50 mm x 50 mm) whose surface had been cleaned, three coating films of the colored composition with different thicknesses were formed using a spin coater (product name: MS-A100, manufactured by Mikasa Co., Ltd.) and heated at 90°C. and dried for 10 minutes. The x and Y values of the dried coating film were measured using a spectrophotometer (trade name: CM-5, manufactured by Konica Minolta). A calibration curve was created from the obtained x and Y values, and the corrected Y value when x=0.265 was calculated. The coated film was heat-treated at 230° C. for 30 minutes, and the corrected Y value was calculated in the same manner as above. Further, ΔY was calculated from the corrected Y values before and after the heat treatment.

<Production of block copolymer>
(Block copolymer No. 1)
22.7 g of BMA, 137.9 g of PCL5, 0.82 g of AIBN, and 40.1 g of PMA were placed in a flask equipped with an argon gas introduction tube and a stirrer, and after replacing with argon, 7.49 g of BTEE and 9.23 g of DBDT were added. The A block was polymerized by reacting at 60° C. for 7 hours. The polymerization rate was 99.2%.

A mixed solution of 81.3 g of DMAEMA, 8.0 g of Vt, and 22.3 g of PMA, which had been substituted with argon in advance, was added to the reaction solution, and the mixture was reacted at 60° C. for 11 hours to polymerize the B block. The polymerization rate was 99.0%. In addition, the monomers in the first stage of polymerization remaining in the reaction solution were also polymerized, and the polymerization rate of the monomers in the first stage of polymerization remaining in the reaction solution was 100%.

After the reaction was completed, the reaction solution was poured into stirring n-heptane. The precipitated polymer was suction filtered and dried to obtain block copolymer No. I got 1. The obtained block copolymer No. No. 1 had an Mw of 15,310, a PDI of 1.58, and an amine value of 114 mgKOH/g. The content of each structural unit in the copolymer was calculated from the charging ratio of monomers used in the polymerization reaction and the polymerization rate.

(Block copolymer No. 2 to 4)
Block copolymer No. Block copolymer No. 1 was produced in the same manner as in production method No. 1. 2 to 4 were produced. Table 1 shows the monomers, organic tellurium compounds, organic ditelluride compounds, azo polymerization initiators, solvents, reaction conditions, and polymerization rates used. Further, Table 2 shows the composition, Mw, PDI, and amine value of each block copolymer. The content of each structural unit in the copolymer was calculated from the charging ratio of monomers used in the polymerization reaction and the polymerization rate.

<Synthesis of alkali-soluble resin (binder resin)>
A flask equipped with an argon gas introduction tube and a stirrer was charged with methacrylic acid (MAA) (40.0 g), benzyl methacrylate (BzMA) (160.0 g), and propylene glycol monomethyl ether acetate (PMA) (580.0 g). After replacing the mixture with argon, 2,2'-azobis(isobutyronitrile) (AIBN) (4.0 g), n-dodecanethiol (6.0 g), and PMA (20.0 g) were added, and the temperature was raised to 90°C. MAA (80.0 g), BzMA (320.0 g), AIBN (8.0 g), n-dodecanethiol (12.0 g), and PMA (50.0 g) were added to the solution while keeping the solution at 90°C. The mixture was added dropwise over 1.5 hours. 60 minutes after the dropwise addition was completed, the temperature was raised to 110°C, AIBN (0.8 g) and PMA (10.0 g) were added and reacted for 1 hour, and further AIBN (0.8 g) and PMA ( 10.0 g) was added and reacted for 1 hour, and further AIBN (0.8 g) and PMA (10.0 g) were added and reacted for 1 hour.

The resulting reaction solution was cooled to room temperature, and PMA (240.0 g) was added to obtain a solution of an alkali-soluble resin with a nonvolatile content of 39.5%. The weight average molecular weight (Mw) of the alkali-soluble resin was 9,150, the molecular weight distribution (PDI) was 1.92, and the acid value was 128 mgKOH/g.

<Manufacture of colored composition>
The blending composition was adjusted to 11 parts by mass of pigment, 6.8 parts by mass of dispersant (block copolymer No. 1), 6.7 parts by mass of alkali-soluble resin, and 75.5 parts by mass of PMA, and 0.3 mm zirconia was added. 555 parts by mass of beads were added and mixed in a bead mill (trade name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH) for 3 hours to fully disperse the mixture. After the dispersion was completed, the beads were filtered to obtain a colored composition. The pigment contains C. I. Pigment Green 58 (trade name: FASTOGEN (registered trademark) GREEN A310, manufactured by DIC Corporation, polyhalogenated zinc phthalocyanine) was used. Table 3 shows the evaluation results of the viscosity and brightness of the pigment dispersion obtained.

(Coloring composition No. 2 to 4)
Coloring composition No. 1 except that the dispersant (block copolymer) was changed. Coloring composition No. 1 was prepared in the same manner as in the preparation method of No. 1. 2 to 4 were prepared. The viscosity and brightness of the obtained colored composition were evaluated, and the results are shown in Table 3.

As shown in Table 3, block copolymer No. 1 was used as a dispersant. Coloring composition No. 1 was used. No. 1 has excellent dispersibility. Moreover, coloring composition No. No. 1 was able to suppress the decrease in brightness after heating the coating film.

Claims (8)

A colored composition containing a coloring agent, a dispersant, a binder resin, and a dispersion medium,
The coloring material contains a polyhalogenated metal phthalocyanine pigment,
The dispersant contains a block copolymer having an A block and a B block,
The A block has a structural unit represented by general formula (2) ,
The B block has a structural unit represented by general formula (3) and a structural unit represented by general formula (4),
A colored composition characterized in that the content of the structural unit represented by the general formula (4) in the B block is 1% by mass to 23% by mass.

[In general formula (2), n1 represents an integer from 1 to 10. R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an alkylene group having 1 to 10 carbon atoms. R ²³ represents an alkylene group having 1 to 10 carbon atoms. ]

[In formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may be bonded to each other to form a cyclic structure. R ³³ represents a hydrogen atom or a methyl group. X ³¹ represents an amide group, an ester group, or a single bond. Y ³¹ represents a divalent hydrocarbon group. ]

[In formula (4), n represents an integer of 1 to 5. R ⁴¹ represents a chain hydrocarbon group which may have a substituent. ] The colored composition according to claim 1 , wherein the block copolymer has an amine value of 10 mgKOH/g to 200 mgKOH/g. The colored composition according to claim 1 or 2, wherein the B block contains 10% by mass to 99% by mass of the structural unit represented by the general formula (3). The colored composition according to any one of claims 1 to 3 , wherein the mass ratio (A block/B block) of the A block and the B block in the block copolymer is 40/60 to 98/2. thing. The colored composition according to any one of claims 1 to 4 , wherein the block copolymer has a molecular weight distribution (PDI) of 2.5 or less. The colored composition according to any one of claims 1 to 5, wherein the block copolymer is polymerized by living radical polymerization. The colored composition according to any one of claims 1 to 6, which is used for color filters. A color filter comprising a colored layer formed using the colored composition according to claim 7 .