CN102408753A - Alkaline colorant, colored composition, color filter and display element - Google Patents

Abstract

The invention relates to an alkaline colorant, a colored composition, a color filter and a display element. The invention provides an alkaline colorant with higher heat resistance. The alkaline colorant is provided with a negative ion represented by the following formula (1). In the formula (1), R represents an n valence organic group formed by 1-16 atoms, n represents integers of 2-4, wherein the atoms do not comprise hydrogen atoms. R (-SO3-) n (1).

Description

Basic colorant, coloring composition, color filter and display element

technical field

The present invention relates to an alkaline colorant, a coloring composition, a color filter, and a display element, and more specifically, to an alkaline colorant suitable for use in a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, etc. A basic colorant for a color filter, a coloring composition containing the colorant, a color filter including a colored layer containing the colorant, and a display element including the color filter.

Background technique

When producing a color filter using a colored radiation-sensitive composition, a method is known in which a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then the dried coating film is irradiated in a desired pattern shape. Radiation (hereinafter referred to as "exposure") and development are performed to obtain pixels of each color (Patent Documents 1 and 2). Moreover, the method of forming a black matrix using the photopolymerizable composition which disperse|distributed carbon black is also known (patent document 3). Moreover, the method of obtaining the pixel of each color by the inkjet system using a pigment dispersion type colored resin composition is also known (patent document 4).

However, it is known that the use of a dye as a colorant is effective in achieving higher brightness and higher color purity of a display device, or higher resolution of a solid-state imaging device. For example, Patent Document 5 proposes the use of a triarylmethane dye of a specific structure.

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Application Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Application Laid-Open No. 6-35188

[Patent Document 4] Japanese Patent Laid-Open No. 2000-310706

[Patent Document 5] Japanese Unexamined Patent Publication No. 2008-304766

Contents of the invention

However, basic colorants such as the triarylmethane-based dyes proposed in Patent Document 5 have insufficient heat resistance, and will lose their Superiority to the colorimetric properties of pigments. In view of the above background, there is a strong need to develop an alkaline colorant excellent in heat resistance.

Therefore, the subject of this invention is providing the basic coloring agent and coloring composition excellent in heat resistance. Moreover, the subject of this invention is providing the display element provided with the color filter provided with the colored layer containing this coloring agent, and this color filter.

As a result of earnest studies, the inventors of the present invention found that a basic colorant having a specific polyfunctional sulfonate group as an anion part can solve the above-mentioned problems.

That is, the present invention provides a basic coloring agent (hereinafter also referred to as "the present coloring agent") having an anion represented by the following formula (1).

R(-SO ₃ ^- ) _n (1)

[In formula (1), R represents an n-valent organic group composed of 1 to 16 atoms (not including hydrogen atoms), and n represents an integer of 2 to 4. ]

In addition, the present invention provides a coloring composition containing (A) coloring agent, (B) binder resin, and (C) crosslinking agent, and containing this coloring agent as (A) coloring agent ; a color filter having a colored layer containing the present colorant; and a display element including the color filter. Wherein, "colored layer" refers to pixels of each color, black matrix, black spacer, etc. used for the color filter.

This colorant is excellent in heat resistance. If the coloring composition containing this coloring agent is used, even if it passes through a high-temperature heating process, the coloring layer which maintains the excellent chromaticity characteristic can be formed.

Therefore, this colorant is extremely suitable for the production of color filters for color liquid crystal display elements, color separation color filters for solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. kinds of color filters. In addition, the present colorant can also be suitably used for coloring of plastic moldings, colorants for inkjet inks, colorants for color toners, colorants for electrophoretic display elements, and the like.

Detailed ways

Hereinafter, the present invention will be described in detail.

This colorant

This coloring agent is a basic coloring agent in which a cation is used as a chromophoric group, and has an anion represented by the above-mentioned formula (1) as an anion part. That is, it is presumed that the present coloring agent accumulates cations by introducing polyfunctional sulfonate groups as anion moieties, and as a result, the heat resistance of the coloring agent is improved. Examples of the present colorant include triarylmethane-based colorants, methine-based colorants, azo-based colorants, diarylmethane-based colorants, quinoneimine-based colorants, anthraquinone-based colorants, Phthalocyanine-based colorants, xanthene-based colorants.

First, definitions of symbols in the formula (1) will be described.

R represents an n-valent organic group composed of 1 to 16 atoms (excluding hydrogen atoms), and preferably the number of atoms excluding hydrogen atoms is 2 to 12. If the number of atoms excluding hydrogen atoms constituting R exceeds 16, the coloring power of the present coloring agent may decrease.

R is not particularly limited as long as it satisfies the above conditions, and examples include:

1) Substituted or unsubstituted non-aromatic hydrocarbon group (hereinafter also referred to as "characteristic group (r1)"),

2) A group in which a plurality of substituted or unsubstituted non-aromatic hydrocarbon groups are linked by a heteroatom-containing divalent linking group (hereinafter also referred to as "characteristic group (r2)"),

3) A substituted or unsubstituted aromatic hydrocarbon group (hereinafter also referred to as "characteristic group (r3)"),

4) A group in which two substituted or unsubstituted aromatic hydrocarbon groups are linked by a heteroatom-containing divalent linking group or a divalent non-aromatic hydrocarbon group (hereinafter also referred to as "characteristic group (r4)"),

5) A substituted or unsubstituted heterocyclic group (hereinafter also referred to as a "characteristic group (r5)") and the like.

The non-aromatic hydrocarbon group in the above-mentioned characteristic group (r1) is not particularly limited as long as it has no aromatic hydrocarbon group. A group of ∼4 hydrogen atoms, a group in which 2 to 4 hydrogen atoms are removed from a hydrocarbon formed by linking an aliphatic hydrocarbon and an alicyclic hydrocarbon. Specific examples of aliphatic hydrocarbons include alkanes, alkenes, and alkynes, and specific examples of alicyclic hydrocarbons include cycloalkanes, cycloalkenes, condensed polycyclic hydrocarbons, bridged ring hydrocarbons, spirocyclic hydrocarbons, cyclohydrocarbons, and cyclohydrocarbons. terpenes, etc. As the substituent in ^the characteristic group (r1), for example, halo, hydroxyl, alkoxy, carbonyl, amino, etc., are substituted by halo, especially fluorine, on the carbon close to _-SO3- , from which the This colorant is preferable in terms of heat resistance. Typical examples of anions in which R is a characteristic group (r1) include anions represented by the following formula.

In addition, the non-aromatic hydrocarbon group in the above-mentioned characteristic group (r2) is not particularly limited as long as it has no aromatic hydrocarbon group. A group having 1 to 5 hydrogen atoms, a group obtained by removing 1 to 5 hydrogen atoms from a hydrocarbon formed by linking an aliphatic hydrocarbon and an alicyclic hydrocarbon, and the like. Specific examples of the aliphatic hydrocarbon and the alicyclic hydrocarbon include the same compounds as the aliphatic hydrocarbon and alicyclic hydrocarbon in the characteristic group (r1). Examples of the substituent in the characteristic group (r2) include the same substituents as those in the characteristic group (r1). Examples of the heteroatom-containing divalent linking group in the characteristic group (r2) include -O-, -CO-, -COO-, -CONH-, -NHCONH-, -NR ¹ R ² -(R ¹ and R ² independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group), -S-, -SO-, -SO ₂ -, -SS-, a divalent heterocyclic group, and the like. It should be noted that there may be a plurality of heteroatom-containing divalent linking groups in the characteristic group (r2). Representative examples of anions in which R is a characteristic group (r2) include, for example, anions represented by the following formula.

In addition, the aromatic hydrocarbon group in the characteristic group (r3) is not particularly limited, and examples thereof include groups obtained by removing 2 to 4 hydrogen atoms from benzene, biphenyl, naphthalene, phenanthrene, anthracene, pyrene, and the like. Examples of the substituent in the characteristic group (r3) include a halogeno group, a hydroxyl group, an alkoxy group, an amino group, and an alkyl group. Representative examples of anions in which R is a characteristic group (r3) include, for example, anions represented by the following formula.

In addition, examples of the aromatic hydrocarbon group in the characteristic group (r4) include groups obtained by removing 1 to 5 hydrogen atoms from benzene, and the like. Examples of the substituent in the characteristic group (r4) include the same substituents as those in the above-mentioned characteristic group (r3). Examples of the heteroatom-containing divalent connecting group in the characteristic group (r4) include the same groups as the heteroatom-containing divalent connecting group in the above-mentioned characteristic group (r2). Examples of the divalent non-aromatic hydrocarbon group in the characteristic group (r4) include divalent aliphatic hydrocarbon groups such as methylene, alkylene, and vinylene. Representative examples of anions in which R is a characteristic group (r4) include, for example, anions represented by the following formula.

嗪等。作为具有氮原子和硫原子作为构成环的杂原子的杂环系化合物的具体例，可举出吩噻吩噻嗪等。作为特性基(r5)中的取代基，可举出与上述特性基(r3)中的取代基同样的基团。作为R为特性基(r5)的阴离子的代表例，例如可举出下式表示的阴离子。In addition, the heterocyclic group in the above-mentioned characteristic group (r5) is not particularly limited, and examples include groups obtained by removing 2 to 4 hydrogen atoms from a heterocyclic compound having only nitrogen atoms as heteroatoms constituting the ring. , A group in which 2 to 4 hydrogen atoms are removed from a heterocyclic compound having only an oxygen atom as a heteroatom constituting a ring, and a group in which 2 to 4 hydrogen atoms are removed from a heterocyclic compound having only a sulfur atom as a heteroatom constituting a ring A group of hydrogen atoms, a group in which 2 to 4 hydrogen atoms are removed from a heterocyclic compound having a nitrogen atom and an oxygen atom as a heteroatom constituting a ring, a group having a nitrogen atom and a sulfur atom as a heteroatom constituting a ring Groups with 2 to 4 hydrogen atoms removed from heterocyclic compounds. Specific examples of heterocyclic compounds having only nitrogen atoms as heteroatoms constituting the ring include pyrrole, pyridine, indole, isoindole, quinoline, isoquinoline, carbazole, phenanthridine, acridine, etc. . Specific examples of the heterocyclic compound having only an oxygen atom as a hetero atom constituting the ring include furan, pyran, isobenzofuran, isochromene, xanthene and the like. Specific examples of the heterocyclic compound having only a sulfur atom as a hetero atom constituting the ring include thiophene, thianthrene, and the like. Specific examples of heterocyclic compounds having a nitrogen atom and an oxygen atom as heteroatoms constituting the ring include phen

Zinc, etc. Specific examples of heterocyclic compounds having a nitrogen atom and a sulfur atom as heteroatoms constituting the ring include phenothione phenothiazines etc. Examples of the substituent in the characteristic group (r5) include the same substituents as those in the above-mentioned characteristic group (r3). Representative examples of anions in which R is a characteristic group (r5) include, for example, anions represented by the following formula.

On the other hand, the cation contained in the present colorant is not particularly limited as long as it is a cationic chromophore, that is, a cation that forms a basic colorant together with the anion represented by the above formula (1), for example, triaryl Methane-based chromophores, methine-based chromophores, azo-based chromophores, diarylmethane-based chromophores, quinoneimine-based chromophores, anthraquinone-based chromophores, phthalocyanine-based chromophores Group, xanthine chromophore, etc.

As the triarylmethane-based chromophore, one represented by the following formula (2) is preferable. It should be noted that various resonance structures exist in the cation represented by the following formula (2). In the present specification, when a resonance structure exists in a cation represented by each formula, it is considered to be equivalent to the cation represented by the formula.

[In formula (2), Ar represents an aromatic ring; R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 8 carbon atoms, a phenyl group, or an alkene A group with a bonded unsaturated bond; R ⁵ and R ⁶ independently represent a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 8 carbon atoms, a phenyl group, or an ethylenic non-saturated group. A group with a saturated bond; R ⁷ represents a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, -COOR'(R' represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms) or a chlorine atom; R ⁸ and R ¹¹ independently represent a hydrogen atom or an alkyl group with 1 to 8 carbon atoms, or R ⁸ and R ¹¹ together represent an oxygen atom; R ⁹ and R ¹⁰ independently represent a hydrogen atom or an alkyl group with 1 to 8 carbon atoms A group or a chlorine atom; Y represents a hydrogen atom or a group represented by the following formula (3). ]

[In formula (3), R ¹² and R ¹³ independently represent a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 8 carbon atoms, a phenyl group, or an ethylenically unsaturated bond group. ]

The aromatic ring in Ar is preferably an aromatic ring having 6 to 20 carbon atoms (more preferably 6 to 10 carbon atoms), and specific examples include a benzene ring, a naphthalene ring, a biphenyl ring, and an anthracene ring.

An alkyl group having 1 to 8 carbon atoms as R ³ to R ¹¹ in the above formula (2) (R' including -COOR' in R ⁷ ) and R ¹² and R ¹³ in the above formula (3), For example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-amyl, hexyl, heptyl, octyl, isooctyl , tert-octyl, 2-ethylhexyl, etc.

Examples of cycloalkyl groups having 3 to 8 carbon atoms of R ³ to R ⁶ in the above formula (2) and R ¹² and R ¹³ in the above formula (3) include cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, etc.

The group having an ethylenically unsaturated bond among R ³ to R ⁶ , R ¹² and R ¹³ is not particularly limited, and examples thereof include CH ₂ =CH-COO-R ¹⁴ -, CH ₂ =C(CH ₃ )-COO-R ¹⁴ -, CH ₂ =CH-Ph-R ¹⁴ -, CH ₂ =C(CH ₃ )-Ph-R ¹⁴ - and CH ₂ =CH-CO- (R ¹⁴ represents 1 carbon atom ~4 alkanediyl, Ph represents phenylene) and the like.

Examples of the alkanediyl group having 1 to 4 carbon atoms in ^R14 include methylene, ethylene, ethane-1,1-diyl, propane-1,1-diyl, propane-1 , 2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4 - Diji et al.

In the present invention, among the cations represented by the above formula (2), the cation represented by the following formula (4) is particularly preferable from the viewpoint of improving brightness and color purity.

[In formula (4), R ³ , R ⁴ , R 5 , R ⁶ , R ¹³ and R ¹³ and R ³ , R ⁴ , R ⁵ , R ⁶ , ^{R 12 in} formula (2) and (3) above Synonymous with ^R13 . ]

In the above formula (4), R ³ , R ⁴ , R ¹² and R ¹³ are preferably an alkyl group or phenyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), and as R ⁵ , An alkyl group, cyclohexyl group or phenyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms) is preferred, and R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms). Alkyl, cyclohexyl, phenyl or hydrogen atom.

As a representative example of the cation represented by said formula (2), the cation represented by the following formula is mentioned, for example.

In addition, as the methine-based chromophore, those represented by the following formulas (5-1) to (5-3) are preferable.

[In the formulas (5-1) to (5-3), R ¹⁵ represents a hydrogen atom or a halogen atom; R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ independently represent an alkyl group with 1 to 6 carbon atoms; R ²⁰ represents a substituted or unsubstituted alkyl group with 1 to 6 carbon atoms; G represents -CH=CH-, -CH=CH-NR ²¹ -, -CH=N-NR ²¹ - or -N=N-NR ²¹ -(R ²¹ represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms); R ^a represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. ]

As R ^a , groups represented by the following formulas (5a) to (5g) are preferable.

[In formulas (5a) to (5g), R ²² and R ²⁹ independently represent an alkyl group with 1 to 6 carbon atoms; R ²³ represents a substituted or unsubstituted alkyl group with 1 to 6 carbon atoms; R ²⁴ , R ²⁶ , R ²⁷ and R ²⁸ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms or an alkoxy group with 1 to 6 carbon atoms; R ²⁵ and R ³⁰ independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group. ]

As a substituent of the said alkyl group, a halogen atom, a cyano group, a hydroxyl group etc. are mentioned.

As a representative example of the cation represented by said formula (5-1) - (5-3), the cation represented by the following formula is mentioned, for example.

As the azo-based chromophore, those represented by the following formulas (6-1) to (6-6) are preferable.

[In formulas (6-1) to (6-6), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁷ independently represent substituted or unsubstituted alkyl groups with 1 to 6 carbon atoms ; R ³⁶ and R ⁴⁰ independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group; R ³⁸ represents a carbon atom An alkyl group with the number 1 to 6; R ³⁹ represents a group forming a quaternary ammonium; R ^b represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. ]

R ³⁹ is preferably -NR ⁴¹ C _m H _2m N ⁺ R ⁴² R ⁴³ R ⁴⁴ (m is an integer of 1 to 5; R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁴² , R ⁴³ and R ⁴⁴ independently represent an alkyl group having 1 to 6 carbon atoms), -COC _m H _2m N ⁺ R ⁴² R ⁴³ R ⁴⁴ (m, R ⁴² , R ⁴³ and R ⁴⁴ have the same meaning as above), - C _m H _2m N ⁺ (NH ₂ ) R ⁴⁵ R ⁴⁶ (m has the same meaning as above; R ⁴⁵ and R ⁴⁶ independently represent an alkyl group with 1 to 6 carbon atoms), or the following formula (6-i) or A group represented by (6-ii).

[In the formulas (6-i) and (6-ii), R ⁴¹ and m have the same meaning as above. ]

As said R ^b , groups represented by the following formulas (6a) to (6e) and substituted or unsubstituted phenyl groups are preferable.

[In the formulas (6a) to (6d), R ⁴⁷ represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, a phenyl group or a benzyl group; R ⁴⁸ represents a hydrogen atom, a substituted or unsubstituted carbon atom with 1 to 6 Alkyl, phenyl or benzyl; R ⁵⁰ represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms or a phenyl group; R ⁵¹ and R ⁵² independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms ; R ⁴⁹ , R ⁵³ , R ⁵⁴ and R ⁵⁵ independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group . ]

As a substituent of the said alkyl group, a halogen atom, a hydroxyl group, a cyano group, _-CONH2 etc. are mentioned. Examples of the substituent for the phenyl group include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a nitro group, and the like.

As a representative example of the cation represented by said formula (6-1) - (6-6), the cation represented by the following formula is mentioned, for example.

The diarylmethane-based chromophore is preferably represented by the following formula (7-1) or (7-2).

[In formulas (7-1) and (7-2), R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ independently represent an alkane with 1 to 6 carbon atoms. R ⁶⁰ , R ⁶⁵ and R ⁶⁶ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

As a representative example of the cation represented by said formula (7-1) - (7-2), the cation represented by the following formula is mentioned, for example.

As the quinoneimine-based chromophore, those represented by the following formulas (8-1) to (8-3) are preferable.

[In formulas (8-1) to (8-3), R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R 72 , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸⁰ , ^{R 81} , R ⁸² , R ⁸³ and R ⁸⁴ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, phenyl or benzyl; R ⁷³ and R ⁷⁹ independently represent an alkyl group with 1 to 6 carbon atoms or an aryl group with 6 to 20 carbon atoms; R ⁷⁸ represents -NR ⁸⁵ R ⁸⁶ (R ⁸⁵ and R ⁸⁶ represent independently substituted or unsubstituted an alkyl group with 1 to 6 carbon atoms), a hydroxyl group, a nitro group or a cyano group; Q represents an oxygen atom or a sulfur atom. ]

As a substituent of the said alkyl group, a halogen atom, a hydroxyl group, a cyano group etc. are mentioned.

As a representative example of the cation represented by said formula (8-1) - (8-3), the cation represented by the following formula is mentioned, for example.

The anthraquinone-based chromophore is preferably represented by the following formula (9-1) or (9-2).

[In formulas (9-1) and (9-2), R ⁸⁷ , R ⁹² and R ⁹³ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl; R ⁸⁸ and R ⁹⁴ independently represent substituted or unsubstituted alkanediyl; R ⁸⁹ , R ⁹⁰ , R ⁹¹ , R ⁹⁵ , R ⁹⁶ and R ⁹⁷ independently represent C1-6 alkyl. ]

Examples of the substituents for the above-mentioned alkyl group and phenyl group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, and a cyano group. Moreover, as said alkanediyl group, the same thing as the said alkanediyl group is mentioned, Moreover, as a substituent, a hydroxyl group, a cyano group, a nitro group, etc. are mentioned.

As a representative example of the cation represented by said formula (9-1) or (9-2), the cation represented by the following formula is mentioned, for example.

The phthalocyanine-based chromophore is preferably represented by the following formula (10).

CuPC-T (10)

[In the formula (10), CuPC represents a copper phthalocyanine residue; T represents a group represented by the following formula (10a) or (10b). ]

[In formulas (10a) and (10b), R ⁹⁸ , R ⁹⁹ , R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms or a phenyl group; p independently represent an integer of 2 to 8; m has the same meaning as above. ]

As a representative example of the cation represented by said formula (10), the cation represented by the following formula is mentioned, for example.

As the xanthene-based chromophore, a substance represented by the following formula (11) is preferable.

[In formula (11), R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ independently represent a hydrogen atom, -R ¹¹³ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Wherein, the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by a halogen atom, -R ¹¹³ , -OH, -OR ¹¹³ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ¹¹³ , -SO ₃ R ¹¹³ , -SO ₂ NHR ¹¹⁴ or -SO ₂ NR ¹¹⁴ R ¹¹⁵ are substituted.

R ¹¹⁰ and R ¹¹¹ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ¹¹² represents -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ¹¹³ , -SO ₃ R ¹¹³ , -SO ₂ NHR ¹¹⁴ or -SO ₂ NR ¹¹⁴ R ¹¹⁵ .

r represents an integer of 0 to 5, and when r is an integer of 2 or more, a plurality of R ¹¹² may be the same or different.

R ¹¹³ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. Wherein, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, and the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom, a carbonyl group or -NR ¹¹³ -.

R ¹¹⁴ and R ¹¹⁵ independently represent a chained alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or -Z, or a combination of R ¹¹⁴ and R ¹¹⁵ with 1 carbon atoms ~10 heterocyclyl. Wherein, the hydrogen atom contained in the alkyl group and cycloalkyl group can be substituted by hydroxyl, halogen atom, -Z, -CH=CH ₂ or -CH=CHR ¹¹³ , and the methylene contained in the alkyl group and cycloalkyl group The group may be substituted by an oxygen atom, carbonyl or -NR ¹¹³ -, and the hydrogen atom contained in the heterocyclic group may be substituted by -R ¹¹³ , -OH or -Z.

M represents a sodium atom or a potassium atom.

Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. Wherein, the hydrogen atoms contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted by -OH, R ¹¹³ , -OR ¹¹³ , -NO ₂ , -CH=CH ₂ , -CH=CHR ¹¹³ or halogen atoms. ]

The saturated hydrocarbon group in R ¹¹³ may be linear, branched, or cyclic as long as it has 1 to 10 carbon atoms, and may have a crosslinked structure. Specifically, in addition to the same alkyl group as ^R in the above formula (2), nonyl, decyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecanyl . Examples of the group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group.

唑基、异

唑基、噻唑基、异噻唑基、咪唑基、吡唑基、嘧啶基等。As the heterocyclic group having 1 to 10 carbon atoms formed by combining R ¹¹⁴ and R ¹¹⁵ with each other, the same groups as the heterocyclic group in the above-mentioned characteristic group (r5) can be mentioned. In addition, as the carbon atom number in Z 5 to 10 aromatic heterocyclic groups include furyl, thienyl, pyridyl, pyrrolyl,

Azolyl, iso

Azolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrimidinyl, etc.

Examples of the aromatic hydrocarbon group in R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ and Z include phenyl, naphthyl and the like.

Examples of -SO ₃ R ¹¹³ in R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹² include methylsulfonyl, ethylsulfonyl, hexylsulfonyl, and decanesulfonyl. In addition, examples of -CO ₂ R ¹¹³ include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, cyclohexyloxycarbonyl, and methoxypropyloxycarbonyl. wait. In addition, R ¹¹⁴ and R ¹¹⁵ in -SO ₂ NHR ¹¹⁴ and -SO ₂ NR ¹¹⁴ R ¹¹⁵ are preferably branched chain alkyl groups having 6 to 8 carbon atoms, alicyclic hydrocarbon groups having 5 to 7 carbon atoms, Allyl group, aralkyl group having 8 to 10 carbon atoms, hydroxy-containing alkyl group having 2-8 carbon atoms, alkoxy-containing alkyl group having 2-8 carbon atoms, and aryl group.

Specific examples of the cation represented by formula (11) include cations represented by the following formula.

Examples of other cationic chromophores include cations represented by the following formulas.

This colorant can be produced by a known method, for example, the method similar to the Example of Unexamined-Japanese-Patent No. 2003-206415 and JP-A-2007-503477 is mentioned. The coloring agent thus obtained is soluble in various organic solvents represented by ethyl lactate, and has excellent heat resistance.

coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention will be described.

-(A) Colorant-

The coloring composition of this invention contains this coloring agent as (A) coloring agent. This coloring agent can be used individually or in mixture of 2 or more types.

This coloring agent dissolves in an organic solvent to exhibit blue to red coloring, so this coloring agent can be used alone or appropriately mixed with other coloring agents, so that it can be used for coloring such as forming blue pixels, red pixels, and black colored layers. combination.

As a colorant other than this colorant, a color and a material can be selected suitably according to a use. Specifically, as a colorant other than this colorant, any of pigments, dyes, and natural pigments can be used, but since the colored layer constituting the color filter is required to have high color purity, brightness, contrast, and light-shielding properties etc., so the use of pigments and/or dyes is preferred.

The above-mentioned pigments may be any of organic pigments and inorganic pigments, and examples of organic pigments include compounds classified by pigments in the Color Index (issued by C.I.: The Society of Dyers and Colourists, Inc.). Specifically, organic pigments having the following color index (C.I.) names are exemplified.

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. C.I. Pigment Yellow 180, C.I. Pigment Yellow 211;

C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. C.I. Pigment Orange 49, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 68, C.I. Pigment Orange 70, C.I. Pigment Orange 71, C.I. Pigment Orange 72, C.I. Pigment Orange 73, C.I. Pigment Orange 74;

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red 264, C.I. Pigment Red 272;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38;

C.I. Pigment Blue 1, C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 60, C.I. Pigment Blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58;

C.I. Pigment Brown 23, C.I. Pigment Brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

In addition, examples of the above-mentioned inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, chrome yellow, zinc yellow, red iron (red iron oxide (III)), cadmium red, ultramarine blue, and Prussian blue. , chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc.

In the present invention, the pigment may be purified and used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. In addition, the pigment can be used after modifying the particle surface with a resin as desired. Examples of the resin for modifying the surface of pigment particles include vehicle resins described in JP-A-2001-108817 and various resins for dispersing pigments that are commercially available. As the resin coating method on the surface of carbon black, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, etc. can be used, for example. In addition, the organic pigment is preferably used by making primary particles finer by a so-called salt grinding method. As the salt grinding method, for example, the method disclosed in JP-A-08-179111 can be used.

Moreover, as said dye, it can select suitably from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, etc., For example, the dye which has the following color index (C.I.) name is mentioned.

C.I. Solvent Yellow 4, C.I. Solvent Yellow 14, C.I. Solvent Yellow 15, C.I. Solvent Yellow 24, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 94, C.I. Solvent Yellow 98, C.I. Solvent Yellow 162, C.I. Solvent Yellow 179;

C.I. Solvent Red 45, C.I. Solvent Red 49,

C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent Orange 56;

C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent Blue 67;

C.I. Acid Yellow 17, C.I. Acid Yellow 29, C.I. Acid Yellow 40, C.I. Acid Yellow 76;

C.I. Acid Red 91, C.I. Acid Red 92, C.I. Acid Red 97, C.I. Acid Red 114, C.I. Acid Red 138, C.I. Acid Red 151;

C.I. Acid Orange 51, C.I. Acid Orange 63;

C.I. Acid Blue 80, C.I. Acid Blue 83, C.I. Acid Blue 90;

C.I. Acid Green 9, C.I. Acid Green 16, C.I. Acid Green 25, C.I. Acid Green 27.

In the present invention, other colorants may be used alone or in combination of two or more.

From the point of view of forming a pixel with high brightness and excellent color purity or a black matrix with excellent light-shielding properties, the content of the (A) colorant in the solid content of the coloring composition is usually 5 to 70% by mass, preferably 5 to 70% by mass. 5 to 60% by mass. The solid content mentioned here refers to components other than the solvent mentioned later.

When a pigment is used as another colorant in the present invention, it can be used together with a dispersant and a dispersing aid as necessary. As the above-mentioned dispersant, suitable dispersants such as cationic, anionic and nonionic can be used, for example, polymer dispersants are preferred. Specifically, polyurethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, polyethylene glycol diester-based dispersants, Sorbitan fatty acid ester-based dispersants, polyester-based dispersants, acrylic-based dispersants, etc.

Such dispersants can be obtained through commercial channels. For example, as acrylic dispersants, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (manufactured by BYK CHEMIE Co., Ltd. above) can be cited. As a dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (manufactured by BYK CHEMIE) and Solsperse 76500 (manufactured by LUBRIZOL Co., Ltd.) can be mentioned. Examples of imine-based dispersants include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and examples of polyester-based dispersants include Adisper PB821, Adisper PB822, Adisper PB880, and Adisper PB881 (manufactured by Ajinomoto Fine Chemicals Co., Ltd.).

In addition, examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. In addition, the content of a dispersing agent and a dispersing aid can be determined suitably within the range which does not interfere with the object of this invention.

-(B) Binder resin-

Although it does not specifically limit as binder resin in the coloring composition of this invention, Resin which has an acidic functional group, such as a carboxyl group and a phenolic hydroxyl group, is preferable. Among them, polymers having carboxyl groups (hereinafter referred to as "carboxyl group-containing polymers") are preferable, for example, ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "unsaturated monomers (b1 )") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(meth)acryloyloxyethyl]ester, ω-carboxypoly Caprolactone mono(meth)acrylate, p-vinylbenzoic acid, etc.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

Moreover, as said unsaturated monomer (b2), for example,

N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate , Benzyl (meth)acrylate, polyethylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polyethylene glycol Alcohol (polymerization degree 2-10) mono(meth)acrylate, polypropylene glycol (polymerization degree 2-10) mono(meth)acrylate, (meth)cyclohexyl acrylate, (meth)isobornyl acrylate , tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, dihydrobiscyclopentadienyl (meth)acrylate (dicyclopentenyl(meth)acrylate), glycerin mono( Meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-cyclo Oxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethane (meth)acrylates such as oxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl base)-3-ethyloxetane such as vinyl ether; polystyrene, polymethyl(meth)acrylate, poly(meth)acrylate n-butyl, polysiloxane such as Macromonomers with a single (meth)acryloyl group at the end of the molecular chain, etc.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 70% by mass, more preferably 10 to 60% by mass. quality%. By copolymerizing the unsaturated monomer (b1) within such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of copolymers of unsaturated monomers (b1) and unsaturated monomers (b2) include, for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10 -31308 communiqué, JP-A-10-300922, JP-11-174224, JP-11-258415, JP-2000-56118, JP-2002-296778, Copolymers disclosed in JP-A-2004-101728 and the like.

In addition, in the present invention, for example, as JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-09-325494, JP-A-11- As disclosed in JP-A-140144 and JP-A-2008-181095, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acryloyl group on a side chain can also be used as the binder resin.

The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. If the Mw is too small, there is a possibility that the remaining film rate of the obtained film will decrease, or the pattern shape, heat resistance, etc. will be damaged, or the electrical characteristics will be deteriorated. On the other hand, if it is too large, there will be a decrease in resolution, or There is a possibility that the pattern shape is damaged, or dry foreign matter is likely to be generated during application by the slit nozzle method.

In addition, the ratio (Mw/Mn) of the weight average molecular weight of the binder resin in the present invention to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5.0 , and more preferably 1.0 to 3.0.

The binder resin in the present invention can be produced by a known method, and can also be disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, pamphlet of International Publication No. 07/029871, etc. method to control its structure, Mw, Mw/Mn.

In the present invention, the binder resins may be used alone or in combination of two or more.

In this invention, content of binder resin is 10-1000 mass parts normally with respect to 100 mass parts of (A) colorants, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkaline developability may decrease, or the storage stability of the obtained coloring composition may decrease. It may be difficult to achieve the target color density.

-(C) Cross-linking agent-

In the present invention, the (C) crosslinking agent refers to a compound having two or more polymerizable groups. As a polymerizable group, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, N-alkoxymethylamino group etc. are mentioned, for example. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and it is particularly preferable to use a compound having two or more ( A meth)acryloyl compound and a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone-modified Polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethanes obtained by reacting hydroxyl-containing (meth)acrylates with polyfunctional isocyanates (meth)acrylate, the polyfunctional (meth)acrylate which has a carboxyl group obtained by reacting the (meth)acrylate which has a hydroxyl group, and an acid anhydride, etc.

Among them, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol; Aliphatic polyols of more than 3 yuan. Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate, glycerol dimethacrylate, etc. As said polyfunctional isocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. Examples of acid anhydrides include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic dianhydride, Tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

In addition, examples of the caprolactone-modified polyfunctional (meth)acrylate include compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. Examples of the above-mentioned alkylene oxide-modified polyfunctional (meth)acrylates include ethylene oxide and/or propylene oxide-modified di(meth)acrylates of bisphenol A, rings of isocyanuric acid, Tri(meth)acrylate modified with ethylene oxide and/or propylene oxide, ethylene oxide and/or propylene oxide modified tri(meth)acrylate of trimethylolpropane, ethylene oxide of pentaerythritol alkane and/or propylene oxide modified tri(meth)acrylates, ethylene oxide and/or propylene oxide modified tetra(meth)acrylates of pentaerythritol, ethylene oxide and/or rings of dipentaerythritol Propylene oxide-modified penta(meth)acrylate, ethylene oxide and/or propylene oxide-modified hexa(meth)acrylate of dipentaerythritol, and the like.

Moreover, as a compound which has the said 2 or more N-alkoxymethyl amino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure, etc. are mentioned, for example. It should be noted that the so-called melamine structure and benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as the basic skeleton, and also include melamine, benzoguanamine or their condensed concept of things. Specific examples of compounds having two or more N-alkoxymethylamino groups include N, N, N', N', N", N"-hexa(alkoxymethyl)melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycoluril, etc.

Among these polyfunctional monomers, polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, and caprolactone-modified polyfunctional (meth)acrylic acid esters are preferred. ) acrylates, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates with carboxyl groups, N, N, N', N', N", N"-hexa(alkoxy Methyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. In view of the high strength of the colored layer, the excellent surface smoothness of the colored layer, and the fact that it is difficult to generate smudges (ground stains) and film residues on the substrate of the unexposed part and the light-shielding layer, it is necessary to use more than 3 yuan of fat Among the polyfunctional (meth)acrylates obtained by reacting polyhydroxyl compounds and (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among polyfunctional (meth)acrylates having a carboxyl group, compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride and compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are particularly preferable.

In this invention, (C) crosslinking agent can be used individually or in mixture of 2 or more types.

The content of the (C) crosslinking agent in the present invention is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, relative to 100 parts by mass of the (A) colorant. At this time, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, when alkali developability is imparted to the coloring composition of the present invention, alkali developability may decrease, and floating may easily occur on the unexposed portion on the substrate or on the light-shielding layer. fouling, film residue, etc.

-(D) Photopolymerization initiator-

The coloring composition of this invention can contain (D) photoinitiator. Thereby, radiation sensitivity can be imparted to a coloring composition. The (D) photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the above-mentioned (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet rays, deep ultraviolet rays, electron beams, and X-rays.

盐系化合物、苯偶姻系化合物、二苯甲酮系化合物、α-二酮系化合物、多环醌系化合物、重氮系化合物、酰亚胺磺酸酯系化合物、盐系化合物等。Examples of such photopolymerization initiators include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyl oxime-based compounds,

Salt-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polycyclic quinone-based compounds, diazo-based compounds, imidesulfonate-based compounds, Salt compounds, etc.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and O-acyl oxime-based compounds.

Among the preferred photopolymerization initiators in the present invention, specific examples of thioxanthone-based compounds include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone Xanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diiso Propylthioxanthone, etc.

In addition, specific examples of the aforementioned acetophenone-based compounds include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl -2-Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholin Linylphenyl) butan-1-one, etc.

In addition, specific examples of the above-mentioned biimidazole-based compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4 , 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

唑等硫醇系供氢体，4，4’-双(二甲氨基)二苯甲酮、4，4’-双(二乙氨基)二苯甲酮等胺系供氢体。本发明中，供氢体可以单独使用或将两种以上混合使用，从可以进一步改善感光度的观点考虑，优选将一种以上的硫醇系供氢体与一种以上的胺系供氢体组合使用。In addition, when using a biimidazole type compound as a photoinitiator, it is preferable to use a hydrogen donor together from a viewpoint which can improve sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. As the hydrogen donor, for example, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole,

Thiol-based hydrogen donors such as azoles, and amine-based hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. From the viewpoint of further improving the sensitivity, it is preferable to combine one or more thiol-based hydrogen donors with one or more amine-based hydrogen donors. Use in combination.

In addition, specific examples of the above-mentioned triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, oxazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethene Base]-4,6-bis(trichloromethyl)-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl) base)-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxy Phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-( Triazine compounds having a halomethyl group, such as 4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

In addition, specific examples of O-acyl oxime compounds include: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), ethyl Ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl Base-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl Base-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1 -(O-acetyl oxime) etc.

In the present invention, when photopolymerization initiators other than biimidazole-based compounds such as acetophenone-based compounds are used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminophenethyl Ketone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene) Cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

In this invention, it is preferable that content of a photoinitiator is 0.01-120 mass parts with respect to 100 mass parts of (C) crosslinking agents, and it is especially preferable that it is 1-100 mass parts. At this time, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if it is too large, the formed colored layer tends to be easily peeled off from the substrate during development.

-(E)Solvent-

The coloring composition of the present invention contains the above-mentioned components (A) to (C) and other components optionally added, and is usually mixed with a solvent to prepare a liquid composition.

As said solvent, if it disperses or dissolves (A)-(C) component and other components which comprise a coloring composition, does not react with these components, and has moderate volatility, it can select and use suitably.

Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propylene Ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Alcohol monoalkyl ethers;

Lactate alkyl esters such as methyl lactate and ethyl lactate;

Methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol and other (cyclo)alkyl alcohols;

Ketone alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Diethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. (poly)alkylene glycol monoalkyl ether acetate kind;

Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers;

Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones;

Propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate and other diacetates;

Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxypropionate Alkoxy carboxylates such as -3-methoxybutyl propionate;

Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate , isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters kind;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. Diethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3- Butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl acetate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate , isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, etc.

In the present invention, solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but from the viewpoint of the coatability and stability of the obtained coloring composition, it is preferable that the total concentration of the components of the coloring composition other than the solvent is 5 to 50% by mass, especially Preferably it is an amount of 10 to 40% by mass.

-additive-

The coloring composition of the present invention may contain various additives as necessary.

Examples of additives include: fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-cyclo Oxypropoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Adhesion promoters such as trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis(4-methyl-6-tert Butylphenol), 2,6-di-tert-butylphenol and other antioxidants; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxy UV absorbers such as benzophenones; anti-flocculants such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino -1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and other residue improvers ;Mono[2-(meth)acryloyloxyethyl]succinate, mono[2-(meth)acryloyloxyethyl]phthalate, ω-carboxypolycaprolactone mono(methyl ) developability improvers such as acrylates; siloxane oligomers having reactive functional groups disclosed in JP-A-2008-242078 and the like.

The coloring composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in JP-A-2008-58642, JP-A-2010-132874, and the like. When using both the colorant and the pigment as the colorant, as shown in Japanese Patent Application Laid-Open No. 2010-132874, the following method can be adopted: After the dye solution containing the colorant is passed through the first filter, the filter that has passed through the second The dye solution in the first filter is mixed with a separately prepared pigment dispersion or the like, and the resulting coloring composition is passed through the second filter to prepare it. In addition, the method of dissolving the dye containing this coloring agent, the above-mentioned (B) to (C) components, and if necessary, the above-mentioned (D) component and additive components in the (E) solvent, and dissolving the obtained solution After passing through the first filter, the solution that passed through the first filter is mixed with a separately prepared pigment dispersion liquid, and the obtained coloring composition is passed through a second filter to prepare it. In addition, the following method may also be adopted: after the dye solution containing the coloring agent is passed through the first filter, the dye solution passed through the first filter is mixed with the above-mentioned (B)-(C) components, and the above-mentioned ( D) to (E) components and additive components are mixed and dissolved, the obtained solution is passed through a second filter, and the solution passed through the second filter is further mixed with a separately prepared pigment dispersion liquid, and the obtained coloring composition is passed through A 3rd filter is thus prepared.

Color filter and manufacturing method thereof

The color filter of the present invention includes a colored layer containing the present coloring agent.

As a method of manufacturing a color filter, the following methods are mentioned first. First, a light-shielding layer (black matrix) is formed on the surface of the substrate as necessary so as to divide portions where pixels are formed. Next, after applying a liquid composition of, for example, a blue radiation-sensitive composition containing the present coloring agent on the substrate, prebaking is performed to evaporate the solvent to form a coating film. Next, after exposing this coating film through a photomask, it develops using an alkaline developing solution, and dissolves and removes the unexposed part of a coating film. Thereafter, a pixel array in which blue pixel patterns are arranged in a predetermined sequence is formed by post-baking.

Next, using each colored radiation-sensitive composition of green or red, the coating, pre-baking, exposure, development, and post-baking of each colored radiation-sensitive composition were carried out in the same manner as above, and sequentially applied on the same substrate. A green pixel array and a red pixel array are formed. In this way, a color filter in which a pixel array of three primary colors of red, green, and blue is arranged on a substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above order.

In addition, the black matrix can be formed by patterning a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, and it is also possible to use a colored radiation-sensitive composition in which a black colorant is dispersed, and The above-described pixel formation is performed in the same manner. The coloring composition of the present invention can also be favorably used for the formation of the black matrix.

As a board|substrate used when forming a color filter, glass, silicon, polycarbonate, polyester, aramid, polyamide-imide, polyimide etc. are mentioned, for example.

In addition, these substrates may be subjected to appropriate pretreatments such as reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, and vacuum deposition, as necessary.

When coating the colored radiation-sensitive composition on the substrate, suitable coating methods such as spray coating, roll coating, spin coating (spin coating), slot die coating, and bar coating can be used. method, particularly preferably spin coating method and slot die coating method.

Prebaking is usually performed by combining drying under reduced pressure and drying under heat. Drying under reduced pressure is usually carried out to 50-200Pa. In addition, the conditions for drying by heating are usually about 70 to 110° C. for 1 to 10 minutes.

The coating thickness is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm in terms of film thickness after drying.

As a light source of radiation used when forming pixels and/or black matrices, for example, light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, argon lamps, etc. Laser light sources such as ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers are preferred, but radiation with a wavelength in the range of 190 to 450 nm is preferred.

Generally, the exposure dose of radiation is preferably 10 to 10000 J/m ² .

In addition, as the above-mentioned alkaline developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo[5.4.0]-7-undeca Aqueous solutions of carbene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc.

Water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added in an appropriate amount to the above-mentioned alkaline developer. In addition, washing with water is usually performed after alkali image development.

As a developing treatment method, a shower developing method, a spray developing method, a dip developing method, a immersion (immersion) developing method, etc. are applicable. The image development conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually 120-280°C for 10-60 minutes. From the viewpoint of the heat resistance of the colorant, the post-baking temperature is preferably 240°C or lower, particularly preferably 230°C or lower.

The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

In addition, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. In this method, first, partition walls having a light-shielding function are formed on the surface of the substrate. Next, a liquid composition such as a blue coloring composition containing the present coloring agent is ejected from the formed partition wall by an inkjet device, and prebaking is performed to evaporate the solvent. Next, after exposing this coating film as needed, post-baking is performed to harden it, and a blue pixel is formed.

Next, using each coloring composition of green or red, a green pixel pattern and a red pixel pattern were sequentially formed on the same substrate in the same manner as above. Thus, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above order.

It should be noted that the above-mentioned barrier ribs not only perform a light-shielding function, but also perform a function of preventing color mixing of the coloring compositions of various colors discharged into the divided regions, so the film thickness is thicker than that of the black matrix used in the above-mentioned first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate used for forming the color filter, the light source of radiation, the methods and conditions of the pre-baking and post-baking are the same as those of the above-mentioned first method. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the height of the partition wall.

On the pixel pattern obtained in this way, after forming a protective film as needed, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to make a color filter. The spacer is usually formed using a radiation-sensitive composition, and may be made into a light-shielding spacer (black spacer). At this time, using a colored radiation-sensitive composition in which a black colorant is dispersed, the colored composition of the present invention can also be favorably used to form the black spacer.

The color filter of the present invention thus obtained has extremely high brightness and color purity, and thus is extremely useful for color liquid crystal display devices, color image pickup tube devices, color sensors, organic EL display devices, electronic paper, and the like.

display element

The display element of this invention is provided with the color filter of this invention. As a display element, a color liquid crystal display element, an organic EL display element, electronic paper, etc. are mentioned.

The color liquid crystal display element provided with the color filter of this invention may be transmissive type or reflective type, and an appropriate structure can be employ|adopted. For example, the following structure can be adopted: a color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are oppositely arranged through a liquid crystal layer; A structure is employed in which a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed are opposed to each other via a liquid crystal layer. The latter structure can significantly increase the aperture ratio, and has the advantage that a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display device including the color filter of the present invention may include a backlight unit using white LEDs as light sources in addition to cold cathode fluorescent tubes (CCFL: Cold Cathode Fluorescent Lamp). Examples of white LEDs include white LEDs that combine a red LED, a green LED, and a blue LED to obtain white light through color mixing, and combinations that combine a blue LED, a red LED, and a green phosphor to obtain white light through color mixing. Combining blue LEDs, red light-emitting phosphors and green light-emitting phosphors to obtain white light through color mixing, white LEDs to obtain white light through color mixing of blue LEDs and YAG-based phosphors, combining blue LEDs, Combination of orange-emitting phosphors and green-emitting phosphors to obtain white light by color mixing, white LEDs that obtain white light by combining ultraviolet LEDs, red-emitting phosphors, green-emitting phosphors, and blue-emitting phosphors .

In the color liquid crystal display element equipped with the color filter of the present invention, TN (Twisted Nematic, twisted nematic) type, STN (Super Twisted Nematic, super twisted nematic) type, IPS (In-Planes Switching, in-plane switching) can be applied. Switching) type, VA (Vertical Alignment, vertical alignment) type, OCB (Optically Compensated Birefringence, optically compensated bending alignment) type and other appropriate liquid crystal modes.

Moreover, the organic electroluminescence display element provided with the color filter of this invention can employ|adopt a suitable structure, for example, the structure disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned.

Moreover, the electronic paper provided with the color filter of this invention can employ|adopt a suitable structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

[Example]

Hereinafter, an Example is given and the embodiment of this invention is demonstrated more concretely. However, the present invention is not limited to the following Examples.

<Synthesis and evaluation of this colorant>

1. Synthesis of this colorant

Example 1

1.4 g (2.72 mmol) of CI basic blue 7, 0.384 g (1.36 mmol) of dipotassium isophthalate (manufactured by Wako Pure Chemical Industries, Ltd.), 20 ml of chloroform, and 10 ml of of water and stirred at room temperature for 7 hours. After separating and removing the water layer, the organic layer was washed twice with water, concentrated under reduced pressure, and the obtained solid was dried under reduced pressure to obtain 1.36 g of a blue-black solid (84.0% yield). Let this be compound A. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of Compound A is shown below, and it was confirmed that it was the target compound.

¹ H-NMR: δ9.05(brs, 1H), 8.73(s, 1H), 8.70(d, 1H), 8.01(d, 1H), 7.01-7.45(m, 9H), 6.67(d, 4H) , 6.59(d, 1H), 3.65(q, 2H), 3.50(q, 8H), 2.42(brs, 1H), 1.41(t, 3H), 1.24(t, 12H)

Example 2

In Example 1, instead of dipotassium m-benzenedisulfonate, 3,3'-dithiobis(1-propanesulfonate) disodium (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and the procedure was the same as in Example 1. The colorant was synthesized, and it was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement. Let this be compound B. The ¹ H-NMR spectrum of Compound B is shown below.

¹ H-NMR: δ8.81(brs, 1H), 8.61(d, 1H), 7.09-7.56(m, 7H), 6.69(d, 4H), 6.62(d, 1H), 3.69(q, 2H) , 3.52(q, 8H), 2.97(t, 4H), 2.81(t, 4H), 2.24(q, 4H), 1.42(t, 3H), 1.24(t, 12H)

Example 3

In Example 1, instead of CI Basic Blue 7, CI Basic Blue 11 (triarylmethane dye represented by the following formula) was used, and a colorant was synthesized in the same manner as in Example 1, and ¹ H-NMR ( Solvent: deuterated chloroform) measurement, confirmed to be the target compound.

Example 4

In Example 1, 1,1,2,2,3,3-hexafluoropropane-1,3-dilithium disulfonate (manufactured by Mitsubishi Materials Co., Ltd.) was used instead of dipotassium isobenzenedisulfonate. Other than that, the colorant was synthesized in the same manner as in Example 1, and it was confirmed that it was the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement. Let this be Compound C. The ¹ H-NMR spectrum of Compound C is shown below.

¹ H-NMR: 68.18 (d, 2H), 7.89 (brs, 4H), 7.15-7.51 (m, 16H), 6.90 (d, 8H), 6.79 (d, 2H), 3.62 (q, 16H), 3.56 (q, 4H), 1.43(t, 6H), 1.29(t, 24H)

Example 5

In Example 1, instead of CI Basic Blue 7, CI Basic Violet 16 (methine dye represented by the following formula) was used, and a colorant was synthesized in the same manner as in Example 1, and ¹ H-NMR ( Solvent: deuterated chloroform) measurement, confirmed to be the target compound.

Example 6

In Example 1, instead of ^CI Basic Blue 7, CI Basic Blue 41 (an azo-based dye represented by the following formula) was used. : deuterated chloroform) measurement, confirmed to be the target compound.

Example 7

In Example 1, instead of CI Basic Blue 7, CI Basic Blue 3 (a quinone imine dye represented by the following formula) was used, and a colorant was synthesized in the same manner as in Example 1, and ¹ H-NMR ( Solvent: deuterated chloroform) measurement, confirmed to be the target compound.

Example 8

In Example 1, instead of CI Basic Blue 7, CI Basic Blue 22 (an anthraquinone-based dye represented by the following formula) was used, and a colorant was synthesized in the same manner as in Example ¹ . : deuterated chloroform) measurement, confirmed to be the target compound.

Example 9

In Example 1, instead of CI Basic Blue 7, CI Basic Red 1 (xanthene-based dye represented by the following formula) was used, and 1, 1, 2, 2, 3, 3 were used instead of dipotassium isophthalate. - Hexafluoropropane-1,3-dilithium disulfonate. A colorant was synthesized in the same manner as in Example 1 except that it was confirmed to be the target compound by ¹ H-NMR (solvent: deuterochloroform) measurement. Let this be compound D.

Example 10

In Example 1, CI Basic Yellow 21 (methine dye represented by the following formula) was used instead of CI Basic Blue 7, and 1, 1, 2, 2, 3 were used instead of dipotassium isophthalic acid, A colorant was synthesized in the same manner as in Example 1 except that 3-hexafluoropropane-1,3-disulfonic acid dilithium salt was confirmed to be the target compound by ¹ H-NMR (solvent: deuterochloroform) measurement. Let this be Compound E.

Comparative Synthesis Example 1

In Example 1, instead of dipotassium m-benzenedisulfonate, sodium p-toluenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used. A colorant was synthesized in the same manner as in Example 1, and ¹ H-NMR (solvent: deuterated chloroform) and confirmed that it was the target compound (p-toluenesulfonate of the above-mentioned compound b). This was designated as compound F.

Comparative Synthesis Example 2

In Example 1, instead of dipotassium m-benzenedisulfonate, hydrated bathophenanthroline disulfonate disodium (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and a colorant was synthesized in the same manner as in Example 1, and after ¹ H -NMR (solvent: deuterated chloroform) measurement confirmed that it was a compound represented by the following formula. This was designated as compound G.

2. Evaluation of this colorant

Compound A obtained in Example 1 was dissolved in ethyl lactate at 10% by mass or more, and its solution turned blue. All the coloring agents obtained in Examples 2 to 10 were dissolved in ethyl lactate at 10% by mass or more.

In addition, for the coloring agents obtained in Examples 1 to 10, the temperature at which the mass decreased by 5% by thermogravimetric-differential thermal simultaneous measurement analysis was 230° C. or higher. On the other hand, C.I. Basic Blue 7 and C.I. Basic Blue 11 were all less than 200° C. in terms of the 5% mass reduction temperature analyzed by thermogravimetric-differential calorimetric simultaneous measurement.

<Preparation of pigment dispersion>

Preparation Example 1

Using 15 parts by mass of C.I. Pigment Blue 15:6 as a colorant, 12.5 parts by mass (solid content concentration = 40 mass%) of BYK-LPN21116 (manufactured by BYK Chemie (BYK)) as a dispersant, and 72.5 parts by mass of propylene glycol mono Methyl ether acetate was used as a solvent and treated with a bead mill to prepare a pigment dispersion (A-1).

Preparation example 2

A pigment dispersion (A-2) was prepared in the same manner as in Preparation Example 1 except that C.I. Pigment Violet 23 was used as a colorant instead of C.I. Pigment Blue 15:6.

Preparation example 3

A pigment dispersion liquid (A-3) was prepared in the same manner as in Preparation Example 1 except that C.I. Pigment Red 254 was used as a colorant instead of C.I. Pigment Blue 15:6.

Preparation Example 4

Pigment dispersion (A-4) was prepared in the same manner as in Preparation Example 1 except that C.I. Pigment Green 58 was used as a colorant instead of C.I. Pigment Blue 15:6.

Preparation Example 5

A pigment dispersion liquid (A-5) was prepared in the same manner as in Preparation Example 1 except that C.I. Pigment Red 177 was used as a colorant instead of C.I. Pigment Blue 15:6.

Preparation Example 6

A pigment dispersion liquid (A-6) was prepared in the same manner as in Preparation Example 1 except that C.I. Pigment Yellow 150 was used as a colorant instead of C.I. Pigment Blue 15:6.

<Preparation of dye solution>

Preparation Example 7

Dye solution A was prepared by mixing 5 parts by mass of compound A as a coloring agent and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation example 8

Dye solution B was prepared by mixing 5 parts by mass of compound B as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 9

Dye solution C was prepared by mixing 5 parts by mass of compound C as a colorant and 95 parts by mass of ethyl lactate as a solvent.

Preparation Example 10

Dye solution D was prepared by mixing 5 parts by mass of compound D as a colorant and 95 parts by mass of ethyl lactate as a solvent.

Preparation Example 11

Dye solution E was prepared by mixing 5 parts by mass of compound E as a colorant and 95 parts by mass of ethyl lactate as a solvent.

Preparation Example 12

5 parts by mass of compound F as a colorant and 95 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution F.

Preparation Example 13

5 parts by mass of compound G as a coloring agent and 95 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution G.

Preparation Example 14

Dye solution H was prepared by mixing 5 parts by mass of C.I. Basic Blue 7 as a colorant and 95 parts by mass of propylene glycol monomethyl ether as a solvent.

<Synthesis of binder resin>

100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. Heating to 80°C, at the same temperature, drop 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, methacrylic acid -15 parts by mass of 2-hydroxyethyl ester, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, succinic acid mono(2-acryloyloxyethyl) A mixed solution of 15 parts by mass of ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was kept at the temperature and polymerized for 2 hours. Then, the temperature of the reaction solution was raised to 100° C., and polymerization was further performed for 1 hour to obtain a binder resin solution (solid content concentration=33% by mass). The obtained binder resin had Mw=12200 and Mn=6500. This binder resin is referred to as "binder resin (B1)".

<Preparation and Evaluation of Coloring Composition>

Example 11

12.6 parts by mass of pigment dispersion liquid (A-1), 25.3 parts by mass of dye solution A, 16.1 parts by mass of binder resin (B1) solution as binder resin, M- 402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass and Sanwa Chemical Co., Ltd. MW-30 (N, N, N', N', N", N "-hexa(methoxy (methyl) melamine is the main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butane as photopolymerization initiator 2.2 parts by mass of 1-ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR1) having a solid content concentration of 20% by mass.

On the glass substrate, the coloring composition (CR1) was apply|coated using the spin coater, and it prebaked for 10 minutes with the hot plate of 80 degreeC, and formed the coating film. By changing the number of rotations of the spin coater and performing the same operation, three coating films having different film thicknesses were formed.

Next, after cooling these substrates to room temperature, each coating film was exposed to radiation of each wavelength including 365nm, 405nm and 436nm at an exposure dose of 2000J/ ^m2 using a high-pressure mercury lamp without a photomask. Then, shower development was performed for 90 seconds by spraying a developing solution comprising a 0.04% by mass potassium hydroxide aqueous solution at 23° C. on these substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm). Then, this substrate was washed with ultrapure water, air-dried, and post-baked for 30 minutes in a clean oven at 230° C. to form a cured film for evaluation.

For the obtained three cured films, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), with a C light source and a 2-degree field of view, the chromaticity coordinate values (x, y) and stimulus in the CIE colorimetric system were measured. value(Y). In addition, the film thickness of the obtained cured film was measured using Alpha-Step IQ manufactured by KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulus value (Y) and the film thickness of chromaticity coordinate value y=0.080 were calculated|required. Table 1 shows the evaluation results. The greater the stimulus value (Y), the higher the light transmittance (brightness), and the thinner the film thickness, the higher the tinting strength.

The substrate on which the cured film was formed was sandwiched between two polarizers, and the polarizer on the front side was rotated while irradiating with a fluorescent lamp (wavelength range 380 to 780 nm) from the back side, and passed through a luminance meter LS-100 (Minolta Co., Ltd.) Determine the maximum and minimum values of transmitted light intensity. Next, for each cured film, the value obtained by dividing the maximum value by the minimum value was used as a contrast ratio. From the measurement results, the contrast ratio at the chromaticity coordinate value y=0.080 was calculated. Table 1 shows the evaluation results.

Example 12

18.5 parts by mass of pigment dispersion liquid (A-1), 22.3 parts by mass of dye solution B, 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of Toagosei Co., Ltd. as a crosslinking agent Manufactured M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1 as a photopolymerization initiator - 2.2 parts by mass of ketone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR2) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR2) instead of coloring composition (CR1). Table 1 shows the evaluation results.

Example 13

18.5 parts by mass of pigment dispersion liquid (A-1), 21.4 parts by mass of dye solution C, 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of Toagosei Co., Ltd. as a crosslinking agent Manufactured M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1 as a photopolymerization initiator - 2.2 parts by mass of ketone and ethyl lactate as a solvent were mixed to prepare a coloring composition (CR3) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR3) instead of coloring composition (CR1). Table 1 shows the evaluation results.

Example 14

17.6 parts by mass of pigment dispersion liquid (A-3), 11.7 parts by mass of dye solution D, 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of Toagosei Co., Ltd. as a crosslinking agent Manufactured M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1 as a photopolymerization initiator - 2.2 parts by mass of a ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369) and ethyl lactate as a solvent were mixed to prepare a coloring composition (CR4) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR4) instead of coloring composition (CR1). But at this time, the chromaticity coordinate value y, stimulus value (Y), film thickness and contrast ratio of chromaticity coordinate value x=0.650 are calculated. Table 1 shows the evaluation results.

Example 15

11.7 parts by mass of pigment dispersion liquid (A-4), 46.9 parts by mass of dye solution E, 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of Toagosei Co., Ltd. as a crosslinking agent Manufactured M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1 as a photopolymerization initiator - 2.2 parts by mass of a ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369) and ethyl lactate as a solvent were mixed to prepare a coloring composition (CR5) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR5) instead of coloring composition (CR1). But at this time, the chromaticity coordinate value x, stimulus value (Y), film thickness and contrast ratio of chromaticity coordinate value y=0.590 are calculated. Table 1 shows the evaluation results.

Comparative example 1

18.1 parts by mass of the pigment dispersion (A-1), 4.5 parts by mass of the pigment dispersion (A-2), 16.1 parts by mass of the binder resin (B1) solution as the binder resin, and 5.5 parts by mass of the crosslinking agent Parts of Toagosei Co., Ltd. M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) as a photopolymerization initiator 2.2 parts by mass of ) butan-1-one and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR6) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR6) instead of coloring composition (CR1). Table 1 shows the evaluation results.

Comparative example 2

18.1 parts by mass of pigment dispersion liquid (A-1), 24.2 parts by mass of dye solution H, 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of Toagosei Co., Ltd. as a crosslinking agent Manufactured M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1 as a photopolymerization initiator - 2.2 parts by mass of ketone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR7) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR7) instead of coloring composition (CR1). Table 1 shows the evaluation results.

Comparative example 3

17.5 parts by mass of pigment dispersion liquid (A-1), 21.4 parts by mass of dye solution F, 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of Toagosei Co., Ltd. as a crosslinking agent Manufactured M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1 as a photopolymerization initiator - 2.2 parts by mass of ketone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR8) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR8) instead of coloring composition (CR1). Table 1 shows the evaluation results.

Comparative example 4

16.5 parts by mass of pigment dispersion liquid (A-1), 22.5 parts by mass of dye solution G, 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of Toagosei Co., Ltd. as a crosslinking agent Manufactured M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1 as a photopolymerization initiator - 2.2 parts by mass of ketone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR9) having a solid content concentration of 20% by mass.

It evaluated similarly to Example 11 except having used coloring composition (CR9) instead of coloring composition (CR1). Table 1 shows the evaluation results.

Comparative Example 5

15.6 parts by mass of pigment dispersion (A-3), 3.9 parts by mass of pigment dispersion (A-5), 16.1 parts by mass of binder resin (B1) solution as binder resin, 5.5 parts by mass of crosslinking agent Parts of Toagosei Co., Ltd. M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) as a photopolymerization initiator ) butane-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369) 2.2 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition with a solid content concentration of 20 mass % ( CR10).

It evaluated similarly to Example 14 except having used coloring composition (CR10) instead of coloring composition (CR4). Table 1 shows the evaluation results.

Comparative Example 6

11.7 parts by mass of the pigment dispersion (A-4), 7.8 parts by mass of the pigment dispersion (A-6), 16.1 parts by mass of the binder resin (B1) solution as the binder resin, and 5.5 parts by mass of the crosslinking agent Parts of Toagosei Co., Ltd. M-402 and 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) as a photopolymerization initiator ) butane-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369) 2.2 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition with a solid content concentration of 20 mass % ( CR11).

It evaluated similarly to Example 15 except having used coloring composition (CR11) instead of coloring composition (CR5). Table 1 shows the evaluation results.

【Table 1】

In Table 1, "B15:6" refers to C.I. Pigment Blue 15:6, "R254" refers to C.I. Pigment Red 254, "G58" refers to C.I. Pigment Green 58, "V23" refers to C.I. Pigment Violet 23, and "BB -7" refers to C.I. Basic Blue 7, "R177" refers to C.I. Pigment Red 177, and "Y150" refers to C.I. Pigment Yellow 150.

Claims (8)

1. an alkali stain has the negatively charged ion that following formula (1) is represented,

R(-SO ₃ ^-) _n (1)

In the formula (1), R representes that n representes 2～4 integer by the n valency organic group of 1～16 atomic building, and wherein said atom does not comprise Wasserstoffatoms.

2. alkali stain as claimed in claim 1; Wherein, said R replaces or does not have substituted non-aromatic hydrocarbon base, replacement or do not have substituted a plurality of non-aromatic hydrocarbon base to be contained heteroatomic divalent and link group, the replacement that group links or do not have substituted aryl radical, replacement or do not have substituted 2 aryl radicals and contained heteroatomic divalent and link group that group or divalent non-aromatic hydrocarbon base link, or replace or do not have a substituted heterocyclic radical.

3. alkali stain as claimed in claim 1, it is that triarylmethane is that tinting material, methyne are that tinting material, azo are that tinting material, diarylmethanes are that tinting material, quinonimine are that tinting material, anthraquinone are that tinting material, phthalocyanine are that tinting material or xanthene are tinting material.

4. alkali stain as claimed in claim 2, it is that triarylmethane is that tinting material, methyne are that tinting material, azo are that tinting material, diarylmethanes are that tinting material, quinonimine are that tinting material, anthraquinone are that tinting material, phthalocyanine are that tinting material or xanthene are tinting material.

5. coloured composition, it is to contain (A) tinting material, (B) resin glue and (C) coloured composition of linking agent,

Wherein, as (A) tinting material, contain each described alkali stain in the claim 1～4.

6. coloured composition as claimed in claim 5 wherein, further contains (D) Photoepolymerizationinitiater initiater.

7. a colour filter possesses the pigmented layer that contains each described alkali stain in the claim 1～4.

8. a display element possesses the described colour filter of claim 7.