KR20130040726A

KR20130040726A - Colorant, coloring composition, color filter and display device

Info

Publication number: KR20130040726A
Application number: KR1020120113309A
Authority: KR
Inventors: 에이지 요네다; 사토시 에바타; 히데유키 요시자와; 유카리 야마구치; 아츠시 이토; 야스노리 가와베
Original assignee: 제이에스알 가부시끼가이샤
Priority date: 2011-10-14
Filing date: 2012-10-12
Publication date: 2013-04-24
Also published as: TWI628240B; JP6028478B2; CN103048880A; CN103048880B; JP2013100463A; TW201321449A

Abstract

The present invention provides a coloring composition capable of forming a colored layer capable of achieving both good voltage retention, high contrast and high heat resistance when a dye is used as the colorant.
The solution of the present invention comprises the following components (A), (B) and (C):
(A) a colorant containing a dye represented by the following formula (1),
(B) binder resin, and
(C) crosslinking agent
It is a coloring composition characterized by containing.

[In Formula (1), X <^-> is an anion, a is an integer determined so that the said compound may be electrically neutral, m is an integer of 0-5, R <^1> -R <^4> is respectively independently C6-C10 R ⁵ is independently -SO ₃ ^- etc., R ⁶ is monovalent saturated hydrocarbon group etc., R ⁷ is monovalent hydrocarbon group etc., R ⁸ and R ⁹ are respectively Independently a monovalent saturated aliphatic hydrocarbon group or the like, R ¹⁰ is a monovalent hydrocarbon group or the like, R ¹¹ is a monovalent hydrocarbon group or the like, Q is a C6-C10 monovalent aromatic hydrocarbon group or the like, M is a sodium atom And the like. Provided that the compound meets the requirements of at least one of the following (i) to (vi):
(i) R ¹ to R ⁴ At least one aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ^7, and -SO ₂ NHSO ₂ R ¹¹ ; to be.
(ii) R ¹ to R ⁴ At least one of is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms.
(iii) at least one of R ¹ to R ⁴ is —R ⁶ or has at least one substituent selected from the group consisting of —R ⁶ , —OR ⁶ , —CO ₂ R ⁶ and —SO ₃ R ^6; Aromatic hydrocarbon group. However, the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.
(iv) at least one of m R ⁵ is -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ .
(v) at least one of m R ⁵ is —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms.
(vi) at least one of m available R ⁵ is —CO ₂ R ⁶ or —SO ₃ R ⁶ . Provided that the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms]

Description

Colorants, coloring compositions, color filters and display elements {COLORANT, COLORING COMPOSITION, COLOR FILTER AND DISPLAY DEVICE}

This invention relates to a coloring agent, a coloring composition, a color filter, and a display element, More specifically, in manufacture of the color filter used for a transmissive or reflective color liquid crystal display element, a solid-state image sensor, an organic EL display element, an electronic paper, etc. It relates to a colorant which is preferably used, a color composition containing the colorant, a color filter having a colored layer formed using the coloring composition, and a display element comprising the color filter.

In the production of a color filter using a colored radiation-sensitive composition, after coating and drying a pigment-dispersed colored radiation-sensitive composition on a substrate, the dried coating film is irradiated with a desired pattern shape (hereinafter referred to as "exposure"). The method (patent documents 1-2) of obtaining the pixel of each color is known by developing. Moreover, the method (patent document 3) which forms the black matrix using the photopolymerizable composition which disperse | distributed carbon black is also known. Moreover, the method (patent document 4) which obtains the pixel of each color by the inkjet system using the pigment dispersion type colored resin composition is also known.

In recent years, high contrast of a liquid crystal display element and high definition of a solid-state image sensor are strongly requested | required, and application of dye as a coloring agent is examined in order to implement these. For example, Patent Document 5 proposes the use of specific xanthene dyes.

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 6-35188 Japanese Patent Application Laid-Open No. 2000-310706 Japanese Patent Publication No. 2010-254964

However, when the dye proposed in patent document 5 is used, there exists a problem that contrast of a pixel becomes low. On the other hand, when dye is used, many problems arise that the voltage retention and heat resistance of a color filter deteriorate. For this reason, the development of the coloring composition suitable for manufacture of the color filter which can make favorable voltage retention, high contrast, and high heat resistance compatible is calculated | required strongly.

Therefore, the subject of this invention is providing the coloring composition which can form the colored layer which can achieve favorable voltage retention, high contrast, and high heat resistance, when dye is used as a coloring agent, and the coloring agent applicable to the said coloring composition. Is to provide. Moreover, the subject of this invention is providing the color filter which comprises the colored layer formed from the said coloring composition, and the display element provided with the said color filter.

In view of such a situation, the present inventors earnestly researched and discovered that the said subject can be solved by using the dye which has a specific structure as a coloring agent, and came to complete this invention.

That is, the present invention provides the following components (A), (B) and (C):

(A) a colorant containing a dye represented by the following formula (1),

(B) binder resin, and

(C) crosslinking agent

It is to provide a coloring composition comprising a.

[In formula (1),

X ⁻ represents an anion;

a is an integer determined such that the compound is electrically neutral;

m represents the integer of 0-5. Provided that when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different;

R ¹ to R ⁴ are each independently a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atoms included in the aromatic hydrocarbon group are a halogen atom, -R ⁶ , -OH, -OR ⁶ , _{^{_{-SO 3 -, -SO 3 H,}}} -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NH 2, -SO 2 NHR 8, -SO 2 NR 8 R ⁹ , -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , which may be substituted;

R ⁵ are each independently a _{^{_{-SO 3 -, -SO 3 H,}}} -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8, -SO 2 NR 8 R ⁹ , —SO ₂ —ON═CR ⁷ R ¹⁰ , —SO ₂ NHNHR ⁷ , —SO ₂ SR ⁷ or —SO ₂ NHSO ₂ R ¹¹ ;

R ⁶ is a monovalent saturated hydrocarbon group (the hydrogen atom in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ -in the saturated hydrocarbon group is substituted with -O-, -CO-, or -NR ^7- ). May be);

R ⁷ represents a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-);

R ⁸ and R ⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group (the hydrogen atom contained in the saturated aliphatic hydrocarbon group may be substituted with —OH, a halogen atom, —Q, —CH═CH ₂ or —CH═CHR ⁶⁾ . And -CH ₂ -included in the saturated aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -NH-, or -NR ^6- ;

R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group (the hydrogen atom included in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-) or- R ¹¹ is represented;

R ¹¹ represents a monovalent hydrocarbon group which may have a substituent;

Q is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms (The at least one hydrogen atom included in the aromatic hydrocarbon group and the heterocyclic group may be selected from -R ⁶ , -OR ^6, and -CH. Is substituted with at least one member selected from the group consisting of = CHR ⁶ , and the remaining hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group may be substituted with -OH, -NO ₂ , -CH = CH _2, or a halogen atom; Present);

M represents a sodium atom or a potassium atom.

Provided that the compound meets the requirements of one or more of the following (i) to (vi).

(i) R ¹ to R ⁴ At least one aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ^7, and -SO ₂ NHSO ₂ R ¹¹ ; to be.

(ii) R ¹ to R ⁴ At least one of is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms.

(iii) R ¹ to R ⁴ At least one of is -R ⁶ or an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -R ⁶ , -OR ⁶ , -CO ₂ R ⁶ and -SO ₃ R ⁶ . However, the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.

(iv) at least one of m R ⁵ is -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ .

(v) at least one of m R ⁵ is —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms.

(vi) at least one of m available R ⁵ is —CO ₂ R ⁶ or —SO ₃ R ⁶ . Provided that the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms]

The present invention also provides a color filter comprising a coloring layer formed using the coloring composition, and a display element comprising the color filter. Here, the " colored layer " means each color pixel, a black matrix, a black spacer, and the like used in the color filter.

Moreover, this invention provides the dye represented by the said General formula (1).

By using the coloring composition of this invention, the coloring layer excellent in voltage retention, contrast, and heat resistance can be formed. Therefore, the coloring composition of this invention can be used very suitably for manufacture of various color filters, including the color filter for display elements, the color filter for color separation of a solid-state image sensor, the color filter for organic electroluminescent display elements, and the color filter for electronic paper. have.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Coloring composition

Hereinafter, the structural component of the coloring composition of this invention is demonstrated.

- (A) Colorant -

The coloring composition of this invention contains the dye (henceforth "a dye (a1)") represented by the said General formula (1) as (A) coloring agent.

In general formula (1), X <^-> includes a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonic acid anion, a nitrogen anion, a methion anion, etc., for example.

R ¹ to R ⁴ and the carbon number of 6 to a monovalent aromatic hydrocarbon group of 10 at Q is preferably a monovalent aryl group having 6 to 10 carbon atoms and, more specifically, phenyl group, benzyl group, o- tolyl, m- tolyl A reel group, p-tolyl group, a naphthyl group, etc. are mentioned. Moreover, as a halogen atom which can be substituted by the said aromatic hydrocarbon group, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.

The monovalent saturated hydrocarbon group in R ⁶ may be either a saturated aliphatic hydrocarbon group or a saturated alicyclic hydrocarbon group. The saturated aliphatic hydrocarbon group may be in any form of linear and branched phases. The saturated aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, specifically, an alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group and iso Butyl, sec-butyl, tert-butyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, 1-methyldecyl, 2-methyldecyl, dodec Real group, 1-methyl undecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyl octyl group, hexadecyl group, octadecyl group, nonadecyl group, eico And an acid-1-yl group. -CH ₂ -included in the monovalent saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ^7- , and -CH ₂ -included in the monovalent saturated hydrocarbon group is substituted with -O-. Examples thereof include methoxypropyl group, ethoxypropyl group, methoxyhexyl group, ethoxypropyl group, 2-ethylhexyloxypropyl group and the like.

Moreover, as said saturated alicyclic hydrocarbon group, a C3-C30 saturated alicyclic hydrocarbon group is preferable, Specifically, a C3-C30 cycloalkyl group, a saturated condensed polycyclic hydrocarbon group, a saturated temporary exchange hydrocarbon group, a saturated spiro hydrocarbon group, etc. Can be mentioned. More specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecanyl group, decahydro-2-naphthyl group, tri Cyclo [5.2.1.0 ^2,6 ] decane-8-yl group, a pentacyclo pentadecanyl group, an isobornyl group, an adamantyl group, etc. are mentioned. Especially, a C3-C12 saturated alicyclic hydrocarbon group is preferable and a C3-C8 saturated alicyclic hydrocarbon group is more preferable.

In addition, the same thing as the above-mentioned is mentioned as a halogen atom which can be substituted by the said saturated hydrocarbon group.

As -CO ₂ R ⁶ , for example, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, isobutyloxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group , Cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyloxycarbonyl group, decanyloxycarbonyl group, tri Cyclodecarbonyloxycarbonyl group, methoxypropyloxycarbonyl group, ethoxypropyloxycarbonyl group, hexyloxypropyloxycarbonyl group, 2-ethylhexyloxypropyloxycarbonyl group, methoxyhexyloxycarbonyl group, undecylcarbonyl group, dodecylcarbonyl group, tetradecylcarbon Group, and the like t- dodecyl group, hexadecyl group, octadecyl group.

As —SO ₃ R ⁶ , for example, methanesulfonyl group, ethanesulfonyl group, hexanesulfonyl group, decansulfonyl group, undecylsulfonyl group, dodecylsulfonyl group, tetradecylsulfonyl group, t-dodecylsulfonyl group, hexa A decyl sulfonyl group, an octadecyl sulfonyl group, etc. are mentioned.

The monovalent hydrocarbon group in R ⁷ , R ¹⁰ and R ¹¹ may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. In addition, the aliphatic hydrocarbon group may be in any form of linear and branched phases. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be saturated hydrocarbon groups or unsaturated hydrocarbon groups. In addition, the position of the unsaturated bond of an unsaturated hydrocarbon group may be either in the molecular chain and the terminal of a molecular chain, and may have it in arbitrary positions. Moreover, in R <^7> , an alkoxy group, a phenoxy group, an alkylcarbonyl group, a benzoyl group etc. are mentioned as monovalent hydrocarbon group connected by -O- or -CO-.

As a substituent of the monovalent hydrocarbon group in R <^11> , a halogen atom, a C1-C20 alkyl group, a trifluoromethyl group, an amino group, a nitro group, etc. are mentioned, for example. The position and number of substituents are arbitrary, and when it has two or more substituents, the said substituents may be same or different. Moreover, the thing similar to the above-mentioned is mentioned as a specific example of the halogen atom which can be substituted by a hydrocarbon group, and a C1-C20 alkyl group.

As said aliphatic hydrocarbon group, a C1-C20 aliphatic hydrocarbon group is preferable, Specifically, a C1-C20 alkyl group, a C2-C16 alkenyl group, and a C2-C12 alkynyl group are mentioned. As a specific example of an alkyl group, the thing similar to the above-mentioned is mentioned. As the alkenyl group, for example, an ethenyl group, 1-propenyl group, 1-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-ethyl- 2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group, etc. are mentioned. Examples of the alkynyl group include an ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2-octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group, etc. are mentioned.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms, specifically, a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a cross-exchange hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene hydrocarbon group. And the like can be mentioned. As these specific examples, a dicyclopentenyl group, a tricyclopentenyl group, etc. are mentioned in addition to having been similar to the above-mentioned.

As said aromatic hydrocarbon group, a C6-C30 aromatic hydrocarbon group is preferable, and the thing similar to what was mentioned above is mentioned specifically ,.

Moreover, the thing similar to the above-mentioned is mentioned as a halogen atom which can be substituted by the said hydrocarbon group.

Especially, as R <^7> , an aliphatic hydrocarbon group and an aromatic hydrocarbon group are preferable, A C1-C20 alkyl group and a C6-C30 aromatic hydrocarbon group are more preferable, A C1-C15 alkyl group and a C6-C10 aromatic hydrocarbon group are preferable. More preferred. As such an aromatic hydrocarbon group, an aromatic hydrocarbon group linked by -O- or -CO- is also preferable.

Moreover, as R <^10> , an aliphatic hydrocarbon group is preferable, A C1-C10 alkyl group is more preferable, A C1-C4 alkyl group is more preferable, As R <^11> , an aromatic hydrocarbon group is preferable, A C6-C10 aryl group is preferable. More preferred.

The monovalent saturated aliphatic hydrocarbon group in R ⁸ and R ⁹ may be in any of linear and branched forms. As said saturated aliphatic hydrocarbon group, a C1-C24 saturated aliphatic hydrocarbon group is preferable, In addition to the alkyl group of C1-C20 in R <^6> mentioned above, a Hen- icosan-1-yl group and a docoic acid-1- A diary, a trichoic acid-1-yl group, a tetrakosan-1-yl group, etc. are mentioned. As a halogen atom which can be substituted by the said saturated aliphatic hydrocarbon group, the thing similar to the above-mentioned is mentioned.

-SO ₂ NHR ⁸ is methyl sulfamoyl group, ethyl sulfamoyl group, propyl sulfamoyl group, isopropyl sulfamoyl group, butyl sulfamoyl group, isobutyl sulfamoyl group, pentyl sulfamoyl group, isopentyl sulfamoyl group, neo Pentyl sulfamoyl group, hexyl sulfamoyl group, heptyl sulfamoyl group, octyl sulfamoyl group, 2-ethylhexyl sulfamoyl group, nonyl sulfamoyl group, decyl sulfamoyl group, undecyl sulfamoyl group, 1-methyldecyl group, 2 -Methyldecyl sulfamoyl group, dodecyl sulfamoyl group, 1-methyl undecyl sulfamoyl group, 1-ethyldecyl sulfamoyl group, tridecyl sulfamoyl group, tetradecyl sulfamoyl group, t-dodecyl sulfamoyl group, pentadecyl sulfone A pamoyl group, a 1-heptyl octyl sulfamoyl group, a hexadecyl sulfamoyl group, an octadecyl sulfamoyl group, a docosan-1-yl sulfamoyl group, etc. are mentioned.

Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms in Q include pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, piperidyl group, piperidino group, piperazinyl group and homopipera. Alicyclic heterocyclic groups such as a genyl group, a morpholinyl group, and a thiomorpholinyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a quinolyl group, an isoquinolyl group, a phthalazinyl group, a naphthyl group Dinyl group, quinoxalinyl group, thienyl group, furyl group, pyranyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, thiazolyl group, oxazolyl group, indolyl group, indazolyl group And aromatic heterocyclic groups such as benzoimidazolyl group and furinyl group. As a halogen atom which can be substituted by the said heterocyclic group, the thing similar to the above-mentioned is mentioned.

m is an integer of 0-5, Preferably it is 0-3, More preferably, it is 1 or 2.

M is a sodium atom or a potassium atom.

In addition, the dye (a1) is required to satisfy the requirements of at least one of the following (i) to (vi).

(i) at least one of R ¹ to R ⁴ is at least 1 selected from the group consisting of -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ^7, and -SO ₂ NHSO ₂ R ¹¹ ; It is an aromatic hydrocarbon group which has a substituent of a species.

(vi) at least one of m available R ⁵ is —CO ₂ R ⁶ or —SO ₃ R ⁶ . However, the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.

Furthermore, if the dye (a1) satisfies at least one of the requirements (i), (ii) and (iv) to (vi), then -R ⁶ , -OR ⁶ , -CO ₂ R ⁶ , 1-valent saturated hydrocarbon group represented by R ⁶ in the -SO ₃ R ^6, does not necessarily require that the number of carbon atoms is 11 or more.

Further, the dye (a1) the requirements (i) to (v) in the case satisfying one or more of, one represented by R ⁶ in the _{^{_{-CO 2 R 6, -SO 3 R}}} 6 of the requirements (vi) monovalent The saturated hydrocarbon group does not necessarily need to have 11 or more carbon atoms.

In this case, the monovalent saturated hydrocarbon group represented by R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

Further, the dye (a1) R ⁸ according to the requirements (i) and (iii) to (vi), if satisfying at least one of _{^{_{a, -SO 2 NHR 8, -SO 2}}} NR 8 R 9 in the requirement (ii) The monovalent saturated aliphatic hydrocarbon group represented by R ⁹ is not necessarily required to have 11 or more carbon atoms.

Further, the dye (a1) R ⁸ according to the requirements (i) to (iv) and (vi) when satisfying at least one of _{^{_{a, -SO 2 NHR 8, -SO 2}}} NR 8 R 9 in the requirement (v) The monovalent saturated aliphatic hydrocarbon group represented by R ⁹ is not necessarily required to have 11 or more carbon atoms.

In this case, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms.

In the formula (1), a is an integer such that the dye (a1) is determined to be electrically neutral, and the dye (a1) in which a is 0 is R ¹ to R ⁴ One of the -SO ₃ ^-, or an aromatic hydrocarbon group substituted by, or one of the two R ⁵ m in -SO ₃ ^- a. Specifically, it can represent with following General formula (1-1). On the other hand, when a is 1, the dye (a1) has a substituent other than -SO ₃ ^- as a substituent when at least one of R ¹ to R ⁴ is a C6-C10 monovalent aromatic hydrocarbon group having a substituent. and, R ⁵ is -SO ₃ ^- not. Specifically, it can represent with following General formula (1-2).

[In formula (1-1),

R ¹ to R ⁵ and m are R ¹ to R ^5, and m and copper in the chemical formula (1), respectively. Provided that R ¹ to R ⁴ One of the -SO ₃ ^-, or an aromatic hydrocarbon group substituted by, one or m any of R ⁵ in the -SO ₃ ^- a]

[In formula (1-2),

X ^-, R ¹ to R ⁵ and X are m in the above formula (1) respectively, ^- a, R ¹ to R ^5, and m and copper. However, R ¹ to R ^4, if one or more of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent, the aromatic hydrocarbon group as a substituent -SO ₃ ^-, and having a substituent other than, R ⁵ is -SO ₃ ^- Not]

Moreover, the compound represented by following General formula (2) is mentioned as a more preferable aspect.

[In formula (2),

R ^1a to R ^4a are each independently a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ^7, or -SO ₂ NHSO ₂ R ¹¹ ;

R ^5a are each independently -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ ;

R ¹¹ represents a monovalent hydrocarbon group which may have a substituent;

M represents a sodium atom or a potassium atom.

n represents the integer of 0-4. Provided that when n is an integer of 2 or more, a plurality of R ^5a may be the same or different;

(i) R ^1a to at least one of R ^4a is _{^{-SO 2 -ON = CR 7 R 10}} , -SO 2 NHNHR 7, -SO 2 SR 7 and -SO ₂ NHSO at least one selected from the group consisting of ₂ R ¹¹ It is an aromatic hydrocarbon group which has a substituent of a species.

(ii) At least one of R ^1a to R ^4a is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of —SO ₂ NHR ⁸ and —SO ₂ NR ⁸ R ⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms.

(iii) at least one of R ^1a to R ^4a is —R ⁶ or has at least one substituent selected from the group consisting of —R ⁶ , —OR ⁶ , —CO ₂ R ⁶ and —SO ₃ R ^6; Aromatic hydrocarbon group. However, the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms.

(iv) n it is the more than one of R ^5a where _{^{-SO 2 -ON = CR 7 R 10}} , -SO 2 NHNHR 7, -SO 2 SR 7 or -SO ₂ NHSO ₂ R ^11.

(v) at least one of the n R ^{5a 's} is -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms.

(vi) at least one of the n available R ^5a is —CO ₂ R ⁶ or —SO ₃ R ⁶ . Provided that the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms]

In Formula (2), the C6-C10 monovalent aromatic hydrocarbon group in R <^1a> -R <^4a> is ^synonymous with the C6-C10 monovalent aromatic hydrocarbon group in R <^1> -R <^4> mentioned above, and is a specific aspect Is as described above. In addition, specific embodiments of R ⁶ to R ¹¹ , Q, and M are also as described above.

Further, -SO ₃ ^- is preferably at the ortho position or the para position of the phenyl group, and more preferably at the ortho position.

Dye (a1) can be manufactured by an appropriate method, for example, the method similar to the Example of Unexamined-Japanese-Patent No. 2010-254964 is mentioned. The dye (a1) thus obtained is soluble in various organic solvents including ketones such as cyclohexanone and has excellent heat resistance.

In this invention, dye (a1) can be used individually or in mixture of 2 or more types.

The coloring composition of this invention can further contain another coloring agent (henceforth a "coloring agent (a2)") with a dye (a1) as a coloring agent. It does not specifically limit as a coloring agent (a2), A color and a material can be selected suitably according to a use.

As the other coloring agent (a2), any of pigments, dyes other than dyes (a1), and natural dyes can be used, but organic pigments and organic dyes are preferable in the sense of obtaining pixels with high brightness and color purity, and especially organic pigments desirable.

Examples of the organic pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists, Inc.). Among them, Japanese Patent Application Laid-Open No. 2001-081348 and Japanese Patent Publication No. 2010-026334, Japanese Patent Publication No. 2010-191304, Japanese Patent Publication No. 2010-237384, Japanese Patent Publication No. 2010-237569, Japanese Patent Publication No. 2011-006602, Japanese Patent Lake pigment, CI described in Unexamined-Japanese-Patent No. 2011-145346, etc. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211, C.I. Pigment Orange 38, C.I. Organic pigments other than lake pigments, such as pigment violet 23, are preferable. Among the lake pigments, triarylmethane-based lake pigments, xanthene-based lake pigments and azo-based lake pigments are preferable, and triarylmethane-based lake pigments and xanthene-based lake pigments are more preferable.

It is preferable to use the coloring composition of this invention for formation of a blue pixel. In this case, it is preferable that (A) coloring agent contains at least 1 sort (s) chosen from the group which consists of a blue pigment, a blue dye, a purple pigment, and a purple dye as another coloring agent with this coloring agent. In this case, the content ratio of the present colorant is preferably 0.1 to 80% by mass, more preferably 1 to 80% by mass, still more preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass of all the colorants. Do.

When using a pigment as a coloring agent (a2) in this invention, a pigment may be refine | purified by the recrystallization method, the reprecipitation method, the solvent washing method, the sublimation method, the vacuum heating method, or a combination thereof. In addition, a pigment can also be used, modifying the particle surface with resin as needed. As resin which modifies the particle surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or commercially available various pigment dispersion resin are mentioned, for example. As a resin coating method of the carbon black surface, it is described, for example in Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc. Method may be employed. In addition, the organic pigment is preferably used to refine the primary particles by so-called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. 08-179111 can be employ | adopted, for example.

When using a pigment as a coloring agent (a2) in this invention, you may further contain a well-known dispersing agent and a dispersal auxiliary agent. Known dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyesters. Examples of the dispersant and the acrylic dispersant include pigment derivatives and the like.

Such dispersants are commercially available, and are, for example, Disperbyk-2000, Dispervik-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, manufactured by BYK) as acrylic dispersants Dispervic -161, dispervic -162, dispervic -165, dispervic -167, dispervic -170, dispervic -182 (above, manufactured by BYK Corporation), and Solsper As a polyester dispersant, 76500 (Lubricazole Co., Ltd.) was used as a polyethyleneimine-based dispersant, and azisper PB821, Azisper PB822, Azisper PB880 and Azisper PB881 (above, Ajinomoto Fine Techno Co., Ltd. product) etc. are mentioned, respectively.

In addition, examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

In this invention, a coloring agent (a2) can be used individually or in mixture of 2 or more types.

(A) Since the content rate of a coloring agent forms a pixel with high brightness | luminance and excellent color purity, or a black matrix excellent in light-shielding property, it is 5-70 mass% in solid content of a coloring composition normally, Preferably it is 5-60 mass%. to be. Solid content is components other than the solvent mentioned later here.

(B) binder resin

Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer which has a carboxyl group (henceforth a "carboxyl group-containing polymer") is preferable, and is copolymerized different from the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth "unsaturated monomer (b1)"). And copolymers with possible ethylenically unsaturated monomers (hereinafter referred to as " unsaturated monomers (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate. and p-vinyl benzoic acid.

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 maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide;

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

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, polyethylene glycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) (Meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, propylene glycol Acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) Meth) acrylate, 3,4-epoxide (Meth) acrylic acid esters such as cyclocyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyl oxetane ;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Vinyl ethers such as;

And a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

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 50% by mass, more preferably 10 to 40% by mass. By copolymerizing an unsaturated monomer (b1) in such a range, the coloring composition excellent in alkali developability and storage stability can be obtained.

As a specific example of the copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined Japanese patent publication Japanese Patent Application Laid-Open No. 10-31308, Japanese Patent Publication No. 10-300922 Japanese Patent Publication No. 11-174224, Japanese Patent Publication No. 11-258415, Japanese Patent Publication No. 2000 And copolymers disclosed in JP-A-56118, JP-A-2004-101728, and the like.

Moreover, in this invention, for example, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent As disclosed in Japanese Patent Application Laid-Open No. 09-325494, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095 and the like, the side chain has a polymerizable unsaturated bond such as a (meth) acryloyl group. A carboxyl group-containing polymer can also be used as binder resin.

The binder resin in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably 3,000. To 50,000. If Mw is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be damaged, or the electrical characteristics may be deteriorated. There exists a possibility that a dry foreign material may generate easily at the time of application | coating by a nozzle system.

Moreover, ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) of binder resin in this invention becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0. In addition, Mn here means the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

Although the binder resin in this invention can be manufactured by a well-known method, it is disclosed, for example by Unexamined-Japanese-Patent No. 2003-222717, 2006-259680, international publication 07/029871, etc. The structure, Mw, and Mw / Mn can also be controlled by the method.

In this invention, binder resin can be used individually or in mixture of 2 or more types.

Content of binder resin in this invention is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. When the content of the binder resin is too small, for example, alkali developability may decrease or the storage stability of the resulting colored composition may decrease. On the other hand, when the content of the binder resin is too high, the concentration of the colorant decreases relatively. There is a fear that it is difficult to achieve the color density.

-(C) crosslinking agent-

In the present invention, the (C) crosslinking agent refers to a compound having two or more polymerizable groups. As a group which can superpose | polymerize, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxy methylamino group, etc. are mentioned, for example. In the present invention, as the crosslinking agent (C), a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate and a caprolactone-modified polyfunctional (meth) compound obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid. Polyfunctional urethane (meth) acrylate obtained by making acrylate, alkylene oxide modified polyfunctional (meth) acrylate, (meth) acrylate which has a hydroxyl group, and polyfunctional isocyanate react, and the (meth) acrylate which has a hydroxyl group, The polyfunctional (meth) acrylate etc. which have a carboxyl group obtained by making an acid anhydride react are mentioned.

Here, as said aliphatic polyhydroxy compound, For example, bivalent aliphatic polyhydroxy compound, such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol; And tri- or higher aliphatic polyhydroxy compounds such as glycerin, trimethylol propane, pentaerythritol and dipentaerythritol. As (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol, for example Penta (meth) acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. As the acid anhydride, for example, anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydro phthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid Tetrabasic acid dianhydrides such as dianhydride and benzophenone tetracarboxylic dianhydride.

Moreover, as said caprolactone modified polyfunctional (meth) acrylate, the compound described in Paragraph [0015]-[0018] of Unexamined-Japanese-Patent No. 11-44955 is mentioned, for example. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include di (meth) acrylate and isocyanuric acid modified by at least one selected from ethylene oxide of bisphenol A and propylene oxide of bisphenol A. At least one selected from tri (meth) acrylate modified by at least one selected from ethylene oxide and propylene oxide of isocyanuric acid, ethylene oxide of trimethylolpropane and propylene oxide of trimethylolpropane Tri (meth) acrylate modified by at least one species selected from tri (meth) acrylate modified by species, ethylene oxide of pentaerythritol and propylene oxide of pentaerythritol, and ethylene jade of pentaerythritol Tetra (meth) acrylate modified with at least one selected from seed and propylene oxide of pentaerythritol , Pentane (meth) acrylate modified by at least one selected from ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol, ethylene oxide of dipentaerythritol and propylene of dipentaerythritol Hexa (meth) acrylate modified with at least 1 sort (s) chosen from oxide, etc. are mentioned.

Moreover, as a compound which has the said 2 or more N-alkoxy methylamino group, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has one or more triazine ring or a phenyl substituted triazine ring as a basic skeleton, and is a concept containing melamine, benzoguanamine, or condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra (Alkoxymethyl) benzoguanamine, N, N, N ', N'- tetra (alkoxymethyl) glycoluril, etc. are mentioned.

Among these crosslinking agents, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone-modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate, Polyfunctional (meth) acrylate having a carboxyl group, N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra (alkoxymethyl) benzo Guanamine is preferred. In the polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, trimethylol propane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and di In the polyfunctional (meth) acrylate which pentaerythritol hexaacrylate has a carboxyl group, the compound obtained by making pentaerythritol triacrylate and succinic anhydride react, and dipentaerythritol pentaacrylate and succinic anhydride obtained The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and it is difficult to generate background contamination, film residue, etc. on the substrate and the light shielding layer of the unexposed part.

In the present invention, the (C) crosslinking agent may be used alone or in combination of two or more thereof.

10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and, as for content of (C) crosslinking agent in this invention, 20-500 mass parts is especially preferable. In this case, when there is too little content of a crosslinking agent, there exists a possibility that sufficient sclerosis | hardenability may not be obtained. On the other hand, when there is too much content of a crosslinking agent, when alkali developability is provided to the coloring composition of this invention, alkali developability will fall and it will become easy to produce background contamination, a film residue, etc. on the board | substrate or light-shielding layer of an unexposed part. There is this.

Photoinitiator

The coloring composition of this invention can be made to contain a photoinitiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photoinitiator used for this invention is a compound which generate | occur | produces the active species which can start superposition | polymerization of (C) crosslinking agent by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, and X-rays.

As such a photoinitiator, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, O-acyl oxime type compound, an onium salt type compound, a benzoin type compound, a benzophenone type compound, for example , α-diketone compounds, polynuclear quinone compounds, diazo compounds, imidesulfonate compounds, onium salt compounds and the like.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. As a photoinitiator, at least 1 sort (s) chosen from the group of a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, and an O-acyl oxime type compound is preferable. Moreover, 2 or more types chosen from the group of these compounds can also be mixed and used.

As a specific example of a thioxanthone type compound among the preferable photoinitiators in this invention, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl Thioxanthone, 2, 4- dichloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

In addition, specific examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. are mentioned. .

In addition, specific examples of the biimidazole-based compound 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-trichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

In addition, when using a biimidazole type compound as another photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure. As a hydrogen donor, For example, mercaptan-type hydrogen donors, such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; Amine hydrogen donors, such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donor may be used alone or in combination of two or more thereof, but in combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors, the sensitivity may be further improved. desirable.

In addition, specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2 [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-tri Azine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) And triazine compounds having halomethyl groups, such as -4,6-bis (trichloromethyl) -s-triazine.

In addition, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4- Tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2, 2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As a commercial item of an O-acyl oxime type compound, NCI-831, NCI-930 (above, the product made from Adeka Corporation) etc. can also be used.

When using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound in this invention, a sensitizer can also be used together. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone and 4-dimethylaminopropiophenone. Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

-menstruum-

The coloring composition of this invention contains the said (A)-(C) component and the other component added arbitrarily, Usually, a solvent is mix | blended and it is manufactured as a liquid composition. The solvent may be appropriately selected and used as long as it disperses or dissolves the components (A) to (C) or other components constituting the coloring composition, does not react with these components, and has suitable volatility.

Of these solvents, for example,

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 monoethyl ether, diethylene glycol mono- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;

Keto 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 monoethyl ether acetate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, or lactams

And the like.

Among these solvents, in terms of solubility, pigment dispersibility, coating properties, and the like (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones, Diacetates, alkoxycarboxylic acid esters and other esters are preferable, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether Acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6- Hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 Methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl pyruvate and the like are preferable.

In this invention, a solvent can be used individually or in mixture of 2 or more types. When using a mixture of solvents, at least (poly) alkylene glycol monoalkyl ethers, (poly) alkylene glycol monoalkyl ether acetates, (poly) alkylene glycol monoalkyl ether acetates and alkoxycarboxylic acid esters It is preferable to mix and use the compound, lactic acid alkyl ester, and (poly) alkylene glycol monoalkyl ether acetate.

Although content of a solvent is not specifically limited, The quantity which the total concentration of each component except the solvent of a coloring composition becomes 5-50 mass% is preferable, and the quantity which becomes 10-40 mass% is more preferable. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability, and the coloring composition with favorable applicability | paintability and stability can be obtained.

-additive-

The coloring composition of this invention may contain various additives as needed.

As an additive, For example, fillers, such as glass and an alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; Developability improvement agents, such as succinate mono [2- (meth) acryloyloxyethyl], phthalate mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate, etc. are mentioned. Can be.

The coloring composition of this invention can be manufactured by a suitable method, As a manufacturing method thereof, the method disclosed by Unexamined-Japanese-Patent No. 2008-58642, 2010-132874, etc. are mentioned, for example. have. When both a dye and a pigment are used as the colorant, as disclosed in Japanese Unexamined Patent Publication No. 2010-132874, after passing the dye solution through the first filter, the dye solution passed through the first filter is separately prepared. The method of manufacturing by mixing with a pigment dispersion liquid etc. and passing the obtained coloring composition through a 2nd filter can be employ | adopted. Furthermore, after dissolving the dye and the components (B) to (C) and other components used as necessary in the solvent, passing the obtained solution through the first filter, the solution passed through the first filter is prepared separately. The method of manufacturing by mixing with one pigment dispersion liquid and passing the obtained coloring composition through a 2nd filter can also be employ | adopted. Furthermore, after passing a dye solution through a 1st filter, the dye solution which passed the 1st filter, said (B)-(C) component, and the other component used as needed are melt | dissolved, and the solution obtained The method of manufacturing by mixing the solution which passed the 2nd filter, and the solution which passed the 2nd filter with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 3rd filter can also be employ | adopted.

Color filter and its manufacturing method

The color filter of this invention is equipped with the colored layer formed using the coloring composition of this invention.

As a method of manufacturing a color filter, the following method is mentioned first. First, on the surface of a board | substrate, a light shielding layer (black matrix) is formed so that the part which forms a pixel may be divided as needed. Subsequently, after apply | coating the liquid composition of the colored radiation-sensitive composition of red this invention which contains dye (a1) on this board | substrate, for example, it pre-bakes and evaporates a solvent and forms a coating film. Next, after exposing through a photomask to this coating film, it develops using alkaline developing solution and removes and removes the unexposed part of a coating film. Thereafter, post-baking forms a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

Subsequently, using each colored radiation-sensitive composition of green or blue, coating, prebaking, exposure, development, and post-baking of each colored radiation-sensitive composition are carried out in the same manner as described above, and the green pixel array and the blue pixel array are performed. Are formed on the same substrate in turn. Thereby, a color filter is obtained in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate. However, in this invention, at least 1 of red, green, and blue pixel should just be formed by the coloring composition of this invention. The order of forming the pixels of each color is not limited to the above.

In addition, the black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method, but using the colored radiation-sensitive composition in which black pigment is dispersed, It may be formed in the same manner as in the case of pixel formation.

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

In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like as necessary.

When the colored radiation-sensitive composition is applied to the substrate, an appropriate coating method such as spraying method, roll coating method, rotary coating method (spin coating method), slit die coating method or bar coating method can be employed, but in particular spin coating. It is preferable to employ | adopt the method and the slit die coating method.

Prebaking is normally performed combining a reduced pressure drying and heat drying. Drying under reduced pressure is usually performed until it reaches 50-200 Pa. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

Coating thickness is 0.6-8 micrometers normally as a film thickness after drying, Preferably it is 1.2-5 micrometers.

As a light source of radiation used when forming the pixel and / or black matrix, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, Laser light sources, such as an argon ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser, etc. are mentioned, The radiation whose wavelength is 190-450 nm is preferable.

The exposure dose of radiation is generally preferably 10 to 10,000 J / m ² .

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- -Diazabicyclo- [4.3.0] -5-nonene and the like are preferable.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. may be added in an appropriate amount to the alkali developing solution. After the alkali development, it is usually washed with water.

As the developing treatment, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid buildup) developing method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

The post-baking condition is usually about 180 to 280 DEG C for about 10 to 60 minutes.

The film thickness of the thus formed pixel is usually 0.5 to 5 mu m, preferably 1.0 to 3 mu m.

As a second method of manufacturing the color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, or the like is adopted. can do. In this method, the partition which also has a light shielding function is first formed on the surface of a board | substrate. Subsequently, after discharging the liquid composition of the colored thermosetting composition of red this invention containing the dye (a1) by the inkjet apparatus in the formed partition, for example, prebaking is performed and the solvent is evaporated. Subsequently, after exposing this coating film as needed, it hardens | cures by post-baking to form a red pixel pattern.

Next, using the green or blue colored thermosetting composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, the color filter by which the pixel pattern of three primary colors of red, green, and blue is arrange | positioned on a board | substrate is obtained. However, in this invention, at least 1 of red, green, and blue pixel should just be formed by the coloring composition of this invention. The order of forming the pixels of each color is not limited to the above.

In addition, the partition wall has a function of preventing the mixing of the coloring compositions of the respective colors discharged into the compartments as well as the light shielding function, and thus the film thickness is thicker than that of the black matrix used in the first method described above. Therefore, a partition is normally formed using a black radiation sensitive composition.

The method and conditions of the substrate, the light source of the radiation used for forming the color filter, the prebaking and the postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet system is about the same as the height of a partition.

After forming a protective film on the pixel pattern obtained in this way as needed, a transparent conductive film is formed by sputtering. After forming a transparent conductive film, a spacer can be formed further and it can be set as a color filter. Although a spacer is normally formed using a radiation sensitive composition, it can also be set as the spacer (black spacer) which has light shielding property. In this case, a coloring and radiation-sensitive composition in which a black coloring agent is dispersed is used, and the coloring composition of the present invention can be preferably used for forming such a black spacer.

Since the color filter of this invention obtained in this way is extremely high in brightness | luminance and color purity, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, etc.

Display element

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

The color liquid crystal display element provided with the color filter of this invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter may be formed on a substrate separate from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may have a structure opposite to each other via the liquid crystal layer. The substrate in which the color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed, and the substrate in which the ITO (indium oxide doped with tin) electrode is formed, face each other via a liquid crystal layer. It is also possible to take. The latter structure can significantly improve the aperture ratio, and has the advantage that a bright and high precision liquid crystal display element is obtained.

The color liquid crystal display device including the color filter of the present invention may include a backlight unit having a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As a white LED, for example, a white LED which combines a red LED, a green LED, and a blue LED to obtain white light by mixing, and a white LED and a blue LED which combines a blue LED, a red LED and a green phosphor to obtain white light by mixing White LED that obtains white light by mixing by combining red light emitting phosphor and green light emitting phosphor, white LED which obtains white light by mixing of blue LED and YAG fluorescent material, and blue LED, orange light emitting phosphor and green light emitting phosphor in combination The white LED which obtains white light, the ultraviolet-ray LED, the red light emitting fluorescent substance, the green light emitting fluorescent substance, and the blue light emitting fluorescent substance are combined, and the white LED etc. which obtain white light by mixing are mentioned.

The color liquid crystal display device including the color filter of the present invention includes a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching switching (IPS) type, a vertical alignment (VA) type, and an optically compensated birefringence (OCB) type. Appropriate liquid crystal modes such as) can be applied.

Moreover, the organic electroluminescent display element provided with the color filter of this invention can take 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 take a suitable structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

[Example]

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

Synthesis Example 1

25.2 g of chloroform and 1.72 g of dehydrated DMF were added to a 100 mL eggplant flask containing a stirrer, cooled to 10 ° C or lower under a stream of nitrogen, and 2.27 g (1.38 mL, 19.1 mmol) of thionyl chloride was added thereto at 30 ° C. Stirred for a minute. Then, 3.5 g (5.17 mmol) of acid red 289 was added thereto, stirred for 3 hours at 35 ° C. under a nitrogen stream, and then 0.246 g (0.149 mL, 2.07 mmol) of thionyl chloride was added thereto, followed by further stirring at the same temperature for 1.5 hours. Continued. The reaction mixture was cooled to 5 ° C., and 3.26 g (17.6 mmol) of dodecylamine and 5.46 g (54.0 mmol) of triethylamine were added at the same temperature, followed by stirring for 10 minutes, followed by a total of 15 hours of stirring at 40 ° C. . The reaction mixture was concentrated under reduced pressure with a rotary evaporator, and then the solution obtained by adding 12.3 g of methanol was concentrated again until the liquid volume became about half. Then 17.8 g of methanol and 1.23 g of acetic acid were added, and the obtained mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was added dropwise to a large amount of water to precipitate a red solid, which was filtered off by suction filtration and washed with water sufficiently. After wash | cleaning the obtained solid sufficiently with a small amount of diisopropyl ether and then hexane, 4.13 g of solid was obtained by drying under reduced pressure at 60 degreeC for 12 hours (yield 97.2%). By MS spectrum, it was confirmed that the obtained red solid is a compound represented by the following general formula (A1). This compound is called coloring agent (A-1).

Synthesis Example 2

A colorant was synthesized in the same manner as in Synthesis Example 1 except that methylethyl oxime was used in place of dodecylamine in Synthesis Example 1. From the MS spectrum, the obtained solid was confirmed to be a compound represented by the following general formula (A2). This compound is called coloring agent (A-2).

Synthesis Example 3

A colorant was synthesized in the same manner as in Synthesis Example 1 except that benzhydrazide was used instead of dodecylamine in Synthesis Example 1. From the MS spectrum, the obtained solid was confirmed to be a compound represented by the following general formula (A3). This compound is called a coloring agent (A-3).

Synthesis Example 4

A colorant was synthesized in the same manner as in Synthesis Example 1 except that 1-dodecanethiol was used instead of dodecylamine in Synthesis Example 1. From the MS spectrum, the obtained solid was confirmed to be a compound represented by the following general formula (A4). This compound is called a coloring agent (A-4).

Synthesis Example 5

A colorant was synthesized in the same manner as in Synthesis Example 1 except that p-toluenesulfonamide was used instead of dodecylamine in Synthesis Example 1. From the MS spectrum, the obtained solid was confirmed to be a compound represented by the following general formula (A5). This compound is called coloring agent (A-5).

Synthesis Example 6

A colorant was synthesized in the same manner as in Synthesis Example 1 except that Acid Red 52 was used instead of Acid Red 289 in Synthesis Example 1. From the MS spectrum, the obtained solid was confirmed to be a compound represented by the following general formula (A6). This compound is called colorant (A-6).

Comparative Synthesis Example 1

Dye was synthesize | combined according to description of the synthesis example 1 of Unexamined-Japanese-Patent No. 2010-254964. The obtained compound is called coloring agent (A-7).

Solubility Evaluation

The coloring agent (A-1) obtained by the synthesis example 1 was weighed, and cyclohexanone was added so that a coloring agent concentration might be 0.1 weight%, 1 weight%, and 5 weight%. These samples were stirred for 1 hour at 25 ° C using a mix rotor, and then the dissolved state was quickly confirmed by visual observation. As a result, it was confirmed that the colorant (A-1) was completely dissolved at 5 wt% with respect to cyclohexanone.

Similarly, solubility was evaluated about the coloring agent (A-2)-the coloring agent (A-7), and acid red 289. Colorants (A-2) to (A-6) were completely dissolved at 5% by weight relative to cyclohexanone. The colorant (A-7) was completely dissolved at 1% by weight, but not at 5% by weight. Acid red 289 did not dissolve at 0.1 wt%.

Preparation and Evaluation of Dye Solution

Production Example 1

5 mass parts of coloring agents (A-1) and 95 mass parts of ethyl lactate were mixed as a solvent, and the dye solution (A-1) was produced.

Preparation Examples 2 to 6

The dye solution (A-2) to the dye solution (A) in the same manner as in Production Example 1 except that the colorants (A-2) to (A-6) were used instead of the colorant (A-1) in Production Example 1. -6) was prepared.

Production Example 7

Although the coloring agent (A-7) was used instead of the coloring agent (A-1) in the manufacture example 1, the coloring agent (A-7) did not melt | dissolve completely in ethyl lactate, and the dissolution residue was observed. The obtained dye suspension is called dye solution (A-7).

Production Example 8

Acid red 289 was used in place of the colorant (A-1) in Production Example 1, but the acid red 289 was not dissolved in ethyl lactate. The obtained dye suspension is called dye solution (A-8).

Preparation of Pigment Dispersion

Production Example 9

As a colorant, C.I. Pigment Blue 15: 6 using 15 parts by mass, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (40 parts by mass of solid content), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent. Treatment with a bead mill produced a pigment dispersion (A-1).

Synthesis Example 7

100 mass parts of propylene glycol monomethyl ether acetates were thrown into the flask provided with the cooling tube and the stirrer, and it substituted by nitrogen. Heated at 80 캜, 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, and 15 parts by mass of 2-hydroxyethyl methacrylate. , 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate and 2,2'-azobis (2,4-dimethylvalle Ronitrile) 6 parts by mass of a mixed solution was added dropwise over 1 hour, and maintained at this temperature to polymerize for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration of 33% by mass). Obtained binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is called "binder resin (B1)."

&Lt; Preparation and evaluation of colored composition >

Example 1

13.5 parts by mass of the pigment dispersion (A-1), 7.2 parts by mass of the dye solution (A-1), and 9.9 parts by mass of the binder resin (B1) solution as the binder resin, and M-402 (Dipentaery) manufactured by Toagosei Co., Ltd. 15.4 parts by mass of a mixture of lititol hexaacrylate and dipentaerythritol pentaacrylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba Specialty) as a photopolymerization initiator 1.8 mass parts of Chemicals, brand name Irgacure 369) 0.2 mass parts of Megaface F-554 (made by DIC Corporation) as a surfactant, and ethyl lactate as a solvent are mixed, and the coloring composition of 20 mass% of solid content concentration is carried out. Was prepared.

After apply | coating the obtained coloring composition on a glass substrate using a spin coater, it prebaked for 10 minutes with the 80 degreeC hotplate, and formed three coating films from which a film thickness differs.

Subsequently, after cooling the substrate to room temperature, radiation containing each wavelength of 365 nm, 405 nm and 436 nm in the coating film was exposed to an exposure dose of 2,000 J / m ² without interposing a photomask using a high pressure mercury lamp. It exposed. Thus, the blue cured film for evaluation was formed on the board | substrate.

Contrast evaluation

The substrate on which the cured film was formed was sandwiched by two deflection plates, and the deflection plate on the front side was rotated while irradiating a fluorescent lamp (wavelength range of 380 to 780 nm) from the rear side, and the luminance meter LS-100 (Minolta ( Note) the maximum value and the minimum value of the light intensity transmitted through) were measured. And the value which divided the maximum value by the minimum value about each cured film was made into contrast ratio. From the measurement result, the contrast ratio in chromaticity coordinate value y = 0.080 was calculated | required. The evaluation results are shown in Table 1 below.

Evaluation of heat resistance

The board | substrate with which the cured film was formed was post-baked for 1 hour in 230 degreeC clean oven. Color difference (ΔEab *) was measured with respect to the board | substrate before and after postbaking. And when (DELTA) Eab * was less than 3.0, the case where "(circle)" and the case of 3.0 or more and less than 5.0 was evaluated as "(circle)" and the case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 1.

Evaluation of Voltage Retention Rate (%)

A SiO ₂ film was formed on the surface to prevent elution of sodium ions, and after spin coating the obtained colored composition onto a soda glass substrate on which an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape, Prebaking was performed for 1 minute with a hot plate, and the film of 2.0 micrometers in thickness was formed. Subsequently, it exposed to the film by the exposure amount of 700 J / m <^2> without passing through a photomask. Thereafter, the substrate was immersed in a developing solution containing 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. Was performed, and the film was cured to form a permanent cured film. Subsequently, the substrate in which this pixel was formed and the board | substrate which deposited the ITO electrode in the predetermined shape were bonded by the sealing agent which mixed 1.8 mm glass beads, and the liquid crystal cell (MLC6608) made of melt was injected, and the liquid crystal cell was produced. . Subsequently, the liquid crystal cell was put into the 60 degreeC constant temperature layer, and the voltage retention of the liquid crystal cell was measured by the liquid crystal voltage retention measurement system (VHR-1A type, Toyo Technica). The applied voltage at this time was 5.5 V square wave, and the measurement frequency was 60 Hz. Here, voltage retention is a value calculated | required by (the voltage applied by the liquid crystal cell potential difference / 0 millisecond after 16.7 millisecond). If the voltage retention of the liquid crystal cell is 90% or less, the liquid crystal cell means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for a time of 16.7 milliseconds, and cannot sufficiently align the liquid crystal. It may cause.

Examples 2-6 and Comparative Examples 1-2

In Example 1, the coloring composition was produced like Example 1 except having changed the kind and quantity of pigment dispersion liquid and dye solution as shown in Table 1. And it evaluated similarly to Example 1 about the obtained coloring composition. The evaluation results are shown in Table 1.

Claims

The following components (A), (B) and (C):
(A) a colorant containing a dye represented by the following formula (1),
(B) binder resin, and
(C) crosslinking agent
It contains a coloring composition characterized by the above-mentioned.

[In formula (1),
X ⁻ represents an anion;
a is an integer determined such that the compound is electrically neutral;
m represents an integer of 0 to 5, provided that when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different;
R ¹ to R ⁴ are each independently a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atoms included in the aromatic hydrocarbon group are a halogen atom, -R ⁶ , -OH, -OR ⁶ , _{^{_{-SO 3 -, -SO 3 H,}}} -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NH 2, -SO 2 NHR 8, -SO 2 NR 8 R ⁹ , -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , which may be substituted;
R ⁵ are each independently a _{^{_{-SO 3 -, -SO 3 H,}}} -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8, -SO 2 NR 8 R ⁹ , —SO ₂ —ON═CR ⁷ R ¹⁰ , —SO ₂ NHNHR ⁷ , —SO ₂ SR ^7, or —SO ₂ NHSO ₂ R ¹¹ ;
R ⁶ is a monovalent saturated hydrocarbon group (the hydrogen atom in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ -in the saturated hydrocarbon group is substituted with -O-, -CO-, or -NR ^7- ). May be);
R ⁷ represents a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-);
R ⁸ and R ⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group (the hydrogen atom contained in the saturated aliphatic hydrocarbon group may be substituted with —OH, a halogen atom, —Q, —CH═CH ₂ or —CH═CHR ⁶⁾ . And -CH ₂ -included in the saturated aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -NH- or -NR ^6- ;
R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-) or R ¹¹ ;
R ¹¹ represents a monovalent hydrocarbon group which may have a substituent;
Q is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms (The at least one hydrogen atom included in the aromatic hydrocarbon group and the heterocyclic group may be selected from -R ⁶ , -OR ^6, and -CH. Is substituted with at least one member selected from the group consisting of = CHR ⁶ , and the remaining hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group may be substituted with -OH, -NO ₂ , -CH = CH _2, or a halogen atom; Present);
M represents a sodium atom or a potassium atom,
Provided that the compound meets one or more of the following requirements (i) to (vi):
(i) at least one of R ¹ to R ⁴ is at least 1 selected from the group consisting of -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ^7, and -SO ₂ NHSO ₂ R ¹¹ ; An aromatic hydrocarbon group having a substituent of the species
(ii) R ¹ to R ⁴ At least one of which is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ , provided that the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ Have at least 11 carbon atoms
(iii) R ¹ to R ⁴ At least one of -R ⁶ is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -R ⁶ , -OR ⁶ , -CO ₂ R ⁶ and -SO ₃ R ⁶ , provided that R ⁶ Monovalent saturated hydrocarbon groups represented by
(iv) at least one of m R ⁵ is -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹
(v) at least one of m R ⁵ is -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ , provided that the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms
(vi) at least one of m R ⁵ is —CO ₂ R ⁶ or —SO ₃ R ⁶ , provided that the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms]

The compound of claim 1, wherein in Formula (1), a = 0 and R ¹ to R ⁴ Or an aromatic hydrocarbon group substituted by, one or more R ⁵ m with a -SO ₃ ^{- -} either is -SO ₃ of the coloring composition.

The coloring composition of Claim 1 in which the dye represented by the said General formula (1) is represented by following General formula (2).

[In formula (2),
R ^1a to R ^4a are each independently a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ^7, or -SO ₂ NHSO ₂ R ¹¹ ;
R ^5a are each independently -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ ;
R ⁶ is a monovalent saturated hydrocarbon group (the hydrogen atom in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ -in the saturated hydrocarbon group is substituted with -O-, -CO-, or -NR ^7- ). May be);
R ⁷ represents a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-);
R ⁸ and R ⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group (the hydrogen atom contained in the saturated aliphatic hydrocarbon group may be substituted with —OH, a halogen atom, —Q, —CH═CH ₂ or —CH═CHR ⁶⁾ . And -CH ₂ -included in the saturated aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -NH- or -NR ^6- ;
R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group (the hydrogen atom included in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-) or- R ¹¹ is represented;
R ¹¹ represents a monovalent hydrocarbon group which may have a substituent;
Q is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms (The at least one hydrogen atom included in the aromatic hydrocarbon group and the heterocyclic group may be selected from -R ⁶ , -OR ^6, and -CH. Is substituted with at least one member selected from the group consisting of = CHR ⁶ , and the remaining hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group may be substituted with -OH, -NO ₂ , -CH = CH _2, or a halogen atom; Present);
M represents a sodium atom or a potassium atom,
n represents an integer of 0 to 4, provided that when n is an integer of 2 or more, a plurality of R ^5a may be the same or different;
Provided that the compound meets one or more of the following requirements (i) to (vi):
(i) R ^1a to at least one of R ^4a is _{^{-SO 2 -ON = CR 7 R 10}} , -SO 2 NHNHR 7, -SO 2 SR 7 and -SO ₂ NHSO at least one selected from the group consisting of ₂ R ¹¹ An aromatic hydrocarbon group having a substituent of the species
(ii) at least one of R ^1a to R ^4a is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of —SO ₂ NHR ⁸ and —SO ₂ NR ⁸ R ⁹ , provided that R ⁸ , R ⁹ The monovalent saturated aliphatic hydrocarbon group represented should have 11 or more carbon atoms.
(iii) at least one of R ^1a to R ^4a is —R ⁶ or has at least one substituent selected from the group consisting of —R ⁶ , —OR ⁶ , —CO ₂ R ⁶ and —SO ₃ R ^6; Aromatic hydrocarbon group, provided that the monovalent saturated hydrocarbon group represented by R ⁶ has at least 11 carbon atoms
(iv) at least one of n R ^5a is -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹
(v) at least one of n R ^5a is —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ , provided that the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms
(vi) at least one of n R ^5a is —CO ₂ R ⁶ or —SO ₃ R ⁶ , provided that the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms]

The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-3.

The color liquid crystal display element provided with the color filter of Claim 4.

Dye represented by following General formula (1).

[In formula (1),
X ⁻ represents an anion;
a is an integer determined such that the compound is electrically neutral;
m represents an integer of 0 to 5, provided that when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different;
R ¹ to R ⁴ are each independently a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atoms included in the aromatic hydrocarbon group are a halogen atom, -R ⁶ , -OH, -OR ⁶ , _{^{_{-SO 3 -, -SO 3 H,}}} -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NH 2, -SO 2 NHR 8, -SO 2 NR 8 R ⁹ , -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹ , which may be substituted;
R ⁵ are each independently a _{^{_{-SO 3 -, -SO 3 H,}}} -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8, -SO 2 NR 8 R ⁹ , —SO ₂ —ON═CR ⁷ R ¹⁰ , —SO ₂ NHNHR ⁷ , —SO ₂ SR ^7, or —SO ₂ NHSO ₂ R ¹¹ ;
R ⁶ is a monovalent saturated hydrocarbon group (the hydrogen atom in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ -in the saturated hydrocarbon group is substituted with -O-, -CO-, or -NR ^7- ). May be);
R ⁷ represents a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-);
R ⁸ and R ⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group (the hydrogen atom contained in the saturated aliphatic hydrocarbon group may be substituted with —OH, a halogen atom, —Q, —CH═CH ₂ or —CH═CHR ⁶⁾ . And -CH ₂ -included in the saturated aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -NH- or -NR ^6- ;
R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group (the hydrogen atom included in the hydrocarbon group may be substituted with a halogen atom or -R ¹¹ , and the hydrocarbon group may be linked with -O- or -CO-) or- R ¹¹ is represented;
R ¹¹ represents a monovalent hydrocarbon group which may have a substituent;
Q is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms (The at least one hydrogen atom included in the aromatic hydrocarbon group and the heterocyclic group may be selected from -R ⁶ , -OR ^6, and -CH. Is substituted with at least one member selected from the group consisting of = CHR ⁶ , and the remaining hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group may be substituted with -OH, -NO ₂ , -CH = CH _2, or a halogen atom; Present);
M represents a sodium atom or a potassium atom,
Provided that the compound meets one or more of the following requirements (i) to (vi):
(i) at least one of R ¹ to R ⁴ is at least 1 selected from the group consisting of -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ^7, and -SO ₂ NHSO ₂ R ¹¹ ; An aromatic hydrocarbon group having a substituent of the species
(ii) R ¹ to R ⁴ At least one of which is an aromatic hydrocarbon group having at least one substituent selected from the group consisting of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ , provided that the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ Have at least 11 carbon atoms
(iii) at least one of R ¹ to R ⁴ is —R ⁶ or has at least one substituent selected from the group consisting of —R ⁶ , —OR ⁶ , —CO ₂ R ⁶ and —SO ₃ R ^6; Aromatic hydrocarbon group, provided that the monovalent saturated hydrocarbon group represented by R ⁶ has at least 11 carbon atoms
(iv) at least one of m R ⁵ is -SO ₂ -ON = CR ⁷ R ¹⁰ , -SO ₂ NHNHR ⁷ , -SO ₂ SR ⁷ or -SO ₂ NHSO ₂ R ¹¹
(v) at least one of m R ⁵ is -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ , provided that the monovalent saturated aliphatic hydrocarbon group represented by R ⁸ , R ⁹ has 11 or more carbon atoms
(vi) at least one of m R ⁵ is —CO ₂ R ⁶ or —SO ₃ R ⁶ , provided that the monovalent saturated hydrocarbon group represented by R ⁶ has 11 or more carbon atoms]