JP5439860B2 - Colored photosensitive resin composition - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition and a color filter obtained from the colored photosensitive resin composition.

As a color filter material, a colored photosensitive resin composition containing a colorant is conventionally known.
In recent years, color filters are desired to have high definition, high brightness, and high contrast.
A colored photosensitive resin composition containing a pyrazole-based squarylium compound as a dye pigment and a blue pigment Pigment Blue (P.B) 15: 6 as a pigment pigment as a colored photosensitive resin composition for increasing the contrast of a color filter A composition is disclosed (Patent Document 1).

Japanese Patent Application Laid-Open No. 2006-079012

  In the conventional colored photosensitive resin composition, the brightness of the obtained coating film and color filter may not always be sufficient.

［式中、環Ｚ^１および環Ｚ^２は、それぞれ独立に、置換基を有していてもよい複素環を表す。ｌは０以上３以下の整数を表す。ｍは１の整数を表す。］
で表される構造を有する化合物（１）を含む着色感光性樹脂組成物。 As a result of studying the above problems, the present inventors have found that a high-lightness coating film and a color filter can be obtained from a colored photosensitive resin composition containing a certain dye, and have reached the present invention.
The inventors have completed the following inventions [1] to [16].
[1] Including a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E),
The colorant (A) has the formula (1)

[Wherein, ring Z ¹ and ring Z ² each independently represent a heterocyclic ring optionally having a substituent. l represents an integer of 0 or more and 3 or less. m represents an integer of 1; ]
The coloring photosensitive resin composition containing the compound (1) which has a structure represented by these.

［式中、環Ｚ^１、環Ｚ^２、ｌおよびｍは、それぞれ請求項１と同じ。
Ｘ⁻は、ハロゲンアニオン、ＣｌＯ_４ ⁻、ＯＨ⁻、１価の有機カルボン酸アニオン、１価の有機スルホン酸アニオン、１価のホウ素アニオン又は１価の有機金属錯体アニオンを表す。 ］
で表される［１］記載の着色感光性樹脂組成物。

[Wherein, ring Z ¹ , ring Z ² , l and m are the same as those in claim 1, respectively.
X ⁻ represents a halogen anion, ClO ₄ ⁻ , OH ⁻ , monovalent organic carboxylate anion, monovalent organic sulfonate anion, monovalent boron anion or monovalent organometallic complex anion. ]
The colored photosensitive resin composition according to [1], represented by:

［式中、環Ｚ^５及び環Ｚ^６は、それぞれ独立に、置換基を有していてもよいベンゼン環又は置換基を有していてもよいナフタレン環を表す。
Ｙ⁻は、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、ＣｌＯ_４ ⁻、ＯＨ⁻、１価の有機カルボン酸アニオン、１価の有機スルホン酸アニオン、１価のホウ素アニオン又は１価の有機金属錯体アニオンを表す。
ｎは、０以上３以下の整数を表す。
Ａ^１及びＡ^２は、それぞれ独立に、酸素原子、硫黄原子、セレン原子、炭素原子又は窒素原子を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有していてもよい１価の炭素数１〜２０の脂肪族炭化水素基を表す。
Ｒ^３及びＲ^４は、それぞれ独立に水素原子又は１価の炭素数１〜６の脂肪族炭化水素基を表すか、１個のＲ^３と１個のＲ^４とが一緒になって形成された２価の炭素数２〜６の脂肪族炭化水素基を表す。
ａおよびｂは、それぞれ独立に、０以上２以下の整数を表す。］ [3] The colored photosensitive resin composition according to [1], wherein the compound (1) is represented by the formula (2a).

[Wherein, ring Z ⁵ and ring Z ⁶ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
Y ⁻ represents Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , OH ⁻ , monovalent organic carboxylate anion, monovalent organic sulfonate anion, monovalent boron anion or monovalent organometallic complex anion. Represent.
n represents an integer of 0 or more and 3 or less.
A ¹ and A ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom.
R ¹ and R ² each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ³ and one R ⁴ are formed together. And a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
a and b each independently represent an integer of 0 or more and 2 or less. ]

[4] The colored photosensitive resin composition according to [3], wherein n is 1.

[5] The colored photosensitive resin composition according to [3] or [4], wherein Y ⁻ is a monovalent organic sulfonate anion.

［式中、環Ｚ^１、環Ｚ^２、ｌおよびｍは、それぞれ請求項１と同じ。環Ｚ^３および環Ｚ^４は、それぞれ独立に、置換基を有していてもよい複素環を表す。Ｘ^ａ−は、ハロゲンアニオン、ＣｌＯ_４ ⁻、ＯＨ⁻、有機カルボン酸アニオン、有機スルホン酸アニオン、ホウ素アニオン又は有機金属錯体アニオンを表す。ａは、Ｘ^ａ−の価数を表す。ｌ’は０以上３以下の整数を表す。ｍ’は１の整数を表す。Ｌ^１は、置換されていてもよい２価の炭化水素基を表す。］
で表される［１］記載の着色感光性樹脂組成物。 [6] Compound (1) has the following formula (1b)

[Wherein, ring Z ¹ , ring Z ² , l and m are the same as those in claim 1, respectively. Ring Z ³ and ring Z ⁴ each independently represent a heterocyclic ring optionally having a substituent. X ^a− represents a halogen anion, ClO ₄ ⁻ , OH ⁻ , an organic carboxylate anion, an organic sulfonate anion, a boron anion, or an organometallic complex anion. a represents the valence of ^Xa- . l ′ represents an integer of 0 or more and 3 or less. m ′ represents an integer of 1; L ¹ represents a divalent hydrocarbon group which may be substituted. ]
The colored photosensitive resin composition according to [1], represented by:

[7] Compound (1) has the following formula (2b)

[Wherein, each of ring Z ⁷ , ring Z ⁸ , ring Z ⁹ and ring Z ¹⁰ independently represents a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. .
Y ^b− represents a halogen anion, ClO ₄ ⁻ , OH ⁻ , an organic carboxylate anion, an organic sulfonate anion, a boron anion, or an organometallic complex anion. b represents the valence of Y ^b− . When b is 1, each Y ^b− may be the same as or different from each other.
n ² and n ³ each independently represents an integer of 0 or more and 3 or less.
A ³ , A ⁴ , A ⁵ and A ⁶ each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ⁵ and one R ⁶ are formed together Represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
R ⁷ and R ⁸ each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ⁷ and one R ⁸ are formed together. Represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
R ⁹ and R ¹⁰ each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
c, d, e, and f each independently represent an integer of 0 or more and 2 or less.
L ² represents a divalent hydrocarbon group which may be substituted. ]
[6] The colored photosensitive resin composition according to [6].

[8] The colored photosensitive resin composition according to [7], wherein n ² and n ³ are each 1.

[9] The colored photosensitive resin composition according to [7] or [8], wherein Y ^b- is a divalent organic sulfonate anion.

[10] b is ^2, one of ^{Y b-is} a monovalent organic acid anion, another ^{Y b-is} a halogen anion [7] or [8] The colored photosensitive resin composition according object.

[11] The colored photosensitive resin composition according to any one of [1] to [10], wherein the colorant (A) further contains an organic pigment.

[12] The organic pigment is C.I. I. The colored photosensitive resin composition according to [11], which is CI Pigment Blue 15: 6.

[13] C.I. I. Pigment Blue 15: 6 and Compound (1) have a mass ratio of (CI Pigment Blue 15: 6): Compound (1) = 97: 3 to 50:50 [12] Resin composition.

[14] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [13].

[15] The color filter according to [14], which is formed by a photolithographic method or an inkjet method.

［式中、環Ｚ^１および環Ｚ^２は、それぞれ独立に、置換基を有していてもよい複素環を表す。ｌは０以上３以下の整数を表す。ｍは１を表す。］
で表される構造を有する化合物（１）を含む着色剤。 [16] Formula (1)

[Wherein, ring Z ¹ and ring Z ² each independently represent a heterocyclic ring optionally having a substituent. l represents an integer of 0 or more and 3 or less. m represents 1. ]
The coloring agent containing the compound (1) which has a structure represented by these.

  According to the present invention, a coating film and a color filter with high brightness can be obtained.

3 is a graph showing the transmittance of Example 1. 10 is a graph showing the transmittance of Example 4.

  In the colored photosensitive resin composition of the present invention, the colorant (A) contains a compound having a structure represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).

[Wherein, ring Z ¹ and ring Z ² each independently represent a heterocyclic ring optionally having a substituent. l represents an integer of 0 or more and 3 or less. m represents an integer of 1 or 2. ]

Compound (1) can be selected according to the color of the target color filter.
It is preferable that the compound (1) is sufficiently dissolved in the solvent (E). Furthermore, the compound (1) is preferably dissolved in the developer used for pattern formation to such an extent that the pattern can be formed.

In the present invention, the optionally substituted heterocycle contains one or more heteroatoms. The heterocycle may be monocyclic or polycyclic.
The hetero atom may be an atom selected from Group 15 or Group 16 elements in the periodic table, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.
Examples of the heterocyclic ring include indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, and quinoline ring.

Examples of the substituent of the heterocyclic ring include, for example,
Aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl;
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group;
Aryloxy groups such as phenoxy groups;
An aralkyloxy group such as a benzyloxy group;
Groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group;
Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group Alkylsulfamoyl groups such as a famoyl group, n-butylsulfamoyl group, di-n-butylsulfamoyl group;
Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Examples thereof include a nitro group and a cyano group.
When the substituent has a hydrogen atom, the hydrogen atom is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group. , Isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; aryloxy group such as phenoxy group, benzyloxy group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group An aromatic hydrocarbon group such as a group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group; carboxy group; cyano group; nitro group;

As the heterocyclic ring, an indole ring, a benzoindole ring, an indolenine ring, and a benzoindolenin ring are preferable, and an indole ring and a benzoindolenin ring are more preferable.
The heterocycle preferably has one or two alkyl groups or halogen atoms as substituents.
The above l is preferably 1 in terms of brightness.

A compound having the structure of the above formula (1), that is, a compound having a methine chain having rings bonded to both ends is generally referred to as a cyanine dye.
The structure represented by the formula (1), that is, the cyanine dye skeleton is positively charged. The compound (1) is an ionic compound and generally has an anion that is ionically bonded to the cyanine dye skeleton. Examples of such anions include halogen anions, ClO ₄ ⁻ , OH ⁻ , organic carboxylic acid anions, organic sulfonate anions, boron anions, and organometallic complex anions as described below.
When a cis-trans isomer exists as the structure of the above formula (1), any isomer is included in the present invention.

で表される化合物が挙げられる。 Examples of the compound (1) include the following formula (1a)

The compound represented by these is mentioned.

In formula (1a), ring Z ¹ , ring Z ² , l and m have the same definitions as in formula (1).
The ring Z ¹ and the ring Z ² are each preferably an indole ring.
The l is preferably 1.

X ⁻ represents a halogen anion, ClO ₄ ⁻ , OH ⁻ , monovalent organic carboxylate anion, monovalent organic sulfonate anion, monovalent boron anion or monovalent organometallic complex anion.
In the compound of formula (1a), the above X ⁻ is generally ionically bonded to the cyanine dye skeleton.
X ^- it is, specifically,
Halogen anions such as Cl ⁻ , Br ⁻ and I ⁻ ;
Organic carboxylate anions such as benzenecarboxylate ion, alkylcarboxylate ion, trihaloalkylcarboxylate ion, nicotinate ion;
Organic sulfonate anions such as benzenesulfonate ion, naphthalenesulfonate ion, p-toluenesulfonate ion, alkylsulfonate ion;
Boron anions such as BF ₄ ⁻ ;
Organometallic complex ions of azo, bisphenyldithiol, thiocatechol chelate, thiobisphenolate chelate, bisdiol-α-diketone;
Etc.
In the organometallic complex ion, examples of the central metal include group 3 to group 11 transition elements in the periodic table.
Examples of the transition metal include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, Palladium, platinum, copper, silver, gold, cadmium, mercury and the like can be mentioned.
As the organometallic complex, an azo metal complex or a bisphenyldithiol metal complex is preferable, and an azo metal complex is more preferable.
The central metal is preferably cobalt, nickel, or copper in terms of manufacturing cost and ease of handling.
Specifically, the organometallic complex is preferably an azo metal complex or bisphenyldithiol metal complex whose central metal is cobalt, nickel or copper, and an azo metal complex whose central metal is cobalt, nickel or copper. More preferred.

As said X < ^- >, an organic sulfonate anion is preferable. Examples of the organic sulfonate anion include benzene sulfonate ion, naphthalene sulfonate ion, p-toluene sulfonate ion, and alkyl sulfonate ion.

As said compound (1), the compound represented by Formula (2a) is more preferable at the point which makes the brightness of a coating film high.

In formula (2a), ring Z ⁵ and ring Z ⁵ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
Examples of the substituent in the benzene ring and the naphthalene ring include the same groups as the substituents in the above heterocyclic ring.
Ring Z ⁵ and ring Z ⁵ are each preferably an optionally substituted benzene ring, and more preferably an unsubstituted benzene ring.

Y ⁻ represents Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , OH ⁻ , monovalent organic carboxylate anion, monovalent organic sulfonate anion, monovalent boron anion or monovalent organometallic complex anion. Represent.
Specific examples of Y ⁻ include the same groups as X ⁻ described above. Y ⁻ is preferably a monovalent organic sulfonate anion.

n represents an integer of 0 or more and 3 or less.
n is preferably 1 in terms of brightness.

A ¹ and A ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom.
A ¹ and A ² are each preferably a carbon atom.
a and b each independently represent an integer of 0 or more and 2 or less.
a and b are each preferably 2.

R ¹ and R ² each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a 2-propynyl group, and a butyl group. , Isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group Group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group and octyl group.
Examples of the substituent in the aliphatic hydrocarbon group include:
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, benzyloxy group;
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.
R ¹ and R ² are each preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ³ and one R ⁴ are formed together. And a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
Examples of the aliphatic hydrocarbon group represented by R ³ or R ⁴ include an alkyl group having 1 to 6 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group.
R ³ and R ⁴ are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R ³ and R ⁴ are preferably the same group.

で表される化合物が好ましい。 Examples of the compound (1) include the following formula (1b)

The compound represented by these is preferable.

In the formula (1b), ring Z ¹ , ring Z ² , l and m are the same as defined above.
Ring Z ³ and ring Z ⁴ each independently represent a heterocyclic ring optionally having a substituent.
Examples of the heterocyclic ring represented by ring Z ³ or ring Z ⁴ include the same groups as the heterocyclic ring represented by ring Z ¹ or ring Z ² .
Ring Z ¹ , ring Z ² , ring Z ³ and ring Z ⁴ are each preferably an indole ring.

X ^a− represents a halogen anion, ClO ₄ ⁻ , OH ⁻ , an organic carboxylate anion, an organic sulfonate anion, a boron anion, or an organometallic complex anion.
Examples of the halogen anion include Cl ⁻ , Br ⁻ and I ⁻ .
Examples of the organic carboxylate anion include benzenecarboxylate ion, alkylcarboxylate ion, trihaloalkylcarboxylate ion, and nicotinate ion.
Examples of the organic sulfonate anion include benzene sulfonate ion, benzene disulfonate ion, naphthalene sulfonate ion, naphthalene disulfonate ion, p-toluene sulfonate ion, and alkyl sulfonate ion.
As the boron anion, for example, BF ₄ ^- and the like.
Examples of the organic metal complex anion, X ^- include organic metal complex anions listed illustrative.
a represents the valence of ^Xa- . That is, in the formula (1b), X ^a− may be one or two. When two X ^a- are present, each X ^a- may be the same as or different from each other.
l ′ represents an integer of 0 or more and 3 or less.
m ′ represents an integer of 1 or 2.

L ¹ represents a divalent hydrocarbon group which may be substituted.
Examples of L ¹ include:
Aliphatic hydrocarbon groups such as methylene group, ethylene group, vinylene group, trimethylene group, propylene group, propenylene group, tetramethylene group, pentamethylene group, hexamethylene group;
Alicyclic hydrocarbon groups such as cyclopentylene group, cyclohexenylene group, cyclohexadienylene group;
and aromatic hydrocarbon groups such as o-phenylene group, m-phenylene group, p-phenylene group, and naphthylene group.

In L ¹ , one or more hydrogen atoms are substituted with an amino group, a carboxy group, a cyano group, a nitro group, a halogen group, a hydroxy group, or the like as long as the brightness of the obtained coating film is not impaired. It may be.
L ¹ may be bonded to any position of ring Z ¹ and ring Z ³ as long as light absorption characteristics and solubility derived from the structure of formula (1) are not substantially impaired.
L ¹ is preferably an alkylene group having 1 to 16 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 3 to 8 carbon atoms.
As L ¹ , the number of atoms and its main chain is preferably less than 10, more preferably 3 or more, in view of ease of synthesis and solubility in an organic solvent. 8 or less.

  The compound (1) is more preferably a compound represented by the formula (2b) (hereinafter sometimes referred to as “compound (2b)”) in terms of improving the brightness and heat resistance of the coating film.

In formula (2b), ring Z ⁷ , ring Z ⁸ , ring Z ⁹ and ring Z ¹⁰ are each independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. Represents.
Examples of the substituent in the benzene ring and the naphthalene ring include the same groups as the substituents in the above heterocyclic ring.

n ² and n ³ each independently represents an integer of 0 or more and 3 or less.
n ² and n ³ are each preferably 1.
A ³ , A ⁴ , A ⁵ and A ⁶ each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom.
A ³ , A ⁴ , A ⁵ and A ⁶ are each preferably a carbon atom.
c, d, e, and f each independently represent an integer of 0 or more and 2 or less.
c, d, e and f are each preferably 2.

R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ⁵ and one R ⁶ are formed together Represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
R ⁷ and R ⁸ each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ⁷ and one R ⁸ are formed together. Represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
Examples of the aliphatic hydrocarbon group represented by R ⁵ , R ⁶ , R ⁷ or R ⁸ include an alkyl group having 1 to 6 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group.

R ⁹ and R ¹⁰ each represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The aliphatic hydrocarbon may have a substituent.
Examples of the aliphatic hydrocarbon group represented by R ⁹ or R ¹⁰ include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, and a 2-propenyl group. Group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1 -Methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group and the like.
Examples of the substituent in the aliphatic hydrocarbon group include:
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, benzyloxy group;
Halogen groups such as fluoro, chloro, bromo and iodo groups;
A carboxy group, a nitro group, and a cyano group are mentioned.

Y ^b− represents a halogen anion, ClO ₄ ⁻ , OH ⁻ , an organic carboxylate anion, an organic sulfonate anion, a boron anion, or an organometallic complex anion.
b represents the valence of Y ^b− . When b is 1, there are two Y ^{b− in} formula (2b). In this case, each Y ^b− may be the same as or different from each other.
That is, when b is 1, the compound (2b) has the following formula (3b)

(In the formula, ring Z ⁷ , ring Z ⁸ , ring Z ⁹ , ring Z ¹⁰ , n ² , n ³ , A ³ , A ⁴ , A ⁵ , A ⁶ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , c, d, e, f and L ² are the same as those in the formula (2b).
Y ¹ and Y ² are each independently a halogen anion, ClO ₄ ⁻ , OH ⁻ , monovalent organic carboxylate anion, monovalent organic sulfonate anion, monovalent boron anion or monovalent organometallic complex anion. Represents. )
It can also be represented by
Specific examples of the Y ^b- are the same as the groups exemplified as the X ^a- .
When ^Yb- is an organometallic complex anion, an organometallic complex having cobalt, nickel, or copper as a central metal is preferable in terms of production cost and ease of handling.
As the organometallic complex, an azo metal complex or a bisphenyldithiol metal complex is preferable, and an azo metal complex is more preferable.

In the compound (2b), the structural portion represented by the formula (1), that is, the cyanine dye skeleton is positively charged, and Y ^b− is ion-bonded to the cyanine dye skeleton.

^Yb- is preferably an organic sulfonate anion, more preferably a benzenesulfonate ion, a benzenedisulfonate ion, a naphthalenesulfonate ion, a naphthalene disulfonate ion, a p-toluenesulfonate ion, or an alkylsulfonate ion.
When two Y ^b- are present, one Y ^b- is preferably a halogen anion and the other is preferably an organic sulfonate anion.
Such a combination of halogen anion and organic sulfonate anion includes halogen anion and benzene sulfonate ion, halogen ion and naphthalene sulfonate ion, halogen anion and p-toluene sulfonate ion, halogen anion and alkyl sulfonate ion. preferable.

L ² represents a divalent hydrocarbon group which may be substituted. Specific examples of L ² include the same groups as L ¹ .
L ² is preferably an alkylene group having 1 to 16 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 3 to 8 carbon atoms.

As the compound (2b),
In the formula (2b), n ² and n ³ are 1, b = 2, and Y ^b− is an organic sulfonate anion,
In the formula (2b), ^{n 2} and ^{n 3} is 1, a b = ^{1, Y} is one of a halogen anion ^b-, the other one ^{Y b-is} benzene sulfonate ion or naphthalenesulfonate ion Certain compounds are preferred.

The colorant (A) preferably contains an organic pigment in addition to the compound (1).
As an organic pigment, specifically, for example,
C. I. Blue pigments such as CI Pigment Blue 15 (for example, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, 60);
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. And violet color pigments such as CI Pigment Violet 38.
These pigments may be used alone or in combination of two or more.
Examples of the organic pigment include C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 3, and C.I. I. It preferably contains at least one pigment selected from CI Pigment Blue 15: 6; I. It is particularly preferable that pigment blue 15: 6 is contained.

If necessary, the above organic pigment may be treated with rosin; surface treatment with pigment derivatives, etc .; graft treatment on the pigment surface, atomization with sulfuric acid atomization, etc .; or washing with organic solvent or water; ion Removal treatment by an exchange method or the like may be performed.
The organic pigment preferably has a uniform particle size.

When the colorant (A) contains an organic pigment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained by adding a pigment dispersant and performing a dispersion treatment.
The pigment dispersant may be any of cationic, anionic, nonionic, and amphoteric surfactants, such as polyester surfactants, polyamine surfactants, acrylic surfactants, and the like. Is mentioned. These pigment dispersants may be used alone or in combination of two or more.
When the colorant (A) contains a pigment dispersant, the amount used is preferably 1 part by mass or less, more preferably 0.05 parts by mass or more and 0.5 parts by mass or less per 1 part by mass of the organic pigment. is there. It is preferable that the amount of the pigment dispersant used be in the above range since a pigment dispersion in which the pigment is uniformly dispersed can be easily obtained.

Content of a coloring agent (A) is a mass fraction with respect to solid content in a coloring photosensitive resin composition, Preferably it is 10-60 mass%, More preferably, it is 15-55 mass%, Furthermore, Preferably it is 18-50 mass%.
Here, solid content means the sum total of the components except a solvent in a coloring photosensitive resin composition.
When the content of the colorant (A) is in the above range, the colored photosensitive resin composition of the present invention can easily obtain a color filter having a sufficient color density, and further, the binder resin (B). Therefore, it is easy to form a pattern with sufficient mechanical strength.
The content of the organic pigment in the colorant (A) is 20 to 97% by mass, preferably 30 to 95% by mass, and more preferably 40 to 95% by mass.
In particular, the colorant (A) is C.I. I. When the pigment blue 15: 6 and the compound (1) are included, the mass ratio of the two is preferably (CI pigment blue 15: 6): compound (1) = 97: 3 to 50:50, (C.I. Pigment Blue 15: 6): Compound (1) = 97: 3-70: 30 is more preferable.
When the content of the organic pigment in the colorant (A) is within the above range, the colored photosensitive resin composition can easily obtain a color filter with high brightness. Furthermore, when the content is in the above range, it is easy to optimize the transmission spectrum.

The above-mentioned colorant (A), that is, a colorant containing the above-mentioned compound (1) is also one aspect of the present invention.
The colorant of the present invention is useful as a material for the colored photosensitive resin composition as described above. In addition, ink colorants for ink-jet ink recording, paints, printing inks, colorants for plastics, and coloring for various color filters. It is also useful for agents.

The colored photosensitive resin composition of the present invention contains a binder resin (B).
The binder resin (B) preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 in terms of mole fraction in all the structural units constituting the binder resin (B). It is from mol% to 38 mol%. When the binder resin (B) includes a structural unit derived from (meth) acrylic acid, the solubility of the non-pixel part at the time of development is good, and the residue hardly remains in the non-pixel part after development. The content is preferably in the above range.

The binder resin (B) may be a copolymer of (meth) acrylic acid and other monomers.
Examples of other monomers include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, and cyanide. Examples include monomers such as vinyl compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, and macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain. Furthermore, examples of the structural unit derived from monomers other than (meth) acrylic acid include the structural unit represented by the formula (I) and the structural unit represented by the formula (III).

(In each formula, R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
In the present invention, R ¹¹ is preferably a methyl group, and R ¹² is preferably a hydrogen atom.

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, and methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent unit represented by formula (I) (where R ¹¹ represents a methyl group and R ¹² represents a hydrogen atom) / benzyl methacrylate copolymer Compound, a structural unit represented by formula (I) (wherein R ¹¹ represents a methyl group and R ¹² represents a hydrogen atom) / benzyl methacrylate copolymer, methacrylic acid / expressed by formula (III) structural units ^{(wherein, R 11} represents a methyl ^{group, R 12} represents a hydrogen atom.) / steel Such emission copolymer / tricyclodecanyl methacrylate copolymer.

The acid value of the binder resin (B) is usually 50 to 150, preferably 60 to 135, particularly preferably 70 to 135. Since the solubility in the developer is improved, the unexposed part is easily dissolved, and the sensitivity is improved, so that the remaining film ratio after development is improved, and the acid value may be in the above range. preferable.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution. Can do.

Content of binder resin (B) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, and is 15-35 mass% normally, Preferably it is 18-33 mass%, More preferably 21 to 31% by mass. It is preferable that the content of the binder resin (B) is in the above range in that pattern formation is easy and the resolution and the remaining film ratio are improved.

Binder resin having a structural unit represented by formula (I), for example, methacrylic acid / a structural unit represented by formula (I) (wherein R ¹¹ represents a methyl group and R ¹² represents a hydrogen atom). / Benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer and a compound represented by formula (II) (wherein R ¹³ is hydrogen) Which represents an atom).

(In the formula, R ¹³ represents a hydrogen atom.)

Methacrylic acid / constituent component represented by formula (III) (wherein R ¹¹ represents a methyl group and R ¹² represents a hydrogen atom) / styrene copolymer / tricyclodecanyl methacrylate copolymer is benzyl It can be obtained by reacting a monomethacrylate copolymer having a methacrylate, methacrylic acid, or tricyclodecane skeleton with glycidyl methacrylate.

The binder resin (B) has a polystyrene-equivalent weight average molecular weight of usually 5,000 to 35,000, preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000.
It is preferable that the average molecular weight of the binder resin (B) is in the above range because the coating film hardness is improved, the residual film ratio is high, the solubility in the unexposed portion of the developer is good, and the resolution is improved. .
The said average molecular weight is a value converted from the measured value of GPC [gel permeation chromatography].

In particular, the binder resin (B) represented by the formula (IV) is preferable in terms of curability and developability.

  The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) when irradiated with light, and is, for example, polymerizable carbon-carbon unsaturated. Examples thereof include compounds having a bond.

The photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more functional groups (such a photopolymerizable compound is also referred to as a polyfunctional photopolymerizable compound).
Examples of the polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.
The colored photosensitive resin composition of the present invention may contain one or more of the above photopolymerizable compounds (C).
The content of the photopolymerizable compound (C) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on the solid content of the colored photosensitive resin composition. More preferably, it is 20-70 mass%.
Curing sufficiently occurs, the film thickness ratio before and after development is improved, the pattern is less likely to be undercut, and the adhesiveness is good, so the content of the photopolymerizable compound (C) is It is preferable that it exists in the range.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include acetophenone compounds, active radical generators, and acid generators.
Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done.

  The active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can also be used.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Some of the active radical generators generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  Content of a photoinitiator (D) is a mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C), Preferably it is 0.1-20 mass%, More preferably Is 1 to 15% by mass. Since the sensitivity is increased and the exposure time is shortened, the productivity is improved, but since the sensitivity is not too high, the minimum line width of the resolution pattern does not become too thick, the content of the photopolymerization initiator is as described above. It is preferable to be in the range.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation assistant (F). The photopolymerization initiation assistant (F) is usually used in combination with the photopolymerization initiator (D), and is a compound used for promoting the polymerization of the photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator. is there.
Examples of the photopolymerization initiation assistant (F) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  The photopolymerization initiation assistant (F) may be used alone or in combination of two or more. Moreover, as a photopolymerization start adjuvant (F), a commercially available thing can also be used, and as a commercially available photopolymerization start adjuvant (F), brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation auxiliary agent (F) in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4 4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylke / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) ) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, etc., preferably 2-methyl-2-morpholino Examples include -1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

The content of the photopolymerization initiator auxiliary (F) is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator (D).

  The colored photosensitive resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, N-methylpyrrolidone, dimethyl sulfoxide and the like.

  Examples of the ethers and esters include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxypentyl acetate, anisole, phenetol, methyl anisole, ethyl acetate, n-butyl acetate, isobutyl acetate, formic acid Amyl, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate , Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Methyl , Ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.
The said solvent may be used independently and may be used in combination of 2 or more types.
As the solvent (E), diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethers such as propylene glycol monopropyl ether acetate, esters, and ketones are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone are more preferable, and it is more preferable to use these in combination.

  Content of the solvent (E) in a colored photosensitive resin composition is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 70-95 mass%, More preferably, it is 75-90 mass%. . The content of the solvent (E) is preferably in the above-mentioned range in that the flatness at the time of application is good and a color filter having good display characteristics can be easily obtained.

The colored photosensitive resin composition of the present invention may further contain a surfactant (G). Examples of the surfactant (G) include at least one selected from the group consisting of silicone surfactants and fluorine surfactants.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by GE Toshiba Silicone Co., Ltd.).
Examples of the silicone surfactant further include a silicone surfactant having a fluorine atom. Examples of such a silicone surfactant include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (trade name) F142D, F171, F172, F173, F177, F177, F183, R30 (large) Nippon Ink Chemical Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie) and the like.
These surfactants may be used alone or in combination of two or more.
Content of surfactant (G) is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 0.0005-0.6 mass%, More preferably, it is 0.001-0.5 mass%. It is. In view of obtaining a flat coating film, the content of the surfactant (G) is preferably in the above range.

The colored photosensitive resin composition of the present invention can provide a high-contrast coating film.
A color filter formed from the colored photosensitive resin composition of the present invention is also one aspect of the present invention.
The color filter of the present invention can be formed by a photolithographic method or an ink jet method.
As the photolithographic method, for example, the colored photosensitive resin composition of the present invention is applied on a substrate, a volatile component such as a solvent is removed to form a colored layer, and the colored layer is exposed through a photomask. Then, a developing method is mentioned. In this method, the colored photosensitive resin composition may be formed by forming a resin layer obtained from the other colored photosensitive resin composition on a substrate and coating the resin layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.
The components used in this example are as follows, and may be omitted below.
(A-1) Colorant component: C.I. I. Pigment Blue 15: 6

(A-2) Colorant component: The following compound (NK-9402, manufactured by Hayashibara Biochemical Laboratories)

(A-3) Colorant component: The following compound (NK-8635, manufactured by Hayashibara Biochemical Laboratories)

(A-4) Colorant component: The following compound (NK-9422, manufactured by Hayashibara Biochemical Laboratories)

(A-5) Colorant component: The following compound (NK-9424, manufactured by Hayashibara Biochemical Laboratories)

(A-6) Colorant component: The following compound (NK-9425, manufactured by Hayashibara Biochemical Laboratories)

<Synthesis of Resin (B-1)>
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 136 g of propylene glycol monomethyl ether acetate, a solution obtained by adding 3.6 g of azobisisobutyronitrile was added dropwise, and stirring was further continued at 100 ° C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin (B-1) having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate; 1.0 mL / min test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

(C-1) Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
(D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (F-1) photopolymerization initiator assistant: 4,4′-bis (Diethylamino) benzophenone (E-1) solvent: Propylene glycol monomethyl ether acetate (E-2) solvent: Propylene glycol monomethyl ether (E-3) solvent: Cyclohexanone (G-1) Surfactant: Megafax F475 (Dainippon Ink Chemical Industry Co., Ltd.)

Example 1
[Preparation of colored photosensitive resin composition 1]
(A-1) 4.370 parts by mass Acrylic pigment dispersant 1.533 parts by mass (A-2) 0.230 parts by mass (B-1) 3.952 parts by mass (C-1) 5.773 parts by mass (D-1) 1.732 parts by mass (F-1) 0.577 parts by mass (E-1) 77.454 parts by mass (E-3) 4.369 parts by mass (G-1) 0.010 parts by mass Were mixed to obtain a colored photosensitive resin composition 1.

[Formation of pattern]
On the glass substrate [# 1737; manufactured by Corning], the colored photosensitive resin composition 1 obtained above was applied by spin coating, and then dried at 100 ° C. for 3 minutes to volatilize volatile components (solvent). By further cooling, a layer of colored photosensitive resin composition 1 was formed. This colored photosensitive resin composition layer was exposed by irradiating with i-line [wavelength 365 nm] through a photomask. As an i-line light source, an ultra-high pressure mercury lamp was used, and the irradiation light quantity was 150 mJ / cm ² . Then, it heat-processed for 20 minutes at 220 degreeC, and formed the coating film. The film thickness of the coating film was 2.2 μm.

Example 2
[Preparation of colored photosensitive resin composition 2]
(A-1) 4.370 parts by mass Acrylic pigment dispersant 1.533 parts by mass (A-3) 0.230 parts by mass (B-1) 3.952 parts by mass (C-1) 5.773 parts by mass (D-1) 1.732 parts by mass (F-1) 0.577 parts by mass (E-1) 77.454 parts by mass (E-3) 4.369 parts by mass (G-1) 0.010 parts by mass Were mixed to obtain a colored photosensitive resin composition 2. A coating film was obtained in the same manner as in Example 1 except that the colored photosensitive resin composition 2 was used in place of the colored photosensitive resin composition 1.

Example 3
[Preparation of colored photosensitive resin composition 3]
(A-1) 4.370 parts by mass Acrylic pigment dispersant 1.533 parts by mass (A-4) 0.230 parts by mass (B-1) 3.952 parts by mass (C-1) 5.773 parts by mass (D-1) 1.732 parts by mass (F-1) 0.577 parts by mass (E-1) 77.454 parts by mass (E-3) 4.369 parts by mass (G-1) 0.010 parts by mass Were mixed to obtain a colored photosensitive resin composition 3. A coating film was obtained in the same manner as in Example 1 except that the colored photosensitive resin composition 3 was used in place of the colored photosensitive resin composition 1.

[Evaluation 1]
The obtained coating film on the glass substrate was irradiated with a C light source using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and xy chromaticity coordinates in the XYZ color system of CIE ( Bx, By) and brightness were measured.
The results are shown in Table 1.

  From Table 1, excellent brightness was confirmed in each coating film obtained from the colored photosensitive resin compositions of Example 1, Example 2 and Example 3.

1 is a graph showing the transmittance of the coating film obtained in Example 1. FIG.
The transmittance was measured by the same method as the above brightness. The horizontal axis indicates the wavelength, and the vertical axis indicates the transmittance.
As shown in FIG. 1, since the colored photosensitive resin composition of Example 1 contains the colorant of the present invention, the brightness can be further increased by optimizing the transmission spectrum. Also in Examples 2 and 3, the transmission spectrum was equivalent to that in Example 1.

Example 4
[Preparation of colored photosensitive resin composition 4]
(A-1) 4.370 parts by mass Acrylic pigment dispersant 1.533 parts by mass (A-5) 0.46 parts by mass (B-1) 3.952 parts by mass (C-1) 5.773 parts by mass (D-1) 1.732 parts by mass (F-1) 0.577 parts by mass (E-1) 77.454 parts by mass (E-3) 4.369 parts by mass (G-1) 0.010 parts by mass Were mixed to obtain a colored photosensitive resin composition 1.

[Formation of pattern]
On the glass substrate [# 1737; manufactured by Corning], the colored photosensitive resin composition 1 obtained above was applied by spin coating, and then dried at 100 ° C. for 3 minutes to volatilize volatile components (solvent). By further cooling, a layer of the colored photosensitive resin composition 4 was formed. This colored photosensitive resin composition layer was exposed by irradiating with i-line [wavelength 365 nm] through a photomask. As an i-line light source, an ultra-high pressure mercury lamp was used, and the irradiation light quantity was 150 mJ / cm ² . Then, it heat-processed for 20 minutes at 220 degreeC, and formed the coating film. The film thickness of the coating film was 2.2 μm.

Example 5
[Preparation of colored photosensitive resin composition 5]
(A-1) 4.370 parts by mass Acrylic pigment dispersant 1.533 parts by mass (A-6) 0.460 parts by mass (B-1) 3.952 parts by mass (C-1) 5.773 parts by mass (D-1) 1.732 parts by mass (F-1) 0.577 parts by mass (E-1) 77.454 parts by mass (E-3) 4.369 parts by mass (G-1) 0.010 parts by mass Were mixed to obtain a colored photosensitive resin composition 5. A coating film was obtained in the same manner as in Example 4 except that the colored photosensitive resin composition 5 was used instead of the colored photosensitive resin composition 4.

[Evaluation]
About the coating film on the obtained glass substrate, chromaticity and lightness were measured by the same method as the said evaluation 1.
The results are shown in Table 2.

  As shown in Table 2, excellent brightness was confirmed in each coating film obtained from the colored photosensitive resin composition of Example 4 or Example 5.

FIG. 2 is a graph showing the transmittance of the coating film obtained in Example 4. The transmittance was measured by the same method as the above brightness. The horizontal axis indicates the wavelength, and the vertical axis indicates the transmittance.
As shown in FIG. 2, since the colored photosensitive resin composition of Example 4 contains the colorant of the present invention, the brightness can be further increased by optimizing the transmission spectrum. Also in Examples 2 and 3, the transmission spectrum was equivalent to that in Example 1.
Also for Example 5, the transmission spectrum was equivalent to Example 4.

  According to the colored photosensitive resin composition of the present invention, a high-lightness coating film and a color filter can be obtained.

Claims (6)

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and the colorant (A) is represented by the formula ( 2a )

[Wherein, ring Z ⁵ and ring Z ⁶ each independently represent an optionally substituted benzene ring or an optionally substituted naphthalene ring.
Y ⁻ represents Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , OH ⁻ , monovalent organic carboxylate anion, monovalent organic sulfonate anion, monovalent boron anion or monovalent organometallic complex anion. Represent.
n represents an integer of 0 or more and 3 or less.
A ¹ and A ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom.
R ¹ and R ² each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ³ and one R ⁴ are formed together. And a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
a and b each independently represent an integer of 0 or more and 2 or less. ]
The compound (2a) having a structure represented by formula (1) and an organic pigment are included, and the colorant (A) is further contained in an amount of 10 to 60% by mass with respect to the solid content in the colored photosensitive resin composition. Colored photosensitive resin composition. Y ^- is colored photosensitive resin composition of claim 1 wherein the monovalent organic acid anion. Organic pigments include C.I. I. The colored photosensitive resin composition according to claim 1 or 2, which is CI Pigment Blue 15: 6. C. I. The colored photosensitivity according to claim 3 , wherein the mass ratio of Pigment Blue 15: 6 to Compound ( 2a ) is (CI Pigment Blue 15: 6): Compound ( 2a ) = 97: 3 to 50:50. Resin composition. The color filter formed from the coloring photosensitive resin composition of any one of Claims 1-4 . The color filter according to claim 5, which is formed by a photolithography method or an ink jet method.

Images