KR20180022617A - Colored curable resin composition, color filter and display device - Google Patents

Abstract

[PROBLEMS] The chemical resistance of a color filter formed from a conventional colored curable resin composition may not be sufficiently satisfactory.
The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D) SO ₃ ^- group and / or -COO ^- group, and a metal cation having two or more valences.
The present invention also relates to a color filter which is a cured product of the above-mentioned colored curable resin composition and a display device including the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored curable resin composition, a color filter,

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used for the production of a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. As such a colored curable resin composition, a colored curable resin composition containing a compound represented by the following formula is known (Patent Document 1).

[Chemical Formula 1]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-32999

The chemical resistance of the color filter formed of the color-curable resin composition containing the above-described known compounds may not be satisfactory enough.

The present invention includes the following inventions.

[1] A colorant composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D)

Wherein the colorant (A) contains a compound comprising a xanthene skeleton, an anion having a -SO ₃ ^- group and / or a -COO ^- group, and a divalent or higher metal cation.

[2] The colored curable resin composition according to [1], wherein the compound is a compound represented by the formula (Ia-2).

(2)

In formula (Ia-2), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group of 1 to 10 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group of R ³¹ and R ³² , -SO ₃ ^-, -COO ^-, may be substituted monovalent aromatic hydrocarbon group or a halogen atom in the 6 to 10 carbon atoms, hydrogen atoms contained groups aromatic hydrocarbon monovalent art 1, -SO ₃ ^-, -COO ^-, or C 1 And -CH ₃ - included in the monovalent saturated hydrocarbon group of R ³¹ and R ³² may be substituted with -O-, -CO- or -NR ¹¹ -.

R ³³ and R ³⁴ are, independently of each other, -SO ₃ ^-, -COO ^-, represents an alkylsulfonyl group having from 1 to 4 carbon atoms, having from 1 to 4 carbon atoms in the alkyl or sulfanyl group having from 1 to 4 carbon atoms in the.

R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p1 and p2 independently represent an integer of 0 to 5; When p1 is 2 or more, plural R ^{33 s} may be the same or different, and when p 2 is 2 or more, plural R ^{34 s} may be the same or different.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Mr ⁺ represents a metal cation of rvalue.

k represents an integer of 1 to 3; q represents an integer of 1 or more. R represents an integer of 2 or more. n represents an integer of 1 or more. However, k, q, n, and r satisfy k × q = n × r.

[3] The colored curable resin composition according to [1] or [2], which does not contain a dispersant different from the resin (B).

[4] A color filter which is a coated cured product of the colored curable resin composition according to any one of [1] to [3].

[5] A display device comprising the color filter according to [4].

According to the colored curable resin composition of the present invention, a color filter excellent in chemical resistance can be formed.

The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator, wherein the colorant (A) comprises a xanthene skeleton and a --SO ₃ ^- group and / (I) comprising an anion having a -COO ^- group and a metal cation having a valence of 2 or more. The colored curable resin composition of the present invention preferably does not contain a dispersant different from the resin (B). The colored curable resin composition of the present invention may contain a solvent (E) and a leveling agent (F). The present compound (I) also includes tautomers, stereoisomers and salts thereof. Each of the components and functional groups exemplified below can be used alone or in combination.

In the above compound (I), the total number of -SO ₃ ^- group and / or -COO ^- group is preferably 2 to 4, more preferably 2 to 3.

In the above compound (I), the number of -SO ₃ ^- groups is preferably 1 to 4, more preferably 1 to 3.

In the compound (I), the total number of -COO ^- groups is preferably 1 to 3, more preferably 1 or 2.

In the above compound (I), the -SO ₃ ^- group and / or the -COO ^- group may be bonded directly to the xanthan skeleton or may be bonded to the xanthan skeleton through one or more groups selected from -R ⁵⁰ - and -NR ⁵¹ - Or may be combined. -R ⁵⁰ - is preferable that the above combination 3 above and / or 6 of the xanthene skeleton-is preferable, and, -NR ⁵¹ bonded on the 9 xanthene skeleton.

R ⁵⁰ represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ⁵¹ represents a hydrogen atom, a divalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.

Examples of the divalent or higher metal cation include alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion and barium ion, and alkaline earth metal ions such as titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, Transition metal ions and typical metal ions such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion and bismuth ion are preferable and alkaline earth metal ion and transition metal ion are preferable, and calcium ion, magnesium ion Ions, barium ions, manganese ions, iron (III) ions, and cobalt (II) ions are more preferable.

The valence of the metal cation is preferably 2 to 5, more preferably 2 to 4, still more preferably 2 to 3.

The compound (I) is preferably a compound represented by the formula (Ia) (hereinafter sometimes referred to as " compound (Ia) ").

(3)

[In the formula (Ia), R ¹ to R ⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent aromatic group having 6 to 10 carbon atoms which may have a substituent -CH ₂ - included in the monovalent saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -. At least one stage of R ¹ ~ R ^{4 1-valent} saturated hydrocarbon group, and R ¹ ~ R ^{4 1-valent} aromatic hydrocarbon group represented by the represented by the group, as a substituent -SO ₃ ^- group has ^- groups and / or -COO. R ¹ and R ² may be taken together to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be taken together to form a ring containing a nitrogen atom.

R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Mr ⁺ represents a metal cation of rvalue.

k represents an integer of 1 to 3; q represents an integer of 1 or more. R represents an integer of 2 or more. n represents an integer of 1 or more. However, k, q, n, and r satisfy k × q = n × r.

In the following description, the side having negative charge in compound (Ia) may be referred to as anion (Ia-A). The anion (Ia-A) is represented by the formula (Ia-A). The anion (Ia-A) also includes tautomers and stereoisomers thereof.

[Chemical Formula 4]

[In the formula (Ia-A), R ¹ to R ⁷ , k are as defined above.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesyl group, a propylphenyl group and a butylphenyl group. The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ is preferably a phenyl group. Examples of the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁵⁰ and R ⁵¹ include groups in which one of the hydrogen atoms contained in the monovalent aromatic hydrocarbon group in R ¹ to R ⁴ is bonded.

^{R 1 ~ R 4, R 50} , R 51 may have one or two divalent aromatic hydrocarbon group having in the as substituents, -SO ₃ ^-, -COO ^-, halogen atoms, -R ^8, -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- can be exemplified by _{^{Z +, -COOH, -CO 2 R}} 8, -SR 8, -SO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ^10, It is preferable that these substituents substitute hydrogen atoms included in the monovalent or divalent aromatic hydrocarbon group. Among these, as the _{^{substituent, -SO 3 -, -COO -,}} -SO 3 H, -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are _{^{preferred, -SO 3 -, -COO -,}} -SO 3 ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ is the more preferred. Examples of _{^{Z +, -SO 3 - - -SO}} 3 In this case, the N (R ¹¹⁾ ₄ are preferred. When R ¹ to R ⁴ are these groups, the coloring curable resin composition containing the compound (I) of the present invention can form a color filter having less occurrence of foreign matter and excellent in heat resistance.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated aliphatic hydrocarbon group may be -O-, -CO -, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, A straight chain alkyl group such as a methyl group, a butyl group, a heptyl group, a heptyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group and an icosyl group; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group. The monovalent saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. As the divalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁵⁰ and R ⁵¹ , one of the hydrogen atoms contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ is bonded .

R ¹ ~ R ^4, R ⁵⁰ and R ⁵¹ include a hydrogen atom that is monovalent or divalent groups of the saturated hydrocarbon, for _{^{example, -SO 3 -, -COO -,}} 1 -valent aromatic hydrocarbon group having 6 to 10 group or may be substituted with a halogen atom, preferably -COO ^-, may be a monovalent of 6 to 10 carbon atoms optionally substituted aromatic hydrocarbon group or a halogen atom. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may substitute the hydrogen atom of the monovalent or divalent saturated hydrocarbon group of R ¹ to R ⁴ , R ⁵⁰ and R ⁵¹ include a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ And the same groups as the groups exemplified as the monovalent aromatic hydrocarbon group of 1 to 10 carbon atoms.

The hydrogen atom contained in the monovalent saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxyl group or a halogen atom as a substituent.

The ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include, for example, the following.

[Chemical Formula 5]

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an eicosyloxy group Alkyloxy groups, and the like.

Examples of -CO ₂ R ⁸ include alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group and the like .

Examples of -SR ⁸ include alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and icosylsulfanyl group.

Examples of -SO ₂ R ⁸ include an alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include alkyloxys such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and icosyloxysulfonyl group, And the like.

Examples of -SO ₂ NR ⁹ R ^10, for example, sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) Sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group N-1 substituted sulfamoyl groups such as N-1 substituted sulfamoyl groups;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

Examples of the alkyl group having 1 to 6 carbon atoms for R ⁶ and R ⁷ include those having 1 to 6 carbon atoms in the above alkyl groups. Among them, as R ⁶ and R ⁷ , a hydrogen atom is preferable.

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is _{^{a, + N (R 11) 4}} , Na + or K ^+, preferably N ⁺ (R ¹¹⁾ _4.

As the ⁺ N (R ¹¹ ) ₄ , it is preferable that at least two of the four R ^{11 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R < ¹¹ > s is preferably 20 to 80, more preferably 20 to 60. [

k is an integer of 1 to 3, preferably an integer of 1 to 2.

q is an integer of 1 or more, preferably 1 to 5, more preferably 1 to 4, still more preferably 1 to 3.

In the compound represented by the formula (Ia), 2 ~ 4 of -SO ₃ ^- groups are preferably contained, and the one -SO ₃ ^- it is also desirable that contains groups ^- group 1 to 3 -COO.

In the formula (Ia), -SO ₃ ^- group, at least R ¹ ~ R ⁴ substituted with one 1 to 3 of the hydrogen atoms contained more aromatic hydrocarbon groups represented by valence and it is more preferred that at least R ¹ ~ R ⁴ More preferably one or two hydrogen atoms contained in the monovalent aromatic hydrocarbon group represented by R < 2 >

In the formula (Ia), -COO ^- group, a hydrogen atom included in the monovalent saturated hydrocarbon groups represented by one, two, or three, or R ¹ ~ R ⁴ of the hydrogen atoms contained groups monovalent aromatic hydrocarbon group represented by R ¹ ~ R ⁴ the more it preferred that substituted 1 to 3, and which comprises groups monovalent saturated hydrocarbon represented by one or two or R ¹ ~ R ⁴ of the hydrogen atoms contained groups monovalent aromatic hydrocarbon group represented by R ¹ ~ R ⁴ And it is more preferable that 1 to 2 hydrogen atoms are substituted.

In the compound represented by the formula (Ia), the total number of -SO ₃ ^- group and / or --COO ^- group for substituting hydrogen atoms contained in one aromatic hydrocarbon group is preferably one, and it is preferable that one saturated hydrocarbon group It is preferable that the total number of -SO ₃ ^- group and / or -COO ^- group which substitutes for the hydrogen atom contained is one.

Examples of the r-valent metal cation represented by Mr ^< ⁺ > include an alkaline earth metal cation such as a magnesium ion, a calcium ion, a strontium ion and a barium ion such as titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, Transition metal cations such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions and bismuth ions, and alkaline earth metal cations and transition metal cations are preferable, and calcium Ion, magnesium ion, barium ion, manganese ion, iron (III) ion and cobalt (II) ion are more preferable.

r is an integer of 2 or more, preferably 2 to 5, more preferably 2 to 4, still more preferably 2 to 3.

n is an integer of 1 or more, preferably 1 to 3, more preferably 1 to 2.

In equation (Ia), k, q, n, and r satisfy k x q = n x r. For this reason, the compound (Ia) has a valence of 0, that is, an electrically neutral compound.

The combination of r and k is preferably (I) to (VI), more preferably (I) to (IV).

(I) a combination in which r is 2 and k is 1

(II) a combination wherein r is 3 and k is 1

(III) a combination wherein r is 2 and k is 2

(IV) a combination wherein r is 3 and k is 2

(V) r is 2 and k is 3

(VI) a combination in which r is 3 and k is 3

In the compound (Ia), it is preferable that R ¹ and R ⁴ independently of each other are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R ² and R ³ independently represent a substituent Is preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may be present, and R ⁶ and R ⁷ are preferably independently a hydrogen atom.

In the compound (Ia), R ¹ and R ⁴ are each independently a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have at least one group selected from a saturated hydrocarbon group and a -SO ₃ ^- group and, R ² and R ³ are, independently of one another, -COO ^- groups may good number of carbon atoms is more preferred 1-20 monovalent saturated hydrocarbon group, and, R ⁶ and R ⁷ are, independently from each other than a hydrogen atom has desirable.

Two or more compounds (Ia) may be used in combination. When two or more compounds (Ia) are combined, a combination of (I) and (III) or a combination of (II) and (IV) is preferable.

As the compound (Ia), a compound represented by the formula (Ia-1) (hereinafter occasionally referred to as "the compound (Ia-1)") is preferred. The compound (Ia-1) may be a tautomer or a stereoisomer thereof.

[Chemical Formula 6]

In the formula (Ia-1), R ²¹ to R ²⁴ independently represent a hydrogen atom, -R ^26, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R stage at least one of a monovalent aromatic hydrocarbon group represented by the dog ²¹ ~ R ²⁴ 1-valent saturated hydrocarbon group, and R ²¹ ~ R ²⁴ may appear to have, as a substituent -SO ₃ ^- group has ^- groups and / or -COO. R ²¹ and R ²² may be taken together to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be taken together to form a ring containing a nitrogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with -SO ₃ ^- or -COO ^- .

k, q, r, n and Mr ⁺ have the same meanings as defined above.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ include the same groups as those described above as the monovalent aromatic hydrocarbon group of R ¹ to R ⁴ . Hydrogen atoms contained groups aromatic hydrocarbon monovalent art _{^{1, -SO 3 -, -COO -,}} -SO 3 H, -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁵ or -SO ₂ NHR ^25.

Z 1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .

R ²⁵ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a benzyl group.

As the combination of R ²¹ to R ²⁴ , it is preferable that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, hydrogen atoms contained in the monovalent aromatic hydrocarbon group are -SO _{^{3 -, -COO -, -SO 3}} H, -SO 3 - as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. A more preferred combination, R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a group 1-valent aromatic hydrocarbon group of 6 to 10 carbon atoms, hydrogen atoms, aromatic hydrocarbon groups -SO contained monovalent art ₁₃ ^-, - COO ^-, -SO ₃ ^-, which will be substituted with Z1 ⁺ or -SO ₂ NHR ^26.

The ring containing the nitrogen atom formed by R ²¹ and R ²² together and the ring containing the nitrogen atom formed by R ²³ and R ²⁴ together are the same as the ring formed by R ¹ and R ² together . Of these, aliphatic heterocyclic rings are preferred. Examples of the aliphatic heterocycle include the following.

(7)

Examples of the monovalent saturated hydrocarbon group of 1 to 20 carbon atoms represented by R ²⁵ to R ²⁷ include the same groups as those of the monovalent saturated hydrocarbon group represented by R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are-R ²⁶ , -R ²⁶ is preferably independently a methyl group, an ethyl group or a propyl group.

Also, -SO ₃ R ²⁶ and -SO ₂ R ²⁶ as in the NHR ^26, a branched alkyl group having 3 to 20 carbon atoms are preferred, the branched chain alkyl group having a carbon number of 6 to 12 more preferred, and 2-ethylhexyl Is more preferable.

As the ⁺ N (R ²⁷ ) ₄ , it is preferable that at least two of the four R ^{27 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R < ²⁷ > s is preferably from 20 to 80, more preferably from 20 to 60. [ When ⁺ N (R ²⁷ ) ₄ is present in the compound (Ia-1), R ²⁷ may be the same or different.

Formula (Ia-1) compound, 2 to 4 represented by -SO ₃ ^- group is preferably contained, and the one -SO ₃ ^- it is also desirable that contains groups ^- group 1 to 3 -COO.

In the formula _{(Ia-1), -SO 3} - group, at least R ²¹ and R 1 ^24-valent more preferred that the substituted one, two, or three of the hydrogen atoms included in the aromatic hydrocarbon groups, at least represented by R ²¹ to More preferably 1 to 2 hydrogen atoms contained in the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R < ^{24 &} gt ;.

In the formula (Ia-1), 1 ~ 3 of -COO ^- group, R ²¹ ~ R ²⁴ include a hydrogen atom that is a monovalent saturated hydrocarbon groups represented by R ²⁶ is a hydrogen atom or a monovalent aromatic hydrocarbon groups containing 1 indicated by 1 More preferably, one or two hydrogen atoms contained in a monovalent saturated hydrocarbon group represented by R ²⁶ or a hydrogen atom contained in a monovalent aromatic hydrocarbon group represented by R ²¹ to R ²⁴ are substituted .

In the compound represented by the formula (Ia-1), the total number of the -SO ₃ ^- group and / or the --COO ^- group for substituting the hydrogen atom contained in one aromatic hydrocarbon group is preferably one, It is preferable that the total number of -SO ₃ ^- groups and / or -COO ^- groups replacing the hydrogen atoms contained in the hydrocarbon group is one.

In the compound (Ia-1), R ²¹ and R ²³ are preferably, independently of each other, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R ²² and R ²⁴ , Is preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the rivalent metal cation represented by Mr ^< ⁺ > is preferably an alkaline earth metal cation or a transition metal cation.

In the compound (Ia-1), R ²¹ and R ²³ are each independently a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have at least one group selected from a saturated hydrocarbon group and -SO ₃ ^- group More preferably, R ²² and R ²⁴ are each independently a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a -COO ^- group, more preferably a rivalent metal cation represented by Mr ⁺ Magnesium ion, barium ion, manganese ion, iron (III) ion and cobalt (II) ion.

Also, as the compound (Ia), a compound represented by the formula (Ia-2) (hereinafter sometimes referred to as "the compound (Ia-2)") is also preferable. The compound (Ia-2) may be a tautomer or a stereoisomer thereof.

[Chemical Formula 8]

In formula (Ia-2), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group of 1 to 10 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group of R ³¹ and R ³² , -SO ₃ ^-, -COO ^-, may be substituted monovalent aromatic hydrocarbon group or a halogen atom in the 6 to 10 carbon atoms, hydrogen atoms contained groups aromatic hydrocarbon monovalent art 1, -SO ₃ ^-, -COO ^-, or C 1 And -CH ₃ - included in the monovalent saturated hydrocarbon group of R ³¹ and R ³² may be substituted with -O-, -CO- or -NR ¹¹ -.

R ³³ and R ³⁴ are, independently of each other, -SO ₃ ^-, -COO ^-, represents an alkylsulfonyl group having from 1 to 4 carbon atoms, having from 1 to 4 carbon atoms in the alkyl or sulfanyl group having from 1 to 4 carbon atoms in the.

R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p1 and p2 independently represent an integer of 0 to 5; When p1 is 2 or more, plural R ^{33 s} may be the same or different, and when p 2 is 2 or more, plural R ^{34 s} may be the same or different.

R ¹¹ , q, r, n and Mr ⁺ have the same meanings as defined above.]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² include groups having 1 to 10 carbon atoms in R ⁸ .

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted for the hydrogen atom contained in the monovalent saturated hydrocarbon group in R ³¹ and R ³² include the same groups as those in R ¹ .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group and a propoxy group.

R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

R ³³ and R ³⁴ as, -SO ₃ ^-, -COO ^-, or carbon atoms and the alkyl group preferably 1 to 4, -SO ₃ ^-, -COO ^-, or more preferably a methyl group.

p1 and p2 are preferably an integer of 0 to 2, and preferably 1 or 2.

Formula (Ia-2) compound, 2 to 4 represented by -SO ₃ ^- group is preferably contained, and the one -SO ₃ ^- it is also desirable that contains groups ^- group 1 to 3 -COO.

In the formula (Ia-2), have one to 3 of R ³³ and R ³⁴ -SO ₃ ^- group, and more preferably, R ³³ and R 1 ~ ³⁴ 2 -SO ₃ dogs of ^- is more preferably caused.

In the formula (Ia-2), 1 to 3 of R ³³ and R ³⁴ are -COO ^- groups, or 1 to 3 of the hydrogen atoms contained in the monovalent saturated hydrocarbon group in which the -COO ^- group is represented by R ³¹ to R ³² substituted, it is more preferable that the dog one or two of R ³³ and R ³⁴ -COO ^- group, or, -COO ^- groups 1-2 of the hydrogen atoms contained groups monovalent saturated hydrocarbon group represented by R ³¹ ~ R ³² gae Is more preferable.

In the compound represented by formula (Ia-2), 1 -SO ₃ for replacing the hydrogen atom contained aromatic hydrocarbon groups ^- groups and / or -COO ^- total number of the group is preferably in one individual, one saturated It is preferable that the total number of -SO ₃ ^- groups and / or -COO ^- groups replacing the hydrogen atoms contained in the hydrocarbon group is one.

In the compound (Ia-2), it is preferable that R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ³³ and R ³⁴ , -SO ₃ ^- and -COO ^- , and the r-metal cation represented by Mr ⁺ is preferably an alkaline earth metal cation or a transition metal cation, and p 1 and p 2 are each independently an integer of 0 to 4 .

In the compound (Ia-2), R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a -COO ^- group, more preferably R ³³ and R ³⁴ are a Independently, -SO ₃ ^- . More preferably, the r-valent metal cation represented by Mr ⁺ is more preferably a calcium ion, a magnesium ion, a barium ion, a manganese ion, an iron (III) ion or a cobalt (II) ion , And p1 and p2 are each independently 0 or 1.

Examples of the anion (Ia-A) include anions represented by the formulas (Aa-1) to (Aa-88).

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

As the compound (I), the following compounds are preferable.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

Among them, the compounds (I-1) to (I-12), (I-89) to (I-100), (I-177) (I-7), (I-8), (I-95), (I-96), (I-183) -184, I-271, I-272, I-359, I-360, I-388 and I-427.

In the colored curable resin composition of the present invention, the content of the compound (I) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the colored curable resin composition, More preferably 0.5 to 5% by mass.

The term "total amount of solid content" in the present specification means the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component can be measured by a known analytical means such as liquid chromatography or gas chromatography.

≪ Colorant (A) >

The colorant (A) may contain the dye (A1) and the pigment (A2) in addition to the compound (I).

The dye (A1) is not particularly limited and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes and the like. Examples of the dyes include compounds classified in the color index (published by The Society of Dyers and Colourists) as having a color other than the pigment, and known dyes described in the dyeing notes (coloring yarn). According to the chemical structure, the azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, Styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and the description is only of the number, hereinafter), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98 , 99, 117, 162, 163, 167, 189;

C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86,;

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, Solvent dyes,

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76 , 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172 , 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281 , 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C. I. Acid Violet 6 B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45 , 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: , 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147 , 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236 , 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, , CI acid dyes such as 104, 105, 106 and 109,

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84 , 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153 , 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196 , 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246 , 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

CI direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77,

C.I. Disperse Yellow 51, 54, 76;

C. I. Disperse Violet 26, 27;

CI Disperse dyes such as C.I. Disperse Blue 1, 14, 56, 60,

C. I. Basic Red 1, 9, 10;

CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68, 81, 83, 88, 89;

C. I. Basic violet 2;

C. I. Basic dye such as C. I. Basic Green 1;

C. I. Reactive Yellow 2, 76, 116;

C. I. Reactive Orange 16;

C.I. Reactive Red 36;

CI. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

C.I.Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

CI Modern Violet 1, 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

CI modern blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

C.I.Moddant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41,

And C.I. bat dyes such as C. I. Bat Green 1 and the like.

These dyes may be appropriately selected in accordance with the spectral spectrum of a desired color filter.

The pigment (A2) is not particularly limited, and known pigments can be used. For example, pigments classified as pigments in the color index (The Society of Dyers and Colourists) can be mentioned.

As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

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

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

C.I. Green pigments such as Pigment Green 7, 36, and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Pigment black 1, pigment black 7, and the like.

As the pigment, C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like are preferable, and C.I. Pigment Blue 15: 3, 15: 6, and C.I. Pigment violet 23 is more preferable, and C.I. Pigment Blue 15: 6 is more preferable. By including the above pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter can be improved.

The pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group has been introduced, a graft treatment to the surface of the pigment with a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

The pigment preferably has a uniform particle size. By containing a pigment dispersant and carrying out a dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersing agents may be used alone or in combination of two or more. Examples of the pigment dispersant include trade name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyowa Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA) (Manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk (manufactured by Big Chemical).

When a pigment dispersant is used, the amount thereof is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the amount of the pigment dispersant is in the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

In the case of containing the dye (A1) and the pigment (A2), the content ratio of the dye (A1) to the pigment (A2) (dye (A1) / pigment (A2)) in the colorant (A) Is preferably from 1/99 to 99/1, more preferably from 3/97 to 40/60, and still more preferably from 5/95 to 30/70.

The content of the compound (I) in the colorant (A) is preferably from 1 to 99% by mass, more preferably from 30 to 90% by mass, and still more preferably from 40 to 80% by mass, based on the total amount of the colorant (A) Mass%.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 7 to 55% by mass, and still more preferably from 9 to 50% by mass, based on the total solid content. When the content of the colorant (A) is within the above range, the color density when formed into a color filter is sufficient and a sufficient amount of resin or polymerizable compound can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed .

≪ Resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

(A) (hereinafter may be referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a resin having a carbon number of 2 to 4 A copolymer having a structural unit derived from a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter also referred to as "(b)");

The resin (K2) is a copolymer of a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) Hereinafter sometimes referred to as " (c) ");

Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

Resin [K4]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

Resin [K5]: a copolymer having a structural unit derived from (b) and a structural unit derived from (c);

Resin [K6]: a copolymer having (a) added to a structural unit derived from (b), a structural unit further comprising a carbonic acid anhydride and a structural unit derived from (c).

(a) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxycyclo [2.2.1] hept-2-eno anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl] unsaturated monocarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxy group in the same molecule, such as? - (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(b) is a compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenic unsaturated bond Refers to a polymerizable compound. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter may be referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, (Hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydropyrrole group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)") and the like.

(b1-1) having a structure in which a straight chain or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter may be referred to as "(b1-1)"), alicyclic unsaturated And a monomer (b1-2) having a structure in which a hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl Acrylate (for example, Cyclamel M100, manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate , A compound represented by the formula (BI) and a compound represented by the formula (BII).

(23)

[In the formula (BI) and the formula (BII), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

R ^a and R ^b represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Indicates the hand in combination with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

As R ^a and R ^b , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are exemplified, and more preferable examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, , 6-diyl group, and the like.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * - CH ₂ CH ₂ -O- (wherein * represents a bond with O).

Examples of the compound represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among them, the formula (BI-1), the formula (BI-3), the formula (BI-5), the formula (BI-7), the formula (BI- ) Are preferable, and compounds represented by the formula (BI-1), the formula (BI-7), the formula (BI-9) or the formula (BI-15) are more preferable.

≪ EMI ID =

(25)

Examples of the compound represented by the formula (BII) include compounds represented by any one of the formulas (BII-1) to (BII-15). (BII-1), BII-3, BII-5, BII-7, BII-9 or BII-11 to BII- ), And compounds represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15) are more preferable.

(26)

(27)

The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio thereof (compound represented by formula (BI): compound represented by formula (BII)) is preferably 5: 95 to 95: 5, and more preferably from 20:80 to 80:20.

(b2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyloxetane, 3-methyl- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

(b3), a monomer having a tetrahydropyrryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that reliability of the obtained color filter can be further improved, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable because the storage stability of the colored curable resin composition is excellent.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate (referred to in the art as " dicyclopentanyl (meth) acrylate ") as tricyclo [5.2.1.0 ^2,6 ] decan- (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate Quot; dicyclopentenyl (meth) acrylate " (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (Meth) acrylates such as phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] - ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hept- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] 2,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Cyclohexyl [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1 ] Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] , And 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoint of copolymerization reactivity and heat resistance Do.

In the resin [K1], the ratio of the respective structural units derived from among all the structural units constituting the resin [K1]

(a); 2 to 60 mol%

(b); a structural unit derived from 40 to 98 mol%

, ≪ / RTI >

(a) in an amount of 10 to 50 mol%

(b); 50 to 90 mol%

Is more preferable.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the resulting color filter are excellent.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by the Chemical Society of Japan, 1st Edition, 1st Edition, March 1, 1972, Can be prepared by reference to the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by, for example, nitrogen to form a deoxidized atmosphere, . The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and organic peroxides such as benzoyl peroxide As the solvent, any solvent may be used as long as it dissolves the respective monomers. As the solvent (E) of the colored curable resin composition of the present invention, there may be mentioned a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, either a concentrated or diluted solution may be used, or a solid (powder) obtained by re-precipitation or the like may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition of the present invention, The manufacturing process of the composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each other is preferably such that, among all structural units constituting the resin [K2]

(a); 2 to 45 mol%

(b); 2 to 95 mol%

(c) 1 to 65 mol%

, ≪ / RTI >

(a); 5 to 40 mol%

(b); 5 to 80 mol%

(c): 5 to 60 mol%

Is more preferable.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability in forming the colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are excellent There is a tendency.

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In the resin [K3], the ratio of the respective structural units derived from the resin [K3]

(a); 2 to 60 mol%

(c): 40 to 98 mol%

, ≪ / RTI >

(a) in an amount of 10 to 50 mol%

(c): 50 to 90 mol%

Is more preferable.

The resin [K3] can be produced, for example, in the same manner as described for the method of producing the resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carbonic acid and / or a carbonic anhydride having (a) .

First, the copolymer of (a) and (c) is prepared in the same manner as described for the resin [K1]. In this case, the proportion of the structural units derived from each of them is preferably the same as that of the resin [K3].

Next, a cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carbonic acid and / or the carbonic acid anhydride derived from (a) in the copolymer.

Subsequently to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b) a reaction catalyst of a carboxylic acid or a carbonic acid anhydride and a cyclic ether Resin [K4] can be prepared by placing a polymerization inhibitor (for example, hydroquinone or the like) or the like in a flask, for example, at 60 to 130 ° C for 1 to 10 hours .

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting the content within this range, there is a tendency that the balance between the storage stability of the colored curable resin composition, the developability in forming the pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tends to be good. (B1) is preferably used as the resin (K4), and (b1-1) is preferable because the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the charging method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. In addition, in the same manner as in the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of resin [K1]. As in the case of the above, the solution after the reaction may be used as it is, or a solution obtained by concentrating or diluting it, or taken out as a solid (powder) by re-precipitation or the like may be used.

the proportion of the structural units derived from the structural units (b) and (c) is preferably such that the total number of moles of the structural units constituting the above-

(b); 5 to 95 mol%

(c): 5 to 95 mol%

, ≪ / RTI >

(b); 10 to 90 mol%

(c) a structural unit derived from 10 to 90 mol%

Is more preferable.

Further, by reacting a cyclic ether derived from (b) having a copolymer of (b) and (c) with a carboxylic acid or a carbonic acid anhydride of (a) in the same manner as in the production of the resin [K4] , And resin [K5] can be obtained.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) used in the resin [K5] is preferably (b1) and more preferably (b1-1) because the reactivity of the cyclic ether is high and unreacted (b)

Resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether and a carbonic acid or a carboxylic acid anhydride.

Examples of the carbonic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxycyclo [2.2.1] hept-2-ene anhydride. The amount of the carbonic anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (Meth) acrylic acid / 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / vinyltoluene copolymer, glycidyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Resins [K2] such as (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (Meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, [K3] a resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (Meth) acrylate, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / [K4] a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (Meth) acrylic acid to a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate such as a resin obtained by reacting a copolymer of (meth) acrylic acid with And a resin [K6] such as a resin obtained by further reacting a tetrahydrophthalic anhydride with the resin.

Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K2] is particularly preferable.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility to the developing solution of the unexposed portion is good, and the resolution of the coloring pattern tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g in terms of solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of the solid matter. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tends to be improved.

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of being polymerized by an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenic unsaturated bond, Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) , Dipentaerythritol hexa (metha) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta (metha) acrylate, tetrapentaerythritol deca (metha) acrylate, tetrapentaerythritol nona (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa , Propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate Sites, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a color pattern and the chemical resistance of the color filter tend to be improved.

≪ Polymerization initiator (D) >

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and nonimidazole compounds.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1). Herein, * denotes a combined hand.

(28)

　

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy- 1- [9-ethyl-6- ( 3-yl] -3-cyclopentylpropan-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- 3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxime compound is preferably an N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- , And N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine are more preferable. If these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). Among these partial structures, the benzene ring may have a substituent.

[Chemical Formula 29]

　

　

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinyl) phenyl] butane-1-one, 2- (dimethylamino) 1-on. IRGACURE 369, 907, 379 (manufactured by BASF Co., Ltd.) or the like may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1- On oligomers,?,? - diethoxyacetophenone, benzyldimethyl ketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

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-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Dimethyl-2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373), 2 Bis (2-chlorophenyl) -4,4 ', 5,5' -tetraphenylbiimidazole, 2,2'-bis -Tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis 2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid- ), An imidazole compound in which the phenyl group at the 4,4 ', 5,5', 1-position is substituted by a carboalkoxy group (for example, Japanese Patent Hei 7-10913, such as dogs, see JP.) And the like.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like Benzophenone compounds, quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone and camphorquinone, 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, . These are preferably used in combination with the polymerization initiator D1 (particularly amines) described below.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p- Toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium-p-toluenesulfonate, Onium salts such as toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyltosylates, benzoin tosylates, and the like.

As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds and nonimidazole compounds is preferable, and O -Acyloxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity of the color filter tends to be shortened and the exposure time is shortened.

≪ Polymerization initiator (D1) >

The polymerization initiator (D1) is a compound or a sensitizer used for promoting polymerization of a polymerizable compound initiated by polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carbonic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Diethylamino) benzophenone, 4, 4'-bis (dimethylamino) benzophenone (commonly called Mihiraazuketone), 4,4'- 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

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

Examples of the carbonic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chloro Phenylsulfanyl acetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiator (D1) is used, its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Mass part. When the amount of the polymerization initiator (D1) is within this range, it is possible to form a colored pattern with higher sensitivity, and the productivity of the color filter tends to be improved.

≪ Solvent (E) >

The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like. These solvents may be used alone or in combination of two or more.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Butyl propionate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and? -Butyrolactone.

Examples of the ether solvent include 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, propylene Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, And the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, Pentanone, cyclohexanone, and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetoamide and N-methylpyrrolidone.

Among these solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, N-methylpyrrolidone, Propanone, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solids in the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristics are not insufficient when the color filter is formed, so that display characteristics tend to be good.

≪ Leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Concretely, Torei silicone DC3PA, copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA and Copper SH8400 (trade names: TORAY DOW CORNING CO., LTD.), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan Joint- .

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, it is possible to use the florid (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177 copper copper F554 copper R30, RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, EF303, EF351 and EF352 (manufactured by MISBISMaterial Electronics Co., Ltd.) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Tablet Chemical Industry Co., Ltd.).

Examples of the silicon-containing surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Copolymer BL20, Copolymer F475, Copolymer F477 and Copolymer F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content thereof is preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, and more preferably 0.002 mass% or more and 0.1 mass% or less with respect to the total amount of the colored curable resin composition Is not less than 0.003 mass% and not more than 0.05 mass%. The content of the pigment dispersant is not included in the content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other components>

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

&Lt; Process for producing colored curable resin composition &gt;

The colored curable resin composition of the present invention can be obtained, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) F) and other components.

In the case of using the pigment (A2), it is preferable to mix it with a part or the whole of the solvent (E) and disperse it with a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The desired colored curable resin composition can be prepared by mixing the remaining components in the thus obtained pigment dispersion to a predetermined concentration.

The dye (A1) may be previously dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the solution with a filter having a pore size of 0.01 to 1 mu m or so.

The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Among them, the photolithography method is preferable. In the photolithography method, the above-mentioned colored curable resin composition is applied to a substrate, followed by drying to form a colored composition layer, and the colored composition layer is exposed through a photomask to perform development. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask during exposure and / or not developing it. A colored pattern or a colored coating film which is a cured product of the colored curable resin composition of the present invention thus formed can be used as the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited and can be suitably adjusted in accordance with the purpose and application, and is, for example, 0.1 to 30 탆, preferably 0.1 to 20 탆, more preferably 0.5 to 6 탆 .

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silicon on the surface, resin plates such as polycarbonate, polymethylmethacrylate and polyethylene terephthalate, silicon, , Silver, copper / palladium alloy thin film, or the like is formed. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be performed by a known apparatus or condition. For example, it can be manufactured as follows.

First, a colored curable resin composition is coated on a substrate and dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.

Examples of the application method include a spin coating method, a slit coating method, and a slit and spin coating method.

The temperature in the case of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In the case of performing the reduced-pressure drying, it is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The film thickness of the coloring composition layer is not particularly limited and may be suitably selected in accordance with the intended thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm may be cut using a filter that cuts this wavelength region, or light having a wavelength in the vicinity of 436 nm, a wavelength in the vicinity of 408 nm, and a wavelength in the vicinity of 365 nm may be selectively extracted using a band- Maybe. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because uniform light rays can be uniformly irradiated to the entire exposure surface or the photomask and the substrate on which the coloring composition layer is formed can be precisely aligned.

The colored composition layer after exposure is brought into contact with a developing solution to develop a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

The developing method may be any of a paddle method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development.

After development, it is preferable to rinse with water.

In addition, post-baking is preferably performed on the obtained coloring pattern. The post-baking temperature is preferably 150 to 250 占 폚, more preferably 160 to 235 占 폚. The post baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the colored curable resin composition of the present invention, a color filter having excellent chemical resistance can be produced. Such a color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, but the present invention may be carried out by appropriately modifying them in a range that is suitable for the purpose Of course, they are all within the technical scope of the present invention.

In the following description, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

In the following examples, the structure of the compound was confirmed by mass spectrometry (LC: Agilent 1200 type, MASS: Agilent LC / MSD type).

[Synthesis Example 1]

(30)

　

10 parts of a dye represented by the formula (X) (50 parts), 9.0 parts of potassium carbonate and 12.0 parts of 1-bromopropane were added to a flask equipped with a stirrer, RTI ID = 0.0 &gt; C &lt; / RTI &gt; The resulting reaction solution was added to 350 parts of 2N hydrochloric acid, and the mixture was stirred at room temperature for 30 minutes to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 8.0 parts of a compound represented by the formula (A-IM).

(31)

Identification of compounds represented by formula (A-IM)

(Mass spectrometry) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 819.2 and 739.5

Exact Mass: 818.2 and 738.2

[Synthesis Example 2]

1 part of the compound represented by the formula (A-IM), 9.9 parts of distilled water and 0.08 part of sodium hydroxide were added to a flask equipped with a stirrer, a condenser and a cooling tube, and 4 parts of barium chloride dihydrate and 10 parts of distilled water 14 parts were added dropwise to precipitate a solid. (A mixture of the compound (I-359) and the compound (I-360)) represented by the formula (A-1) was obtained by removing the solid by decantation and thoroughly washing with ion- I got wealth.

(32)

[Synthesis Examples 3 to 6]

(A-2) was obtained in the same manner as in Synthesis Example 2 except that barium chloride dihydrate was changed to calcium chloride, manganese chloride tetrahydrate, iron (III) chloride hexahydrate and cobalt chloride hexahydrate, respectively A mixture of the compound (I-95) and the compound (I-96) represented by the formula (A-3), the compound represented by the formula (A-4) (A mixture of the compound (I-183) and the compound (I-184)) represented by the formula (A-5) .

(33)

(34)

(35)

(36)

[Synthesis Example 7]

(37)

A flask equipped with a condenser and a cooling tube was charged with 1 part of Pink Base (manufactured by Xinyou Chemical Co., Ltd.) represented by the formula (Y), 7 parts of N-methylpyrrolidone, 1.0 part of potassium carbonate and 2.0 parts of ethyl 4-bromobutyrate And further stirred at 100 DEG C for 7 hours and a half. After allowing to cool, 20 parts of 2N hydrochloric acid was added to the reaction solution obtained, and the mixture was extracted twice with 45 parts of chloroform, washed with saturated aqueous sodium chloride together with chloroform layer, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was dried under reduced pressure at 60 ° C to obtain 4.1 parts of a compound represented by the formula (A-6-IM1).

(38)

Identification of the compound represented by the formula (A-6-IM1)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 803.5

Exact Mass: 802.3

[Synthesis Example 8]

4.1 parts of the compound represented by the formula (A-6-IM1), 9.8 parts of methanol and 3.5 parts of an aqueous 8% sodium hydroxide solution were added to a flask equipped with a stirrer and a cooling tube, and the mixture was stirred at room temperature for 6 hours. The resulting reaction solution was added to 30 parts of 2N hydrochloric acid, and the mixture was stirred at room temperature for 30 minutes to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 1.0 part of a compound represented by the formula (A-6-IM2) (compound (Aa-75)).

[Chemical Formula 39]

Identification of the compound (compound (Aa-75)) represented by the formula (A-6-IM2)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 747.5

Exact Mass: 746.3

[Synthesis Example 9]

7 parts of the compound (compound (Aa-75)) represented by the formula (A-6-IM2), 61 parts of distilled water and 0.82 part of sodium hydroxide were added to a flask equipped with a stirrer and a cooling tube, And 26.55 parts of a metal salt aqueous solution prepared with 19 parts of distilled water were added dropwise to precipitate a solid. The solid was separated by decantation, washed well with ion-exchanged water, and dried under reduced pressure at 60 캜 to obtain 5.8 parts of a compound (Compound I-427) represented by the formula (A-6).

(40)

[Synthesis Example 10]

Into a flask equipped with a cooling tube and a stirrer were added 3 parts of Pink Base (manufactured by Sekisui Chemical Co., Ltd.) represented by the formula (Y), 21 parts of N-methylpyrrolidone and 1.7 parts of t-butoxy potassium, and the mixture was stirred at room temperature for 30 minutes Then, 1.6 parts of 1-bromopropane was added, and the mixture was stirred at the same temperature for 1 hour. The obtained reaction solution was added to 21 parts of 2N hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.0 parts of a compound represented by the formula (A-7-IM1).

(41)

Identification of compounds represented by formula (A-7-IM1)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 617.5

Exact Mass: 616.2

[Synthesis Example 11]

1 part of the compound represented by the formula (A-7-IM1), 7 parts of N-methylpyrrolidone, 0.5 part of potassium carbonate and 1.0 part of ethyl 4-bromobutyrate were added to a flask equipped with a stirrer, Lt; / RTI &gt; for 5 hours and a half. The obtained reaction solution was added to 35 parts of 2N hydrochloric acid, and the mixture was stirred at room temperature for 30 minutes to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 1.2 parts of a compound represented by the formula (A-7-IM2).

(42)

Identification of a compound represented by the formula (A-7-IM2)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 731.5

Exact Mass: 730.3

[Synthesis Example 12]

1 part of the compound represented by the formula (A-7-IM2), 7 parts of methanol and 2.7 parts of an aqueous 8% sodium hydroxide solution were added to a flask equipped with a stirrer and a cooling tube, and the mixture was stirred at room temperature for 3 hours and a half. The resulting reaction solution was added to 21 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, but crystals were precipitated. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 0.9 part of a compound represented by the formula (A-7-IM3) (compound (Aa-36)).

(43)

Identification of the compound (compound (Aa-36)) represented by the formula (A-7-IM3)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 703.5

Exact Mass: 702.3

[Synthesis Example 13]

5 parts of a compound represented by the formula (A-7-IM3) (compound (Aa-36)), 5 parts of methanol, 62 parts of distilled water and 0.31 part of sodium hydroxide were added to a flask equipped with a stirrer, 1.90 parts of barium chloride dihydrate and 7.50 parts of aqueous metal salt solution prepared to 5.58 parts of distilled water were added dropwise to precipitate a solid. The solid was separated by decantation, washed well with ion-exchanged water, and dried under reduced pressure at 60 占 폚 to obtain 5.1 parts of a compound represented by the formula (A-7) (compound (I-388)).

(44)

[Synthesis Example 14]

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added and heated to 70 캜 with stirring. Subsequently, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) : 50) was dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution. The solution was dropped into a flask kept at 70 占 폚 for 4 hours using a dropping funnel.

[Chemical Formula 45]

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 4 hours using another dropping funnel . After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70 占 폚 for 4 hours and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 占⁰³ , the molecular weight distribution was 2.16, the solid content was 34.8% To obtain a resin B1 solution having an acid value of 81 mg-KOH / g. Resin B1 has the following structural unit.

(46)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in Synthesis Example 14 were measured by the GPC method under the following conditions.

Apparatus: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 占 폚

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL / min

Detector; RI

TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained in the above was regarded as molecular weight distribution.

Examples 1 to 7 and Comparative Example 1

(Preparation of colored curable resin composition)

Each component was mixed with the following composition to obtain a colored curable resin composition.

[Table 9]

In Table 9, each component represents the following compound.

(A-1): A compound represented by the formula (A-1)

(A-2): A compound represented by the formula (A-2)

(A-3): A compound represented by the formula (A-3)

(A-4): A compound represented by the formula (A-4)

(A-5): A compound represented by the formula (A-5)

(A-6): A compound represented by the formula (A-6)

(A-7): A compound represented by the formula (A-7)

(A-x): a mixture of compounds represented by the following formula

(47)

(B-1): Resin B1 (in terms of solid content)

(C-1): dipentaerythritol hexaacrylate (Kayalad (registered trademark) DPHA; manufactured by Nippon Yakuza Co., Ltd.)

(Irgacure (registered trademark) OXE 01, manufactured by BASF) was added to the mixture of (D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl)

(E-1): N-methylpyrrolidone

(E-2): Propylene glycol monomethyl ether acetate

(F-1): polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.)

&Lt; Fabrication of coloring pattern &

The colored curable resin composition was coated on a glass substrate (Eagle 2000; Corning) having a 5 cm edge by spin coating, and then pre-baked at 100 占 폚 for 3 minutes to obtain a colored composition layer. After cooling, the space between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 mu m and the exposure amount (365 nm) was measured using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) ). As the photomask, a 100 μm line and space pattern was formed. After the light irradiation, the coloring composition layer was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 DEG C for 60 seconds, washed with water and then subjected to post-baking in an oven at 230 DEG C for 20 minutes To obtain a colored pattern.

&Lt; Measurement of film thickness &

With respect to the obtained coloring pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.)). The results are shown in Table 10.

<Evaluation of Chemical Resistance>

Spectroscopy was measured using a colorimeter (OSP-SP-200, manufactured by Olympus Co., Ltd.) with respect to the obtained coloring pattern, and the xy chromaticity coordinates (x, y ) And stimulus value Y were measured. The obtained color pattern was immersed in N-methylpyrrolidone at 50 占 폚 for 30 minutes. After the immersion, the xy chromaticity coordinates (x, y) and Y were measured in the same manner as before immersion, and the color difference Eab * was calculated from the measured values by the method described in JIS Z 8730: 2009 (7th Color Difference Calculation Method). Based on the Eab * of the colored curable composition obtained in Comparative Example 1, the improvement rate of chemical resistance was calculated according to the following formula. The results are shown in Table 10.

(%) Of Example k = {(Eab * of Comparative Example 1 - Eab * of Example k) / Eab *} 100 of Comparative Example 1 (wherein k represents an integer of 1 to 7)

[Table 10]

According to the colored curable resin composition of the examples, it was confirmed that the obtained color pattern was excellent in chemical resistance. From this, it can be seen that the colored coating film and the colored pattern obtained from the colored curable resin composition of the present invention are excellent in chemical resistance.

According to the colored curable resin composition of the present invention, a color filter having good chemical resistance can be formed. Such a color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

Claims (5)

(A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D)
The colorant (A) is, xanthene skeleton and -SO ₃ ^- groups and / or -COO ^- colored curable resin composition containing the anion and a compound which contains two or more metal cations having a group. The method according to claim 1,
The colored curable resin composition according to claim 1, wherein the compound is a compound represented by formula (Ia-2).
[Chemical Formula 1]

In formula (Ia-2), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group of 1 to 10 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group of R ³¹ and R ³² , -SO ₃ ^-, -COO ^-, may be substituted monovalent aromatic hydrocarbon group or a halogen atom in the 6 to 10 carbon atoms, hydrogen atoms contained groups aromatic hydrocarbon monovalent art 1, -SO ₃ ^-, -COO ^-, or C 1 And -CH ₃ - included in the monovalent saturated hydrocarbon group of R ³¹ and R ³² may be substituted with -O-, -CO- or -NR ¹¹ -.
R ³³ and R ³⁴ are, independently of each other, -SO ₃ ^-, -COO ^-, represents an alkylsulfonyl group having from 1 to 4 carbon atoms, having from 1 to 4 carbon atoms in the alkyl or sulfanyl group having from 1 to 4 carbon atoms in the.
R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.
p1 and p2 independently represent an integer of 0 to 5; When p1 is 2 or more, plural R ^{33 s} may be the same or different, and when p 2 is 2 or more, plural R ^{34 s} may be the same or different.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
Mr ⁺ represents a metal cation of rvalue.
k represents an integer of 1 to 3; q represents an integer of 1 or more. r represents an integer of 2 or more. n represents an integer of 1 or more. However, k, q, n, and r satisfy k × q = n × r. The method according to claim 1,
And does not contain a dispersant different from the resin (B). A color filter which is a coated cured product of the colored curable resin composition according to claim 1. A display device comprising the color filter according to claim 4.