TWI439809B - Colored photosensitive resin composition - Google Patents

Description

Colored photosensitive resin composition

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

As the color filter material, a colored photosensitive resin composition containing a colorant has been known from the past.

In recent years, for color filters, high definition, high definition, or high contrast is desired.

For the color-sensitive photosensitive resin composition for the purpose of high contrast of color filters, it has been revealed that a pyrazole-based squarylium compound is used as a dye pigment and a blue pigment Pigment Blue (PB) 15:6 as a pigment. A colored photosensitive resin composition of a pigment (JP 2006-079012). On the other hand, further discussion is required on the coloring photosensitive resin composition which achieves the high definition of the color filter.

In order to achieve a method of achieving high definition, high definition, or high contrast of a color filter, the coating film obtained from the colored photosensitive resin composition is considered to improve the performance.

An object of the present invention is to provide a colored photosensitive resin composition which achieves the high definition of the coating film or the color filter.

As a result of the investigation of the above-mentioned problems, the inventors of the present invention have found that a high-quality coating film or a color filter can be obtained from a colored photosensitive resin composition containing a certain dye, and the present invention has been completed.

That is, the inventors of the present invention completed the following inventions [1] to [16].

[1] A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), the colorant ( A) A compound (1) having a structure represented by the formula (1)

[wherein, the ring Z ¹ and the ring Z ² are each independently, and each represents a hetero ring which may have a substituent. 1 represents an integer of 0 or more and 3 or less. m represents an integer of 1].

[2] The colored photosensitive resin composition according to [1], wherein the compound (1) is represented by the following formula (1a):

[wherein, ring Z ¹ , ring Z ² , l and m are each the same as [1].

X ^- represents a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylate anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion].

[3] The colored photosensitive resin composition according to [1], wherein the compound (1) is represented by the formula (2a):

[wherein, the ring Z ⁵ and the ring Z ⁶ are each independently, and 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 ^- , a monovalent organic carboxylate anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion.

n represents an integer of 0 or more and 3 or less.

A ¹ and A ² are each independently and represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom.

R ¹ and R ² each independently represent an 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 a divalent carbon number of 2 to 6 formed by integrating one R ³ and one R ⁴ . Aliphatic hydrocarbon group.

Each of a and b is independent, and represents an integer of 0 or more and 2 or less. ]

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

[5] The colored photosensitive resin composition of [3] or [4], wherein Y ^- is a monovalent organic sulfonate anion.

[6] The colored photosensitive resin composition according to [1], wherein the compound (1) is represented by the following formula (1b):

[wherein, ring Z ¹ , ring Z ² , l and m are each the same as [1]. Ring Z ³ and ring Z ⁴ are each independently and represent a heterocyclic ring which may have 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 X ^a- . 1' 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].

[7] The colored photosensitive resin composition according to [6], wherein the compound (1) is represented by the following formula (2b):

[wherein, ring Z ⁷ , ring Z ⁸ , ring Z ⁹ and ring Z ¹⁰ , each independently, represent 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- can be phased or different.

n ² and n ³ each independently represent an integer of 0 or more and 3 or less.

A ³ , A ⁴ , A ⁵ and A ⁶ are each independently and 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 The carbon number of the aliphatic having 1 to 6 of the hydrocarbon group, or represents an R ⁵ is a R ⁶ together form the divalent carbon atoms, aliphatic 2-6 of A hydrocarbon group.

R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a divalent carbon number 2 to 6 fat formed by integrating one R ⁷ and one R ⁸ . A hydrocarbon group.

R ⁹ and R ¹⁰ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

c, d, e, and f are each independent, and represent an integer of 0 or more and 2 or less.

L ² represents a divalent hydrocarbon group which may be substituted].

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

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

[10] The colored photosensitive resin composition according to [7] or [8], wherein b is 2, one of ^Yb- is a monovalent organic sulfonate anion, and the other ^Yb- is a halogen anion.

[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 colored photosensitive resin composition according to [11], wherein the organic pigment is C.I. Pigment Blue 15:6.

[13] The colored photosensitive resin composition according to [12], wherein the mass ratio of CI Pigment Blue 15:6 to compound (1) is (CI Pigment Blue 15:6): compound (1) = 97:3 to 50 :50.

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

[15] The filter according to [14], wherein the filter is formed by a photolithography method or an inkjet method.

[16] A coloring agent comprising the compound (1) having the structure represented by the formula (1):

[wherein, ring Z ¹ and ring Z ² each independently represent a hetero ring which may have a substituent. 1 Table 0 or more and 3 or less integers. m means 1].

In the colored photosensitive resin composition of the present invention, the colorant (A) contains the formula (1)

A compound having a structure (hereinafter sometimes referred to as "compound (1)").

[wherein, the ring Z ¹ and the ring Z ² are each independently, and each represents a hetero ring which may have a substituent. 1 represents an integer of 0 or more and 3 or less. m represents an integer of 1 or 2. ]

Compound (1) can be selected in accordance with the color of the color filter of interest.

The compound (1) is preferably dissolved in the solvent (E) sufficiently. Further, the compound (1) is preferably dissolved in a developing solution for patterning to such an extent that a pattern can be formed.

In the present invention, a heterocyclic ring which may have a substituent includes 1 or a plurality of hetero atoms. The above heterocyclic ring may be a single ring or a polycyclic ring.

The above hetero atom may be an atom selected from a Group 15 or Group 16 element of the periodic table, such as a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom or a ruthenium atom.

The above heterocyclic ring, such as anthraquinone ring, benzofluorene ring, pseudofluorene ring, benzofluorene ring, Oxazole ring, benzo An azole ring, a thiazole ring, a benzothiazole ring, a benzimidazole ring or a quinoline ring.

The substituent of the above heterocyclic ring is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, tert-butyl, pentyl, isopentyl, neopentyl, An aliphatic hydrocarbon group such as tripentyl; phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, Base, neighbor Base, room Base An aromatic hydrocarbon group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group or a pentyloxy group; An aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group; a group having an ester bond such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an ethoxylated group or a benzhydryloxy group; Aminesulfonyl, dimethylamine sulfonyl, ethylamine sulfonyl, diethylamine sulfonyl, n-propylamine sulfonyl, di-n-propylamine sulfonyl, isopropylamine sulfonate Alkylsulfonyl group such as mercapto, diisopropylamine sulfonyl, n-butylamine sulfonyl, di-n-butylamine sulfonyl; methylsulfonyl, ethylsulfonyl, propyl An alkylsulfonyl group such as a sulfonyl group, an isopropylsulfonyl group, a n-butylsulfonyl group, an isobutylsulfonyl group, a t-butylsulfonyl group or a t-butylsulfonyl group; a fluorine atom; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a nitro group or a cyano group.

Further, when the substituent has a hydrogen atom, the hydrogen atom may be substituted with 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 or an isopropoxy group; Alkoxy group such as butoxy group, isobutoxy group, second butoxy group, third butoxy group, pentyloxy group; aryloxy group such as phenoxy group or benzyloxy group; phenyl group, o-tolyl group, and Tolyl, p-tolyl, xylyl, Base, neighbor Base, room Base An aromatic hydrocarbon group; a carboxyl group; a cyano group; a nitro group;

The above heterocyclic ring is preferably an anthracene ring, a benzofluorene ring, a pseudofluorene ring or a benzofluorene ring, and an anthracene ring or a benzofluorene ring is more preferred.

The above heterocyclic ring preferably has one or two alkyl groups or a halogen atom as a substituent.

The above 1 is preferably 1 in terms of brightness.

A compound having the structure of the above formula (1), that is, a compound having a methane chain in which a ring is bonded at both ends, is generally called a cyanine dye.

The structure represented by the formula (1), that is, the cyanine dye skeleton is positively charged. The above compound (1) is an ionic compound, and generally has an anion bonded by an ionic bond in the cyanine dye skeleton. Examples of such anions include halogen anions, ClO ₄ ^- , OH ^- , organic carboxylate anions, organic sulfonate anions, boron anions, and organometallic complex anions.

In the configuration of the above formula (1), when a cis-trans isomer is present, any of the isomers is included in the present invention.

The above compound (1) is, for example, a compound represented by the following formula (1a).

In the formula (1a), the ring Z ¹ , the ring Z ² , l and m are each the same as defined in the formula (1). The ring Z ¹ and the ring Z ^{2 are} preferably each an anthracene ring.

The above 1 is preferably 1.

X ^- represents a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylate anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion.

In the compound of the formula (1a), the above X ^{- is} generally ionically bonded to the cyanine dye skeleton.

X ^- , specifically, for example: halogen anions such as Cl ^- , Br ^- , I ^- ; organic carboxylate anions such as benzene carboxylate anion, alkyl carboxylate anion, trihaloalkyl carboxylate anion, nicotinic acid anion; An organic sulfonate anion such as a benzenesulfonate anion, a naphthalenesulfonate anion, a p-toluenesulfonate anion or an alkylsulfonate anion; a BF ₄ ^- , an isocyanide; an azo, a biphenyldithiol, or a sulfur phthalate a phenol chelate system, a thiobisphenolate chelate system, a didiol-α-diketone organometallic complex ion;

Among the above organometallic complex ions, a central metal such as a transition element of Group 3 to Group 11 in the periodic table.

The above transition metals are, for example, ruthenium, osmium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, lanthanum, cerium, iron, lanthanum, cerium, cobalt, lanthanum, cerium, nickel, palladium, platinum. , copper, silver, gold, cadmium, mercury, etc.

The above organometallic complex is preferably an azo metal complex or a biphenyldithiol metal complex, and an azo metal complex is more preferable.

The above-mentioned center metal is preferably cobalt, nickel or copper from the viewpoint of production cost and ease of handling.

The above organometallic complex, specifically, a central metal-based cobalt, nickel or copper azo metal complex or a biphenyldithiol metal complex, preferably a central metal cobalt, nickel or copper The azo metal complex is more preferred.

The above X ^{- is} preferably an organic sulfonate anion. The organic sulfonate anion is, for example, a benzenesulfonate anion, a naphthalenesulfonate anion, a p-toluenesulfonate anion, an alkylsulfonate anion or the like.

The compound (1) is more preferably a compound represented by the formula (2a) from the viewpoint of improving the lightness of the coating film.

In the formula (2a), the ring Z ⁵ and the ring Z ⁶ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.

In the benzene ring and the naphthalene ring, the substituent is, for example, the same group as the substituent in the above heterocyclic ring.

Ring Z ⁵ and ring Z ^{6 are} each preferably a substituted benzene ring, and an unsubstituted benzene ring is more preferred.

Y ^- represents Cl ^- , Br ^- , I ^- , ClO ₄ ^- , OH ^- , a monovalent organic carboxylate anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organometallic complex anion .

Specific examples of the above Y ^- are, for example, the same as the above X ^- . The above Y ^{- is} preferably a monovalent organic sulfonate anion.

n represents an integer of 0 or more and 3 or less.

n, in the view of the brightness, 1 is better.

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.

Each of a and b is independent, and represents an integer of 0 or more and 2 or less.

Both a and b are preferably 2.

R ¹ and R ² each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

The aliphatic hydrocarbon group, for example, methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, 2-propynyl, butyl, iso Butyl, t-butyl, tert-butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, neopentyl, third amyl, 1-methylpentyl 2-methylpentyl, 2-penten-4-yl, hexyl, isohexyl, 5-methylhexyl, heptyl, octyl.

In the aliphatic hydrocarbon group, the substituent is, for example, a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a xylyl group, Base, neighbor - Base, room - Base, right - Equivalent aromatic hydrocarbon group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tert-butoxy, pentyloxy, phenoxy Alkoxy groups such as a benzyl group; a halogen group such as a fluorine group, a chlorine group, a bromine group or an iodine group; and a carboxyl group, a nitro group and a cyano group.

R ¹ and R ² each preferably have 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 an aliphatic group in which one R ³ and one R ^{4 are} integrated to form a divalent carbon number of 2 to 6. Hydrocarbyl group.

An aliphatic hydrocarbon group represented by R ³ or R ⁴ , for example, an alkyl group having 1 to 6 carbon atoms. Such an alkyl group is, for example, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group or a third pentyl group.

R ³ and R ⁴ each preferably have 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.

The compound (1) is preferably a compound represented by the following formula (1b).

In the formula (1b), the ring Z ¹ , the rings Z ² , l and m are each the same as defined above. Ring Z ³ and ring Z ⁴ are each independently and represent a heterocyclic ring which may have a substituent.

The heterocyclic ring represented by the ring Z ³ or the ring Z ⁴ is, for example, the same as the hetero ring represented by the ring Z ¹ or the ring Z ² .

The ring Z ¹ , the ring Z ² , the ring Z ³ and the ring Z ^{4 are} each preferably an anthracene 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.

The above halogen anions are, for example, Cl ^- , Br ^- , I ^- and the like.

The above organic carboxylate anion is, for example, a benzoate anion, an alkylcarboxylate anion, a trihaloalkylcarboxylate anion, or a nicotinic anion.

The above organic sulfonate anion is, for example, a benzenesulfonate anion, a benzenedisulfonate anion, a naphthalenesulfonate anion, a naphthalene disulfonate anion, a p-toluenesulfonate anion, or an alkylsulfonate anion.

The above boron anion, such as BF ₄ ^- .

The above organometallic complex anion, for example, X ^- is exemplified by the organometallic complex anion exemplified.

a represents the valence of X ^a- . That is, in the formula (1b), X ^a- may be one or two. When there are two X ^a- , each X ^a- may be the same or different from each other.

1' 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.

The L ¹ : for example, an aliphatic hydrocarbon group such as a methylene group, an ethyl group, a vinyl group, a trimethylene group, a propyl group, a propylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group; An alicyclic hydrocarbon group such as a pentyl group, a cyclohexyl group or a cyclohexylene group; an aromatic hydrocarbon group such as a phenyl group, an exophenyl group, a paraphenyl group or a naphthyl group;

Further, L ¹ may be substituted with an amine group, a carboxyl group, a cyano group, a nitro group, a halogen group, a hydroxyl group or the like as long as it does not impair the range of the brightness of the obtained coating film.

L ¹ may be bonded to any of the ring Z ¹ and the ring Z ³ as long as the light absorption characteristics or solubility derived from the structure of the formula (1) are not substantially impaired.

The 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 more preferably an alkylene group having 3 to 8 carbon atoms.

In the above L ¹ , the number of atoms constituting its main chain is preferably less than 10, more preferably 3 or more and 8 or less, from the viewpoints of ease of synthesis or solubility in an organic solvent.

The compound (1) is more preferably a compound represented by the formula (2b) (hereinafter sometimes referred to as "compound (2b)") from the viewpoint of improving the brightness of the coating film or heat resistance.

In the formula (2b), the ring Z ⁷ , the ring Z ⁸ , the ring Z ⁹ and the ring Z ¹⁰ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. In the benzene ring and the naphthalene ring, the substituent is, for example, the same as the substituent in the above heterocyclic ring.

n ² and n ³ are each independently, and represent 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 are each independently and 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 each preferably have 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 The carbon number of the aliphatic having 1 to 6 of the hydrocarbon group or represents an R ⁵ is a R ⁶ together form the divalent carbon atoms, aliphatic 2-6 of A hydrocarbon group.

R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a divalent carbon number of 2 to 6 which is formed by integrating one R ⁷ and one R ⁸ . Aliphatic hydrocarbon group.

The aliphatic hydrocarbon group represented by R ⁵ , R ⁶ , R ⁷ or R ⁸ is, for example, an alkyl group having 1 to 6 carbon atoms. Such an alkyl group is, for example, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group or a third pentyl group.

Each of R ⁹ and R ¹⁰ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The aliphatic hydrocarbon may have a substituent.

An aliphatic hydrocarbon group represented by the above R ⁹ or R ¹⁰ , for example, methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, 2- Propynyl, butyl, isobutyl, t-butyl, tert-butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, neopentyl, third pentylene Base, 1-methylpentyl, 2-methylpentyl, 2-penten-4-yl, hexyl, isohexyl, 5-methylhexyl, heptyl, octyl and the like.

In the aliphatic hydrocarbon group, the substituent is, for example, a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a xylyl group, Base, neighbor Base, room Base Equivalent aromatic hydrocarbon group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tert-butoxy, pentyloxy, phenoxy Alkoxy groups such as a benzyloxy group; a halogen group such as a fluorine group, a chlorine group, a bromine group or an iodine group; a carboxyl group, a nitro group and a cyano group;

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, in the formula (2b), there are two Y ^b- . In this case, each Y ^b- may be the same or different from each other.

That is, the compound (2b) can have the following formula (3b) when b is 1.

(wherein 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 the formula (2b). Y ¹ and Y ² are each independently, and represent a halogen anion, ClO ₄ ^- , OH ^- , and a monovalent organic carboxylate anion. , a monovalent organic sulfonate anion or a monovalent organometallic complex anion.).

Specific examples of the above Y ^{b- are} the same as those exemplified in the above X ^a- .

When Y ^b- is an organometallic complex anion, an organic metal complex containing cobalt, nickel or copper as a central metal is preferred from the viewpoint of production cost and ease of handling.

The above organometallic complex is preferably an azo metal complex or a biphenyldithiol metal complex, and an azo metal complex is more preferred.

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

The above Y ^{b- is} preferably an organic sulfonate anion, more preferably a benzenesulfonate anion, a benzenedisulfonate anion, a naphthalenesulfonate anion, a naphthalene disulfonate anion, a p-toluenesulfonate anion or an alkylsulfonate anion.

When there are two Y ^{b- groups} , one Y ^b- is a halogen anion and the other is an organic sulfonate anion.

Such a combination of a halogen anion and an organic sulfonate anion is preferably a halogen anion and a benzenesulfonate anion, a halogen anion and a naphthalenesulfonate anion, a halogen anion and a p-toluenesulfonate anion, a halogen anion and an alkylsulfonate anion.

L ² represents a divalent hydrocarbon group which may be substituted. Specific examples of L ² are, for example, the same groups as L ¹ .

The 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 more preferably an alkylene group having 3 to 8 carbon atoms.

Compound (2b): in formula (2b), n ² and n ³ are 1, b is 2, Y ^b- is an organic sulfonate anion compound, or in formula (2b), n ² and n ³ are 1, b is 1, Y ^{b -} a compound in which one is a halogen anion and the other Y ^b- is a benzenesulfonate anion or a naphthalenesulfonate anion is preferred.

The coloring agent (A) preferably contains an organic pigment in addition to the compound (1).

Organic pigments, specifically, for example, 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); CI Pigment Violet 1, CI Pigment Violet 19, CI PigmentViolet 23, C.1. Pigment Violet 29, CI Pigment Violet 32, C.1. Pigment Violet 36, CI Pigment Violet 38 and other purple pigments.

These pigments may be used singly or in combination of two or more.

The above organic pigments preferably contain at least one pigment selected from C. I. Pigment Red Violet 23, C. I. Pigment Blue 15:3, and C. I. Pigment Blue 15:6, and preferably contain C, I, Pigment Blue 15:6.

The above organic pigment may be applied as follows: rosin treatment; surface treatment using a pigment derivative; surface treatment of grafting the pigment surface, micronization treatment by a sulfuric acid micronization method, or the like; or cleaning treatment with an organic solvent or water. Removal treatment by ion exchange method or the like;

It is preferred that the organic pigment has a uniform particle size.

When the coloring agent (A) contains an organic pigment, the pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained by dispersing the pigment dispersant.

The pigment dispersant may be a cationic surfactant, an anionic surfactant, a nonionic surfactant, or a surfactant of any of the two, for example, a polyester-based surfactant, a polyamine-based surfactant, an acrylic surfactant, or the like. These pigment dispersing agents may be used alone or in combination of two or more.

When the coloring agent (A) contains a pigment dispersant, the amount thereof is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less based on 1 part by mass of the organic pigment.

When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in which the pigment is uniformly dispersed is easily obtained, which is preferable.

The content of the coloring agent (A) is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, still more preferably 18 to 50% by mass based on the solid content of the colored photosensitive resin composition. quality%.

Here, the solid content means a total amount of components other than the solvent removed from the colored photosensitive resin composition.

In the colored photosensitive resin composition of the present invention, when the content of the coloring agent (A) is within the above range, a color filter having a sufficient color density can be easily obtained, and since the binder resin (B) is easily contained in a necessary amount, It is easy to form a pattern with sufficient mechanical strength.

In the colorant (A), the content of the organic pigment is 20 to 97% by mass, preferably 30 to 95% by mass, and more preferably 40 to 95% by mass.

In particular, when the colorant (A) comprises CI Pigment Blue 15:6 and the compound (1), the mass ratio of the two is preferably (CI Pigment Blue 15:6): compound (1) = 97:3 to 50:50. (CI Pigment Blue 15:6): Compound (1) = 97:3 to 70:30 is more preferable.

In the coloring photosensitive resin composition, if the content of the organic pigment in the coloring agent (A) is within the above range, a high-density color filter can be easily obtained. Further, when the content is in the above range, the optimization of the transmission spectrum is simple.

The above coloring agent (A), that is, a coloring agent containing the above compound (1), is also one of the present inventions.

The coloring agent of the present invention is useful as a material for coloring a photosensitive resin composition as described above, and is used as an ink coloring agent for inkjet ink recording, a coating material, a printing ink, a coloring agent for plastics, and a coloring agent for various color filters. Etc. Also useful.

The colored photosensitive resin composition of the present invention contains a binder resin (B).

The binder resin (B) preferably contains a constituent unit derived from (meth)acrylic acid. Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid. The content of the constituent unit derived from the (meth)acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 16 mol% or more, based on the molar fraction of all constituent units constituting the binder resin (B). It is 18 mol% or more and 38 mol% or less. When the binder resin (B) contains a constituent unit derived from (meth)acrylic acid, the solubility in the non-pixel portion is good at the time of development, and it is difficult to leave a residue in the non-pixel portion after development, and the content is The above range is preferred.

The above-mentioned binder resin (B) may be a copolymer of (meth)acrylic acid and another monomer.

The other monomer, for example, an aromatic vinyl compound, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid aminoalkyl ester, an unsaturated carboxylic acid glycidyl ester, a vinyl carboxylate, an unsaturated ether , a vinyl cyanide compound, an unsaturated decylamine, an unsaturated sulfonamide, an aliphatic conjugated diene, or a macromolecule of a monomethyl fluorenyl group or a monomethacryl fluorenyl group at the end of a polymer molecular chain Monomers such as body. Further, the constituent unit derived from a monomer other than (meth)acrylic acid is, for example, a constituent unit represented by the formula (I) or a constituent unit represented by the formula (III).

(In each formula, R ¹¹ and R ¹² each independently represent 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.

The above-mentioned binder resin is specifically: methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / A Acrylic acid Ester copolymer, methacrylic acid/styrene/benzyl methacrylate/N-phenylmaleimide copolymer, methacrylic acid/constitutive unit represented by formula (I) (R ¹¹ represents methyl group) R ¹² represents a hydrogen atom.) / benzyl methacrylate copolymer, a constituent unit represented by the formula (I) (except that R ¹¹ represents a methyl group, and R ¹² represents a hydrogen atom.) / benzyl methacrylate copolymer And methacrylic acid/constituting unit represented by the formula (III) (except that R ¹¹ represents a methyl group, R ¹² represents a hydrogen atom), a styrene copolymer/tricyclodecyl methacrylate copolymer or the like is preferable.

The acid value of the above-mentioned binder resin (B) is usually from 50 to 150, preferably from 60 to 135, particularly preferably from 70 to 135. Since the solubility in the developer is improved, the unexposed portion is easily dissolved, and since the sensitivity is improved, the residual film ratio after development is improved, and the acid value is preferably in the above range.

Here, the acid value is determined by measuring the amount (mg) of potassium hydroxide required for neutralizing 1 g of the acrylic polymer, and usually, it can be obtained by titrating with an aqueous potassium hydroxide solution.

The content of the binder resin (B) is usually 15 to 35 mass%, preferably 18 to 33 mass%, more preferably 21 to 31 mass%, based on the mass fraction of the solid content of the coloring photosensitive resin composition. However, the content of the binder resin (B) is preferably within the above range from the viewpoint that the pattern formation is easy, and the resolution or the residual film ratio is improved.

A binder resin having a constituent unit represented by the formula (I), for example, methacrylic acid/constituting unit represented by the formula (I) (except that R ¹¹ represents a methyl group and R ¹² represents a hydrogen atom.) / benzyl methacrylate The copolymer can be obtained by polymerizing methacrylic acid and benzyl methacrylate into a two-component polymer, and then reacting the two-component polymer with a compound represented by the formula (II) (except that R ¹³ represents a hydrogen atom) get.

(wherein R ¹³ represents a hydrogen atom.)

Methacrylic acid / a constituent represented by the formula (III) (except that R ¹¹ represents a methyl group, R ¹² represents a hydrogen atom) / styrene copolymer / tricyclodecyl methacrylate copolymer, which can be made methyl The monomethacrylate copolymer of benzyl acrylate, methacrylic acid and tricyclodecane skeleton is obtained by reacting 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, particularly preferably 7,000 to 28,000.

In order to improve the hardness of the coating film, increase the residual film ratio, and improve the solubility of the unexposed portion with respect to the developing solution, the resolution is improved, and the binder resin (B) preferably has the average molecular weight within the above range.

The above average molecular weight is a value obtained by conversion from a measured value of GPC [gel permeation chromatography].

In particular, the binder resin (B) represented by the formula (IV) is preferred from the viewpoint 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 which can be polymerized by active radicals, acids, and the like generated from the photopolymerization initiator (D) by irradiation with light, for example, a polymerizable carbon-carbon unsaturated bond. Compounds, etc.

The photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more functional groups (such a photopolymerizable compound is also called a polyfunctional photopolymerizable compound).

The polyfunctional photopolymerizable compound is, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate or the like. .

The colored photosensitive resin composition of the present invention may contain one type of the photopolymerizable compound (C), or may contain two or more types.

The content of the photopolymerizable compound (C) is preferably from 5 to 90% by mass, more preferably from 10 to 80% by mass, based on the solid content of the colored photosensitive resin composition, more preferably from 10 to 80% by mass. 20 to 70% by mass.

In order to sufficiently carry out the hardening, the film thickness ratio before and after the development is increased, the pattern is less likely to have a slit, and the adhesion is good, and the content of the photopolymerizable compound (C) is preferably within the above range.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). The photopolymerization initiator (D) is, for example, an acetophenone-based compound, an active radical generator, an acid generator or the like.

The aforementioned acetophenone-based compound, such as diethoxyacetophenone, 2-methyl-2- Phenyl-1-(4-methylthienyl)propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylacetal, 2-hydroxy-2 -methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-( An oligomer of 1-methylvinyl)phenyl]propan-1-one, etc., preferably 2-methyl-2- Porphyrin-1-(4-methylthienyl)propan-1-one and the like.

The living radical generator generates active radicals due to light irradiation. The above-mentioned living radical generating agent, for example, a benzoin compound, a diphenylketone compound, and 9-oxosulfur Compound, three A compound, an oxime compound, or the like.

The aforementioned benzoin-based compound is, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether or the like.

The aforementioned diphenylketone-based compound, for example, diphenyl ketone, methyl ortho-benzoylbenzoate, 4-phenyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulphate, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 2,4,6-trimethyldiphenyl ketone, and the like.

The aforementioned 9-oxygen sulfur a compound such as 2-isopropyl 9-oxosulfur 4-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 1-chloro-4-propoxy 9-oxosulfur Wait.

The aforementioned three a compound such as 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-(2-(furan-2-yl)vinyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The above lanthanoid compound, for example, an O-mercapto lanthanide compound, specific examples thereof, for example, 1-(4-phenylsulfanyl-phenyl)-but-1,2-dione 2-indole-O-benzene Formate, 1-(4-phenylsulfanyl-phenyl)-octane-1,2-dione 2-indole-O-benzoate, 1-(4-phenylsulfanyl-benzene ))-oct-1-ketooxime-O-acetate, 1-(4-phenylsulfanyl-phenyl)-butan-1-one oxime-O-acetate, and the like.

An active radical generator other than the foregoing exemplified, for example: 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxylic acid Methyl ester, titanocene compound, and the like.

The aforementioned acid generators are, for example, 4-hydroxyphenyldimethyl-p-methanesulfonate, 4-hydroxyphenyldimethylhexafluoroantimonate, 4-ethenoxyphenyldimethyl-p-methanesulfonic acid Bismuth salt, 4-ethenyloxyphenyl ‧ methyl benzyl hexafluoroantimonate cerium salt, triphenyl p-toluene sulfonate cerium salt, triphenyl hexafluoroantimonate cerium salt, diphenyl p-toluene sulfonic acid An onium salt such as a phosphonium salt or a diphenylhexafluoroantimonate or a nitrobenzyl tosylate or a benzoin tosylate.

Further, among the above-mentioned living radical generating agents, there are compounds which simultaneously generate an acid together with active radicals. For example, three A photopolymerization initiator is also used as an acid generator.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 20% by mass, more preferably from 1 to 15% by mass, based on the total amount of the binder resin (B) and the photopolymerizable compound (C). However, from the viewpoint that the sensitivity is improved and the exposure time is shortened, the productivity is improved, but the sensitivity is not too high, and the minimum line width of the resolution pattern is not too wide, and the content of the photopolymerization initiator is preferably within the above range.

The coloring photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (F). The photopolymerization initiation aid (F) is usually used in combination with the photopolymerization initiator (D), and is a compound for promoting polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator.

Photopolymerization initiation aid (F), for example: amine compound, alkoxylated compound, 9-oxosulfur A compound or the like.

The aforementioned amine compound, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)diphenyl ketone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis (ethyl ketone) Aminoamino)diphenyl ketone or the like, wherein 4,4'-bis(diethylamino)diphenyl ketone is preferred.

The alkoxy oxime compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, and the like.

The aforementioned 9-oxygen sulfur a compound such as 2-isopropyl 9-oxosulfur 4-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 1-chloro-4-propoxy 9-oxosulfur Wait.

The photopolymerization initiation aid (F) may be used singly or in combination of two or more. Further, as the photopolymerization initiation aid (F), a commercially available photopolymerization initiation auxiliary (F), for example, the trade name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.), or the like can be used.

In the colored photosensitive resin composition of the present invention, a combination of a photopolymerization initiator (D) and a photopolymerization initiator (F), for example, diethoxyacetophenone/4,4'-bis (diethyl) Aminophenyl)diphenyl ketone, 2-methyl-2- -1,4-(4-methylthienyl)propan-1-one/4,4'-bis(diethylamino)diphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane 1-ketone/4,4'-bis(diethylamino)diphenyl ketone, benzyldimethylketal/4,4'-bis(diethylamino)diphenyl ketone, 2 -hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one/4,4'-bis(diethylamino)diphenyl ketone, 1- Hydroxycyclohexyl phenyl ketone / 4,4'-bis(diethylamino)diphenyl ketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] Propan-1-one oligomer/4,4'-bis(diethylamino)diphenyl ketone, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one/4,4'-bis(diethylamino)diphenyl ketone, etc., preferably 2-methyl-2- Phenyl-1-(4-methylthienyl)propan-1-one / 4,4'-bis(diethylamino)diphenyl ketone.

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

The colored photosensitive resin composition of the present invention contains a solvent (E). The solvent (E) is, for example, an ether, an aromatic hydrocarbon, a ketone, an alcohol, an ester, a guanamine, N-methylpyrrolidone, dimethyl azine or the like.

The above ethers or esters, for example: tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 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 single Propyl ether acetate, methyl cyproterone acetate, ethyl cyproterone acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, A Oxypentyl acetate, anisole, phenethyl ether, methyl anisole, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, C Butyl acrylate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxopropionate, ethyl 3-oxopropionate, 3 -methyl methoxypropionate Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxopropionate, ethyl 2-oxopropionate, 2-oxopropane Acid propyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropane Ethyl acetate, methyl 2-oxo-2-methylpropanoate, ethyl 2-oxo-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy Ethyl 2-methylpropionate, methyl trimethylacetate, ethyl trimethylacetate, propyl trimethylacetate, methyl ethyl acetate, ethyl acetate, 2-oxobutyric acid Ester, ethyl 2-oxobutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, and the like.

The aforementioned aromatic hydrocarbons, for example, benzene, toluene, xylene, Wait.

The ketones are, for example, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-heptanone, cyclopentanone, cyclohexanone and the like.

The aforementioned alcohols are, for example, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin or the like.

The above guanamines are, for example, N,N-dimethylformamide, N,N-dimethylacetamide or the like.

These solvents may be used singly or in combination of two or more.

Solvent (E), for example: diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol, diethyl ether, diethylene glycol dipropyl ether, diethylene glycol Ethers or esters such as dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and ketones, propylene glycol monomethyl ether acetate The ester, propylene glycol monomethyl ether and cyclohexanone are preferred, and these are preferably used in combination.

In the coloring photosensitive resin composition, the content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 90% by mass based on the mass fraction of the coloring photosensitive resin composition. The content of the solvent (E) is preferably within the above range from the viewpoint of easily obtaining a color filter having good flatness at the time of coating and good display characteristics.

The colored photosensitive resin composition of the present invention may further comprise a surfactant (G). The surfactant (G) is, for example, at least one selected from the group consisting of an anthrone-based surfactant and a fluorine-based surfactant.

The anthrone-based surfactant is, for example, a surfactant having a siloxane coupling. Specifically, for example, TORAY SILICONE DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same 29SHPA, same SH30PA, polyether modified oyster sauce SH8400 (trade name: TORAY SILICONE), KP321, KP 322 KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu SILICONE), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (GE Toshiba Ketone).

The anthrone-based surfactant is, for example, an anthrone-based surfactant having a fluorine atom. Such an anthrone-based surfactant is, for example, a surfactant having a siloxane coupling and a fluorocarbon chain. Specifically, for example, MEGAFACE (registered trademark) R08, the same BL20, the same F475, the same F477, the same F443 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and the like.

The fluorine-based surfactant is, for example, a surfactant having a fluorocarbon chain. Specifically, for example, FLUORAD (trade name) FC430, FC431 (Sumitomo 3M (share) system), MEGAFACE (trade name) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (large Japan Ink Chemical Industry Co., Ltd., EFTOP (trade name) EF301, EF303, EF351, EF352 (New Akita Chemical Co., Ltd.), SURFLON (trade name) S381, same S382, same SC101, same as SC105 (Asahi Glass Co., Ltd.), E5844 (manufactured by DAIKIN Fine Chemical Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie Co., Ltd.).

These surfactants may be used singly or in combination of two or more.

The content of the surfactant (G) is preferably 0.0005 to 0.6% by mass, and more preferably 0.001 to 0.5% by mass, based on the mass fraction of the coloring photosensitive resin composition. From the viewpoint of obtaining a flat coating film, the content of the surfactant (G) is preferably within the above range.

The colored photosensitive resin composition of the present invention can provide a highly contrasted coating film.

The color filter formed of the colored photosensitive resin composition of the present invention is also one of the inventions.

The color filter of the present invention can be formed by a photolithography method or an inkjet method.

The photolithography method is, for example, a method in which the colored photosensitive resin composition of the present invention is applied onto a substrate, and a volatile component such as a solvent is removed to form a colored layer, and the colored layer is exposed and exposed through a photomask. . In the method, the colored photosensitive resin composition may be formed on a substrate from a resin layer obtained from another colored photosensitive resin composition, and applied to the resin layer.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

The components used in the present embodiment are as follows, and the following description may be omitted.

(A-1) Colorant composition: C. I. Pigment Blue 15:6

(A-2) Coloring agent component: The following compounds (NK-9402, manufactured by Hayashibara Biochemical Research Institute Co., Ltd.)

(A-3) Coloring agent component: The following compounds (NK-8635, manufactured by Hayashibara Biochemical Research Institute Co., Ltd.)

(A-4) Coloring agent component: The following compounds (NK-9422, manufactured by Hayashibara Biochemical Research Institute Co., Ltd.)

(A-5) Coloring agent component: The following compounds (NK-9424, manufactured by Hayashibara Biochemical Research Institute Co., Ltd.)

(A-6) Coloring agent component: The following compounds (NK-9425, manufactured by Hayashibara Biochemical Research Institute Co., Ltd.)

<Synthesis of Resin (B-1)>

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 182 g of propylene glycol monomethyl ether acetate was added, and the gas atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 20.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 A solution of 3.6 g of azobisisobutyronitrile was added dropwise to a mixture of g (0.10 mol) and propylene glycol monomethyl ether acetate (136 g), and stirring was continued at 100 °C. Next, the gas atmosphere in the flask was changed from nitrogen to air, and 35.5 g of propylene methacrylate was added to the flask [0.25 mol, (50 mol% relative to the carboxyl group of the methacrylic acid used in the reaction)] Further, 0.9 g of dimethylaminomethylphenol and 0.145 g of hydroquinone were stirred 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.

The measurement of the polystyrene-equivalent weight average molecular weight of the above resin was carried out under the following conditions using a GPC method.

Device; HLC-8120GPC (TOSOH system)

Pipe string; TSK-GELG2000HXL

Column temperature; 40 ° C

Solvent; THF

Flow rate; 1.0 mL/min

The concentration of the liquid solid component to be tested is 0.001 to 0.01% by mass.

Injection volume; 50μL

Detector; RI

Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH)

(C-1) Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

(D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one

(F-1) Photopolymerization start-up aid: 4,4'-bis(diethylamino)diphenyl ketone

(E-1) Solvent: propylene glycol monomethyl ether acetate

(E-2) Solvent: propylene glycol monomethyl ether

(E-3) Solvent: cyclohexanone

(G-1) Surfactant: MEGAFACEF475 (made by Dainippon Ink Chemical Industry Co., Ltd.)

Example 1

[Preparation of Colored Photosensitive Resin Composition 1]

will

(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

The mixture was mixed to obtain a colored photosensitive resin composition 1.

[Formation of patterns]

The glass substrate [#1737; manufactured by Corning Co., Ltd.] was applied onto the colored photosensitive resin composition 1 obtained by the spin coating method, and then dried at 100 ° C for 3 minutes to volatilize the volatile component (solvent). The mixture was cooled to form a layer of the colored photosensitive resin composition 1. The colored photosensitive resin composition layer was exposed to light by irradiating an i-ray (wavelength: 365 nm) through a photomask. The light source of the i-line uses an ultra-high pressure mercury lamp, and the amount of illumination is 150 mJ/cm ² . Thereafter, heat treatment was carried out at 220 ° C for 20 minutes to form a coating film. The film thickness of this coating film was 2.2 μm.

Example 2

[Preparation of Colored Photosensitive Resin Composition 2]

will

(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

The coloring photosensitive resin composition 2 was obtained by mixing. A coating film was obtained in the same manner as in Example 1 except that the colored photosensitive resin composition 1 was changed to the coloring photosensitive resin composition 2.

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

The coloring photosensitive resin composition 3 was obtained by mixing. A coating film was obtained in the same manner as in Example 1 except that the colored photosensitive resin composition 1 was changed to the coloring photosensitive resin composition 3.

[Evaluation 1]

For the coating film on the obtained glass substrate, a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used, and a C light source was irradiated to measure the xy chromaticity coordinates (Bx, By) in the XYZ color system of CIE. And brightness. The results are shown in Table 1.

Each of the coating films obtained from the colored photosensitive resin compositions of Example 1, Example 2 or Example 3 was confirmed from Table 1 to have excellent lightness.

Fig. 1 shows the transmittance of the coating film obtained in Example 1.

This transmittance was measured in the same manner as the above brightness. The horizontal axis represents the wavelength and the vertical axis represents the transmittance.

As shown in Fig. 1, since the colored photosensitive resin composition of Example 1 contains the coloring agent of the present invention, it is possible to optimize the transmission spectrum to make the brightness higher. In Examples 2 and 3, the transmission spectrum was the same as in Example 1.

Example 4

[Preparation of Colored Photosensitive Resin Composition 4]

will

(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

The colored photosensitive resin composition 4 was obtained by mixing.

[Formation of patterns]

The colored photosensitive resin composition 4 obtained above was applied by spin coating on a glass substrate [#1737; manufactured by Corning Co., Ltd.], and then dried at 100 ° C for 3 minutes to volatilize volatile components, and then cooled to form a colored color. A layer of the photosensitive resin composition 4. The coloring photosensitive resin composition layer was exposed to light by irradiating an i-ray [wavelength: 365 nm] through a mask. The light source of the i-line uses an ultra-high pressure mercury lamp, and the amount of illumination is set to 150 mJ/cm ² . Thereafter, heat treatment was carried out at 220 ° C for 20 minutes to form a coating film. The film thickness of the coating film was 2.2 um.

Example 5

[Preparation of Colored Photosensitive Resin Composition 5]

will

(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

The coloring photosensitive resin composition 5 was obtained by mixing. A coating film was obtained in the same manner as in Example 4 except that the colored photosensitive resin composition 4 was changed to the coloring photosensitive resin composition 5.

[Evaluation]

With respect to the coating film on the obtained glass substrate, the chromaticity and the lightness were measured in the same manner as in the above evaluation 1. The results are shown in Table 2.

As shown in Table 2, each of the coating films obtained from the colored photosensitive resin compositions obtained in Example 4 or Example 5 was confirmed to have excellent lightness.

Fig. 2 shows the transmittance of the coating film obtained in Example 4. This transmittance was measured in the same manner as the above brightness. The horizontal axis represents the wavelength and the vertical axis represents the transmittance.

As shown in Fig. 2, since the colored photosensitive resin composition of Example 4 contains the coloring agent of the present invention, the brightness can be further improved by optimizing the transmission spectrum.

Regarding Example 5, the transmission spectrum was equivalent to that of Example 4.

(industrial use)

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

Figure 1 shows the transmittance of Example 1.

Figure 2 shows the transmittance of Example 4.

Claims (16)

A colored photosensitive resin composition for a color filter comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). The colorant (A) contains the compound (1) having the structure represented by the formula (1): [wherein, ring Z ¹ and ring Z ² are each independently represented by a heterocyclic ring which may have a substituent; 1 represents an integer of 0 or more and 3 or less; m represents 1]. The coloring photosensitive resin composition for a color filter according to the first aspect of the invention, wherein the compound (1) is represented by the following formula (1a): [wherein, ring Z ¹ , ring Z ² , l and m are each the same as the first item of the patent application; X ^- represents a halogen anion, ClO ₄ ^- , OH ^- , a monovalent organic carboxylate anion, a monovalent organic sulfonate Anion, monovalent boron anion or monovalent organometallic complex anion]. The colored photosensitive resin composition for a color filter according to the first aspect of the invention, wherein the compound (1) is represented by the formula (2a): [wherein, ring Z ⁵ and ring Z ⁶ are each independently, and 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 ^- , a monovalent organic carboxylate anion, a monovalent organic sulfonate anion, a monovalent boron anion or a monovalent organic metal complex anion; n represents an integer of 0 or more and 3 or less; and A ¹ and A ² are each independently represent an oxygen atom and sulfur. An atom, a selenium atom, a carbon atom or a nitrogen atom; R ¹ and R ² each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom or 1 An aliphatic hydrocarbon group having a valence of 1 to 6 carbon atoms, or an aliphatic hydrocarbon group having 2 to 2 carbon atoms formed by integrating one R ³ and one R ⁴ ; and a and b are each independently, and represent 0 or more and 2 or less. Integer]. A coloring photosensitive resin composition for a color filter according to claim 3, wherein n is 1. A coloring photosensitive resin composition for a color filter according to claim 3 or 4, wherein Y ^- is a monovalent organic sulfonate anion. The colored photosensitive resin composition for a color filter according to the first aspect of the invention, wherein the compound (1) is represented by the following formula (1b): [wherein, ring Z ¹ , ring Z ² , l and m, each of which is the same as claim 1; ring Z ³ and ring Z ⁴ are each independently, and represent a hetero ring which may have a substituent; X ^a- represents a halogen Anion, ClO ₄ ^- , OH ^- , organic carboxylate anion, organic sulfonate anion, boron anion or organometallic complex anion; a represents the valence of X ^a- ; l' represents an integer of 0 or more and 3; m' Represents 1; L ¹ represents a divalent hydrocarbon group which may be substituted]. The colored photosensitive resin composition for a color filter according to the sixth aspect of the invention, wherein the compound (1) is represented by the following formula (2b): [wherein, ring Z ⁷ , ring Z ⁸ , ring Z ⁹ and ring Z ¹⁰ , each independently, represent a benzene ring or a naphthalene ring which may have a substituent; Y ^b- represents a halogen anion, ClO ₄ ^- , OH ^- , organic carboxylate anion, organic sulfonate anion, boron anion or organometallic complex anion; b represents the valence of Y ^b- , and when b is 1, each Y ^b- may be the same or different; ² and n ³ each independently represent an integer of 0 or more and 3 or less; A ³ , A ⁴ , A ⁵ and A ⁶ are each independently and 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 the carbon number of the aliphatic having 1 to 6 of the hydrocarbon group, or represents an R ⁵ is a R ⁶ together form the divalent carbon atoms, an aliphatic hydrocarbon group having 2 to 6 of; R ⁷ And R ⁸ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an aliphatic hydrocarbon group having 2 to 2 carbon atoms and 2 to 6 formed by integrating one R ⁷ and one R ^{8 .} And R ⁹ and R ¹⁰ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; L ² represents a divalent hydrocarbon group which may be substituted; c, d, e and f are each independently , indicating 0 An integer of 2 or less]. A coloring photosensitive resin composition for a color filter according to the seventh aspect of the invention, wherein n ² and n ^{3 are} each 1 . A coloring photosensitive resin composition for a color filter according to the seventh or eighth aspect of the invention, wherein Y ^b- is a divalent organic sulfonate anion. A coloring photosensitive resin composition for a color filter according to claim 7 or 8, wherein b is 2, one of Y ^b- is a monovalent organic sulfonate anion, and the other Y ^b- is Halogen anion. The coloring photosensitive resin composition for a color filter according to any one of claims 1 to 4, wherein the coloring agent (A) further contains an organic pigment. The coloring photosensitive resin composition for a color filter according to claim 11, wherein the organic pigment is C.I. Pigment Blue 15:6. A coloring photosensitive resin composition for a color filter according to claim 12, wherein a mass ratio of CI Pigment Blue 15:6 to compound (1) is (CI Pigment Blue 15:6): compound (1) =97:3~50:50. A color filter comprising the colored photosensitive resin composition for a color filter according to any one of claims 1 to 13. A filter according to claim 14, wherein the filter is formed by a photolithography method or an inkjet method. A coloring agent for a color filter comprising a compound (1) having a structure represented by the formula (1): [wherein, ring Z ¹ and ring Z ² are each independently represented by a heterocyclic ring which may have a substituent; 1 is an integer of 0 or more and 3 or less; m represents 1].