TWI600968B - Colored curable resin composition - Google Patents

Description

Colored curable resin composition

The present invention relates to a color hardening 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 panel, an electroluminescence panel, or a plasma display panel. As such a color-curable resin composition, as a coloring agent, a color-hardening resin composition containing only xanthene (also known as "dibenzopyran") dye and CI pigment blue is known (JP2010-32999- A).

The conventional colored curable resin composition is not sufficiently satisfactory in comparison with the color filter obtained by the colored curable resin composition.

The present invention encompasses the following inventions.

[1] A colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant contains a xanthene dye and an anthraquinone dye.

[2] The colored curable resin composition according to [1], wherein the content of the anthraquinone dye is 0.1% by mass or more and 70% by mass or less based on the total amount of the coloring agent.

[3] The colored curable resin composition according to [1] or [2], wherein the colorant further contains a pigment.

[4] A color filter comprising the colored curable resin composition according to any one of [1] to [3].

[5] A display device comprising the color filter described in [4].

By the colored curable resin composition of the present invention, a high contrast color filter can be formed.

21‧‧‧ glass substrate

22‧‧‧TFT (switching element)

22a‧‧‧Gate electrode

22b‧‧‧gate insulating film

22c‧‧‧Multi-crystalline enamel film

22d‧‧‧Protective film

23‧‧‧ color filter layer

23A‧‧‧Coloring curable resin composition layer (color filter)

23a‧‧‧Red color filter

23b‧‧‧Green color filter

23c‧‧‧Blue color filter

24‧‧‧pixel electrode

27‧‧‧ Signal Line

29‧‧‧Photosensitive resin film (protective film)

201, 202‧‧‧ connection holes

Fig. 1 is a schematic view showing a method of manufacturing a color filter of the present invention.

Fig. 2 is a schematic view showing a method of manufacturing the color filter of the present invention.

Fig. 3 is a schematic view showing the method of manufacturing the color filter of the present invention.

The colored curable resin composition of the present invention is a color-curable resin composition containing a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and a coloring agent (A) It contains xanthene dye (Aa) and anthraquinone dye (Ab). It is preferred to further contain the solvent (E) and/or the leveling agent (F).

The colored curable resin composition of the present invention can produce a high contrast color filter by containing a xanthene dye (Aa) and an anthraquinone dye (Ab) as a colorant (A).

<Colorant (A)>

The coloring agent (A) contains a xanthene dye (Aa) and an anthraquinone dye (Ab). It is preferred to further contain a pigment (Ad). Further, a dye different from xanthene dye (Aa) and an anthraquinone dye (Ab) (hereinafter also referred to as "dye (Ac)") may be contained.

Xanthene dye (Aa) is a compound containing a xanthene skeleton in the molecule. Dye. Xanthene dye (Aa), for example, CI acid red 51 (hereinafter, the description of CI acid red is omitted, only the number is shown. Others are similarly omitted) 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30 , 102, CI alkaline red 1 (Rose red 6G), 2, 3, 4, 8, CI alkaline red 10 (Rose red B), 11, CI alkaline purple 10, 11, 25, CI solvent red 218, CI mordant red 27, CI reaction red 36 (Bengal rose red B), sulforhodamine G, JP2010-32999-A, xanthene dyes, and xanthene dyes described in JP4492760-B. It is preferred to dissolve in an organic solvent.

Among these, a dye containing a compound represented by the formula (1a) (hereinafter also referred to as "compound (1a)") is preferred for the xanthene dye (Aa). Compound (1a) may be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. In particular, the xanthene dye (Aa) is preferably only the compound (1a).

[In the formula (1a), R ¹ to R ⁴ independently of each other represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, the saturated hydrocarbon group The hydrogen atom may be substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the saturated hydrocarbon group may be contained. -CH ₂ - may be substituted by -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together with a nitrogen atom.

R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

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

m represents an integer from 0 to 5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same or different. However, when R ⁵ is -SO ₃ ^- , m is 1.

a represents an integer of 0 or 1.

X represents a halogen atom.

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

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

R ⁹ and R ¹⁰ each 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 - contained in the saturated aliphatic hydrocarbon group may be -O-, -CO -, -NH- or -NR ⁸ - substituted. R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocyclic ring having a nitrogen atom of 3 to 10 membered rings together with a nitrogen atom.

R ¹¹ independently of each other 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.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a 2,4,6-trimethylphenyl group (mesityl), and a propylphenyl group. Butylphenyl.

The aromatic hydrocarbon group may have a substituent, and examples thereof include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, - CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ or the like. Among these, as the substituent, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ^{10 are} preferred, and more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ . In this case, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ^{4 are the above-} mentioned groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter having less generation of foreign matter and excellent heat resistance.

A ring containing a nitrogen atom formed by R ¹ and R ² together with a nitrogen atom, and a ring containing a nitrogen atom formed by R ³ and R ⁴ together with a nitrogen atom may, for example, be as follows.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ⁸ to R ¹¹ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a decyl group. a linear alkyl group having 1 to 20 carbon atoms such as dodecyl, hexadecyl or eicosyl; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. a branched chain alkyl group having 3 to 20 carbon atoms; 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 or a tricyclodecyl group.

-OR ⁸ , for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosane Oxygen.

-CO ₂ R ⁸ may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tertiary butoxycarbonyl group, a hexyloxycarbonyl group or an eicosyloxycarbonyl group.

-SR ⁸ may, for example, be a methylsulfanyl group, an ethylthio group, a butylthio group, a hexylthio group, a thiol group or an eicosylthio group.

-SO ₂ R ⁸ may, for example, be a methylsulfonyl group, an ethylsulfonyl group, a butasulfonyl group, a hexylsulfonyl group, a sulfonyl group or an eicosylsulfonyl group.

-SO ₃ R ⁸ may, for example, be a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tertiary butyl sulfonyl group, a hexyloxysulfonyl group or an eicosyloxysulfonyl group.

-SO ₂ NR ⁹ R ¹⁰ , for example, sulfamoyl; N-methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonyl, N-iso Propylsulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N- Amylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethyl Propyl)aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl Aminesulfonyl, N-(3-methylbutyl)aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N-(1,3-dimethylbutyl) Aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N- (1,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl) N-monosubstituted amine sulfonyl group such as hexylamine sulfonyl group, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl group, N , N-ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N , N-propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tertiary butylmethylamine sulfonyl, N,N-butylethylamine sulfonate An N,N-disubstituted amine sulfonyl group such as N,N-bis(1-methylpropyl)aminesulfonyl, or N,N-heptylmethylaminesulfonyl.

Further, the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ⁹ and R ¹⁰ may have a substituent, and examples thereof include a hydroxyl group and a halogen atom.

R ^{5 is} preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ⁹ , more preferably -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ⁹ .

m is preferably from 1 to 4, more preferably 1 or 2.

The alkyl group having 1 to 6 carbon atoms of R ⁶ and R ⁷ may, for example, be a carbon number of 1 to 6 in the above-mentioned alkyl group.

The aralkyl group having 7 to 10 carbon atoms of R ¹¹ may, for example, be a benzyl group, a phenylethyl group or a phenylbutyl group.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

The above ⁺ N(R ¹¹ ) ₄ , preferably at least two of the four R ¹¹ are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ¹¹ ) ₄ is present in the compound (1a), if R ^{11 is} such a group, the colored curable resin composition of the present invention containing the compound (1a) can form a filter having less foreign matter. Color.

The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter also referred to as "compound (2a)"). Compound (2a) may be a tautomer thereof.

When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

[In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.

R ²¹ and R ²² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom together with a nitrogen atom.

R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ .

M1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, a plurality of R ²⁵ may be the same or different. However, when R ²⁵ is -SO ₃ ^- , m1 is 1.

A1 represents an integer of 0 or 1.

X1 represents a halogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Z1 ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

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

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ²¹ to R ²⁴ may be, for example, the same as those exemplified as the aromatic hydrocarbon group in the above R ¹ to R ⁴ . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

A combination of R ²¹ to R ²⁴ , preferably R ²¹ and R ²³ are a hydrogen atom, R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group is - SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ^{26 are} substituted. More preferably, R ²¹ and R ²³ are a hydrogen atom, R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^- Z1 ⁺ or - SO ₂ NHR ²⁶ replacement.

When R ²¹ to R ^{24 are} these groups, a color-blocking resin composition of the present invention containing the compound (2a) can form a color filter excellent in heat resistance.

A ring containing a nitrogen atom formed by R ²¹ and R ²² together with a nitrogen atom, and a ring containing a nitrogen atom formed by R ²³ and R ²⁴ together with a nitrogen atom, for example, together with R ¹ and R ² together with a nitrogen atom The rings formed are the same. Among them, an aliphatic heterocyclic ring is preferred. The aliphatic heterocyclic ring may, for example, be as follows.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ²⁶ and R ²⁷ may, for example, be the same as those exemplified as the saturated hydrocarbon group among R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are -R ²⁶ , -R ^{26 is} preferably independently a methyl group or an ethyl group. And, -SO ₃ R ^26, and in the -SO ₂ NHR ²⁶ R ²⁶ in a branched chain alkyl group having a carbon number of preferably from 3 to 20, carbon atoms, branched chain alkyl group having 6 to 12 it is more preferred, and still more preferably It is 2-ethylhexyl. When R ^{26 is} such a group, a color filter having a small amount of foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

The above ⁺ N(R ²⁷ ) ₄ , preferably at least two of the four R ²⁷ are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ²⁷ ) ₄ is present in the compound (2a), the colored curable resin composition of the present invention containing the compound (2a) wherein R ²⁷ is a group of these groups can form a filter which generates less foreign matter. Color.

M1 is preferably from 1 to 4, more preferably 1 or 2.

Compound (1a) containing a compound represented by formula (3a) (hereinafter also referred to as The dye of the "compound (3a)" is more preferable. Compound (3a) may be a tautomer thereof. When the compound (3a) is used, the content of the compound (3a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

[In the formula (3a), R ³¹ to R ³² independently of each other represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. Alternatively, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO- or -NR ¹¹ - Replace.

R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and an alkylsulfonyl group having 1 to 4 carbon atoms.

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

p and q independently represent each other from 0 to 5. When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different.

R ^{11 is} identical to the above. ]

The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² may, for example, be a group having 1 to 10 carbon atoms in R ⁸ .

The aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent may, for example, be the same group as in R ¹ .

The alkoxy group having 1 to 3 carbon atoms may, for example, be a methoxy group, an ethoxy group or a propoxy group.

R ³¹ and R ³² are preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms independently of each other.

The alkyl group having 1 to 4 carbon atoms of R ³³ and R ³⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a secondary butyl group or a tertiary butyl group.

The alkylthio group having 1 to 4 carbon atoms in R ³³ and R ³⁴ may, for example, be a methylthio group, an ethylthio group, a propylthio group, a butylthio group or an isopropylthio group.

The alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ may, for example, be methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl or isopropylsulfonate.醯基等.

R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

p and q are preferably an integer of 0 to 2, more preferably 0 or 1.

The compound (1a) may, for example, be a compound represented by each of the formulae (1-1) to (1-42). Further, in the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group. The compound represented by the formula (1-1) to the formula (1-29) corresponds to the compound (2a), and the compound represented by the formula (1-30) to the formula (1-42) corresponds to the compound (3a).

Among these, preferred are C.I. acid red 289 sulfonamide, C.I. acid red 289 grade 4 ammonium salt, C.I. acid violet 102 sulfonamide or C.I. acid violet 102 grade 4 ammonium salt. Examples of such a compound include a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11), and the formula (1-12).

Further, from the viewpoint of excellent solubility in an organic solvent, a compound represented by the formula (1-30) to the formula (1-39) is preferred.

For the xanthene dye (Aa), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Sino-foreign Chemical Co., Ltd., and "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.) can be used. Further, it is also possible to synthesize a commercially available xanthene dye as a starting material, and refer to JP-A-2010-32999.

An anthraquinone dye (Ab) is a dye containing a compound having an anthracene skeleton in the molecule. The anthraquinone dye (Ab) may, for example, be CI Solvent Yellow 117, 163, 167, 189, CI Solvent Orange 77, 86, CI Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI Solvent Green 3, 28 , 29, 32, 33, CI Acid Red 80, CI Acid Green 25, 27, 28, 41, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112 C. I. Disperse Yellow 51 CI disperse violet 26, 27, CI disperse blue 1, 14, 56, 60, CI direct blue 40, CI mordant red 3, 11, CI mord blue 8 and so on.

The anthraquinone dye (Ab) is preferably dissolved in an organic solvent, more preferably a blue, violet or red anthraquinone dye.

Among these, the anthraquinone dye (Ab) is preferably a dye containing a compound represented by the formula (1b) (hereinafter also referred to as "compound (1b)"). When the compound (1b) is used, the content of the compound (1b) in the anthraquinone dye (Ab) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. In particular, the anthraquinone dye (Ab) is preferably a compound (1b).

[In the formula (1b), A represents a hydroxyl group or -NH-R ⁵² .

R ⁵¹ and R ⁵² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent, or a formula (1b') Base

(In the formula (1b'), R ⁵³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -SO ₃ H, -CO ₂ H, -CO ₂ R ⁵⁴ , -NHCOR ⁵⁴ , -SO ₃ R ⁵⁴ or - SO ₂ NR ⁵⁴ R ⁵⁵ .

R ⁵⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, a hydroxyl group or an amine group.

R ⁵⁵ represents a hydrogen atom and a saturated hydrocarbon group having 1 to 10 carbon atoms.

r represents an integer from 0 to 5. When r is 2 or more, a plurality of R ⁵³ may be the same or different.

X ⁵¹ represents a single bond or an alkaneyl group having 1 to 6 carbon atoms.

The compound (1b), when having -SO ₃ H and/or -CO ₂ H, may also form a salt (for example, a Na salt or a K salt).

The aliphatic hydrocarbon group having 1 to 10 carbon atoms of R ⁵¹ and R ⁵² may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a different group. Propyl, isobutyl, secondary butyl, tert-butyl, isopentyl, neopentyl, 2-ethylhexyl and the like.

The aliphatic hydrocarbon group may have a substituent, and may, for example, be a hydroxyl group. Halogen atom, etc.

The alicyclic hydrocarbon group having 3 to 10 carbon atoms of R ⁵¹ and R ⁵² may, for example, be a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

These alicyclic hydrocarbon groups may have a substituent, and examples thereof include a hydroxyl group, a halogen atom and the like.

The alkyl group having 1 to 6 carbon atoms of R ⁵³ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a secondary butyl group or a tertiary butyl group. , isoamyl, neopentyl and the like.

The saturated hydrocarbon group having 1 to 10 carbon atoms of R ⁵⁴ and R ⁵⁵ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. Chain alkyl; branched chain alkyl such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl A saturated alicyclic hydrocarbon group such as a tricyclic fluorenyl group.

-CO ₂ R ⁵⁴ may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tertiary butoxycarbonyl group, a hexyloxycarbonyl group or an eicosyloxycarbonyl group.

-NHCOR ⁵⁴ may, for example, be N-ethinylamino, N-propyl decylamino, N-butyl decylamino, N-isobutyl decylamino and N-trivalylamino (N-pivaloylamino) ).

-SO ₃ R ⁵⁴ may, for example, be a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tertiary butoxysulfonyl group, a hexyloxysulfonyl group or an eicosyloxysulfonyl group.

-SO ₂ NR ⁵⁴ R ⁵⁵ , for example, N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N -butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonyl, N -(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonyl, N-(2,2-dimethylpropyl)amine sulfonyl, N-(1-methylbutyl)amine sulfonyl, N-(2-methylbutyl)amine sulfonyl, N- (3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-cyclohexylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethyl Butyl)aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N -(1,4-Dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl N-monosubstituted amine sulfonyl such as hexylamine sulfonyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl, N-(5-aminopentyl)amine sulfonyl Sulfhydryl; N,N-dimethylamine sulfonyl, N,N-ethylmethylamine sulfonate , N,N-diethylamine sulfonyl, N,N-propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tertiary butylmethylamine sulfonate N,N, N,N-butylethylaminesulfonyl, N,N-bis(1-methylpropyl)aminesulfonyl, N,N-heptylmethylaminesulfonyl, etc. - a disubstituted amine sulfonyl group or the like.

An alkanediyl group having 1 to 6 carbon atoms of X ⁵¹ may, for example, be a methylene group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group or a butane-1,4- group. Dibasic, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, butane-1,3-diyl, 2-methylpropane-1 , 3-diyl, 2-methylpropane-1,2-diyl, butane-1,4-diyl, 2-methylbutane-1,4-diyl, and the like.

The compound (1b) may, for example, be a compound represented by the formula (2-1) to the formula (2-13).

Anthraquinone dye (Ab), CI solvent blue 35 (compound represented by formula (2-4)), CI solvent blue 45, CI acid blue 80 (compound represented by formula (2-11)), CI solvent blue 104 (a compound represented by the formula (2-12)) and CI solvent blue 122 (a compound represented by the formula (2-13)) are preferred. If these dyes are used, a highly contrasting coating film or pattern can be formed, and the generation of foreign matter is small.

The dye (Ac) is not particularly limited as long as it is a dye different from the xanthene dye (Aa) and the anthraquinone dye (Ab), and examples thereof include an oil-soluble dye and an acid. Dyes such as dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes or sulfonamide derivatives of acid dyes, for example, classified in the color index (published by The Society of Dyers and Colourists) A compound of a dye (other than a pigment) or a dye known as a dye note (color dyeing company). Further, examples of the chemical knot include azo dyes, cyanine dyes, triphenylmethane dyes, indigo dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and methine azo dyes. Squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline dye and nitro dye. Among these, an organic solvent-soluble dye is preferred.

Specifically, for example, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI Solvent Red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34, 35 and other CI solvent dye; 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, 34, 35, 37, 42, 44, 50, 57, 66, 73, 80, 88, 91, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 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, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI acid orange 6, 6, 8, 10, 12, 26 , 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 17, 19; CI Acid Blue 1, 7, 9 , 15, 18, 22, 29, 42, 59, 60, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126 , 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259 , 267, 285, 296, 315, 335; CI acid green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. CI acid dye; 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; CI direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71 , 76, 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, 228, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, CI direct dyes such as 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82; CI basic blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 4 1, 54, 58, 59, 64, 65, 66, 67, 68; CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 65; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant blue 1, 2, 3, 7 , 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; CI The mordant green CI 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53 and other CI mordant dyes.

The pigment (Ad) is not particularly limited, and a known pigment can be used, and for example, a compound classified as a pigment by the dye index (published by The Society of Dyers and Colourists).

The pigment may, for example, be CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, Yellow pigments such as 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI pigments orange 13, 13, 36, 38, 40, 42, 43, 51, 55, 59, Orange pigments such as 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224 , 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; CI pigment purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI pigment green 7, 36, 58 and other green pigments; C.I. Pigment brown 23, 25 and other brown pigments; C.I. Pigment black 1, 7 and other black pigments.

The pigment is preferably a blue pigment such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; a purple pigment such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, preferably It is CI Pigment Blue 15:3, 15:6 and CI Pigment Violet 23, and even more preferably CI Pigment Blue 15:6. When the colored curable resin composition of the present invention is prepared into a blue colored curable resin composition, it is easy to optimize the transmission spectrum by containing the above-mentioned pigment, and the light resistance and chemical resistance of the color filter are also improved. It is getting better.

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

The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of a pigment surface with a polymer compound or the like, a sulfuric acid micronization method, or the like. The micronization treatment, the washing treatment of an organic solvent or water for removing impurities, the removal treatment of an ionic impurity by an ion exchange method, or the like.

The pigment has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersion liquid mentioned above may, for example, be a surfactant, an anionic, a nonionic, an amphoteric, a polyester, a polyamine or an acrylic surfactant. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), and Ajisper. (Ajinomoto Fine-Techno (share) system, Disperbyk (BYK company), etc.

When the pigment dispersant is used, the amount thereof to be used 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 (Ad). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

The content of the xanthene dye (Aa) is preferably 0.1% by mass or more and 70% by mass or less, and more preferably 0.5% by mass or more and 50% by mass or less based on the total amount of the coloring agent (A).

The content of the anthraquinone dye (Ab) is preferably 0.1% by mass or more and 70% by mass or less, and more preferably 0.5% by mass or more and 50% by mass or less based on the total amount of the coloring agent (A).

When the coloring agent (A) contains the pigment (Ad), the content of the pigment (Ad) is preferably 10% by mass or more and 99.8% by mass or less, and more preferably 30% by mass or more based on the total amount of the coloring agent (A). 99% by mass or less.

When the coloring agent (A) contains a dye (Ac), the content of the dye (Ac) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more based on the total amount of the coloring agent (A). 30% by mass or less.

When the colorant (A) is a coloring agent composed of a xanthene dye (Aa), an anthraquinone dye (Ab), and a pigment (Ad), the content ratios of these are preferably xanthene dyes (Aa): 0.1% by mass or more and 70% by mass or less

Anthraquinone dye (Ab): 0.1% by mass or more and 70% by mass or less

Pigment (Ad): 29.9 mass% or more and 99.8 mass% or less; more preferably xanthene dye (Aa): 0.5 mass% or more and 50 mass% or less

Anthraquinone dye (Ab): 0.5% by mass or more and 50% by mass or less

Pigment (Ad): 49.5 mass% or more and 99 mass% or less.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, still more preferably from 10 to 50% by mass, based on the total amount of the solid component. When the content of the coloring agent (A) is in the above range, the color density at the time of forming a color filter is sufficient, and since the composition contains a necessary amount of the resin (B) or the polymerizable compound (C), mechanical strength can be sufficiently formed. The pattern. Here, the "total amount of solid content" in the present specification means the amount by which the content of the solvent is subtracted from the total amount of the colored curable resin composition. The total amount of the solid components and the content of each component relative thereto can be measured, for example, by well-known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, and an alkali-soluble resin is preferred. The resin (B) may, for example, be the following resins [K1] to [K6].

The resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter also referred to as "(a)"), and a cyclic ether structure having a carbon number of 2 to 4. a copolymer of a monomer (b) (hereinafter also referred to as "(b)")) having an ethylenically unsaturated bond; a resin [K2] (a), (b), and a monomer copolymerizable with (a) (c) (except for (a) and (b)) (hereinafter also referred to as "(c)"); copolymer [K3] (a) and (c); resin [K4 (a) copolymer of (c) and (b) reactive resin; resin [K5] (b) and (c) copolymer and (a) reactive resin; resin [K6] (b) and c) the copolymer and (a) react, and then react with the carboxylic anhydride Resin

(a) specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinyl benzyl acid; maleic acid, fumaric acid, citraconic acid, Methyl fumaric acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3 , unsaturated dicarboxylic acids such as 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3- Dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1 Hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxyl a bicyclic unsaturated compound containing a carboxyl group such as -6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4- Vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride , 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydrate, etc. Dicarboxylic acid anhydrate; succinic acid mono [2-(methyl) propylene methoxyethyl ester], phthalic acid mono [2-(methyl) propylene methoxyethyl ester] and the like An acid-unsaturated mono[(meth)acryloxyalkyl]ester; such as an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule of α-(hydroxymethyl)acrylic acid.

Among these, from the viewpoint of copolymerization reactivity or the solubility of the obtained resin to an aqueous alkali solution, acrylic acid, methacrylic acid, and horse are considered. The anhydride is preferred.

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

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

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), having an oxetane group and an ethylenically unsaturated bond The monomer (b2) (hereinafter also referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)"), and the like.

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched chain unsaturated aliphatic hydrocarbon is epoxidized (hereinafter also referred to as "(b1-1)")) A monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter also referred to as "(b1-2)").

(b1-1), for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and propylene oxide Vinyl ether, o-vinylbenzyl epoxidized propyl ether, m-vinylbenzyl epoxidized propyl ether, p-vinylbenzyl epoxidized propyl ether, α-methyl-o-vinyl benzyl epoxidized ether, α -Methyl-m-vinylbenzyl epoxidized propyl ether, α-methyl-p-vinylbenzyl epoxidized propyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4- Bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)benzene Alkene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxy) Methyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6 - Tris(glycidoxymethyl)styrene and the like.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by DAICEL Chemical Industry Co., Ltd.), ( 3,4-Epoxycyclohexylmethyl methacrylate (for example, CYCLOMER A400; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER) M100; a compound represented by the formula (I), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b represents 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 key with O.].

The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a secondary butyl group or a tertiary butyl group.

The alkyl group in which a hydrogen atom is substituted with a hydroxyl group may, for example, be a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group or a 3-hydroxypropyl group. Base, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^a and R ^{b are} preferably, for example, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

The alkanediyl group may, for example, be a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a pentane-1,5- group. Dibasic, hexane-1,6-diyl and the like.

X ^a and X ^{b are} preferably, for example, a single bond, a methylene group, an exoethyl group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O-, more preferably, for example, a single bond, * -CH ₂ CH ₂ -O- (* indicates a bond with O).

The compound represented by the formula (I) may, for example, be a compound represented by the formula (I-1) to the formula (I-15). Preferably, for example, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I) -15) The compound represented. More preferably, for example, a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

The compound represented by the formula (II) may, for example, be a compound represented by the formula (II-1) to the formula (II-15). Preferably, for example, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II) -15) The compound represented. More preferably, for example, a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. Also, these may be mixed in any ratio. When mixed, the mixing ratio, in terms of molar ratio, is preferably Formula (I): Formula (II) is from 5:95 to 95:5, more preferably from 10:90 to 90:10, and even more preferably 20:80 to 80:20.

The monomer (b2) having an oxetane group and an ethylenically unsaturated bond is preferably a monomer having an oxetane group and a (meth) acryloxy group. (b2), for example, 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl 3-methyl propylene oxime Methyl oxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxyethyloxetane, 3 -methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl-3-propenyloxy Ethyl oxetane and the like.

The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group.

(b3) Specifically, for example, tetrahydrofuran methyl acrylate (for example, VISCOAT V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate or the like can be mentioned.

(b) It is preferable to (b1) from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, from the viewpoint of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

(c) may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, or tertiary (meth)acrylic acid. Butyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo [5.2.1.0 ^2.6 ]decane-8-yl (meth)acrylate (in the technical field, conventional It is called "dicyclopentanyl (meth) acrylate." Also known as "tricyclodecyl (meth) acrylate), tricyclo [methyl acrylate] [5.2.1.0 ^2.6 ] decene-8- Base ester (commonly known in the art as "dicyclopentenyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (a) Adamantyl acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. Methyl) acrylates; 2-hydroxyethyl (meth)acrylate, (A) a hydroxyl group-containing (meth) acrylate such as 2-hydroxypropyl acrylate; a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate; bicyclo[2.2. 1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]g 2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo [2.2.1] Hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6- Di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2 - alkene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tridecyl Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo [2.2.1] Bicyclic unsaturated compounds such as hept-2-ene; N-phenyl maleimine, N-cyclohexyl maleimine, N-benzyl maleimide, N-amber醯imino-3-maleimide benzylate, N-succinimide-4-maleimine butyrate, N-succinimide-6-maleimide caproate , N-succinimide-3-maleimide propionate, N-(9-acridinyl) maleimide and other dicarbonyl quinone imines; styrene, α-methyl styrene , m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, methacrylamide, acetic acid Vinyl ester, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide Bicyclo[2.2.1]hept-2-ene.

In the resin [K1], the ratio from the respective structural units is preferably from the structural unit of (a): 2 to 60 mol% in the total structural unit constituting the resin [K1].

Structural unit from (b): 40 to 98 mol%, more preferably structural unit from (a): 10 to 50 mol%

The structural unit from (b): 50 to 90 mol%.

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the development property when the color pattern is formed, and the solvent resistance of the obtained color filter are excellent. tendency.

Resin [K1], for example, can be referred to the document "Experimental method for polymer synthesis" (the method described in the issue of Daisuke Otsuka's Institute of Chemicals, 1st Edition, 1st Brush, March 1, 1972) and the literature. Manufactured from the references cited.

Specifically, for example, a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction container, for example, by replacing oxygen with nitrogen, a deoxidizing atmosphere is formed. Heating while stirring The method of insulation. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and a general user in the field can be used. For example, the polymerization initiator may, for example, be an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) or the like) or organically. In the case of the solvent (such as benzamidine peroxide), the solvent (E) of the colored curable resin composition of the present invention may be, for example, a solvent to be described later.

Further, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. In particular, in the polymerization, the solvent contained in the colored curable resin composition of the present invention is used as a solvent, whereby the solution after the reaction can be directly used in the preparation of the color-curable resin composition of the present invention. Therefore, the manufacturing steps of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio from the respective structural unit is preferably from the structural unit of (a): 2 to 45 mol% in the total structural unit constituting the resin [K2].

Structural unit from (b): 2 to 95 mol%

Structural unit from (c): 1 to 65 mol%, more preferably from (a) structural unit: 5 to 40 mol%

Structural unit from (b): 5 to 80 mol%

The structural unit from (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition is formed, and the color pattern is formed. The developing property and the color filter of the obtained color filter tend to be excellent in heat resistance and mechanical strength.

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

In the resin [K3], the ratio from the respective structural unit is preferably from the structural unit of (a): 2 to 60 mol% in the total structural unit constituting the resin [K3].

Structural unit from (b): 40 to 98 mol%, more preferably, structural unit from (a): 10 to 50 mol%

The structural unit from (b): 50 to 90 mol%.

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

The resin [K4] can be produced by the following method to obtain a copolymer of (a) and (c), and (b) having a cyclic ether having 2 to 4 carbon atoms; Manufactured from carboxylic acid and/or carboxylic anhydride.

First, the copolymer of (a) and (c) is produced in the same manner as the method described in the method for producing the resin [K1]. In this case, the ratio from each structural unit is preferably the same as that of the resin [K3].

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

Continuing the manufacture of the copolymers of (a) and (c), replacing the ambient atmosphere in the flask with nitrogen, and reacting (b), a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, tris(dimethyl) Aminomethyl)phenol, etc.) and polymerization inhibitors (eg hydroquinone, etc.) The resin [K4] can be produced by placing it in a flask, for example, at 60 to 130 ° C for 1 to 10 hours.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. By setting it in this range, the storage stability of the colored curable resin composition, the development of the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are changed. Excellent tendency. Since the cyclic ether has high reactivity and does not easily remain unreacted (b), (b) used in the resin [K4] is preferably (b1), and (b1-1) is more preferable.

The amount of the above-mentioned reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total 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 heat generated by the production equipment or the polymerization. Further, in the same manner as the polymerization conditions, the heat generation amount due to the production equipment or the polymerization can be considered, and the charging method and the reaction temperature can be appropriately adjusted.

In the first stage, the resin [K5] can be obtained in the same manner as the above-mentioned method for producing the resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used.

The ratio of the structural units from (b) and (c), relative to the total number of moles constituting the total structural unit of the above copolymer, is preferably from the structural unit of (b): 5 to 95 mol%, respectively.

Structural unit from (c): 5 to 95 mol%, More preferably from (b) structural units: 10 to 90 mol%

The structural unit from (c): 10 to 90 mol%.

Further, the cyclic ether derived from (b) and the carboxylic acid or carboxyl group (a) having the copolymer of (b) and (c) can be obtained under the same conditions as in the method for producing the resin [K4]. The anhydride is reacted, whereby the resin [K5] is obtained.

The amount of (a) used in the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). Since the cyclic ether is highly reactive and does not easily remain unreacted (b), (b) used in the resin [K5] is preferably (b1), and (b1-1) is more preferable.

The resin [K6] is a resin in which the resin [K5] is further reacted with a carboxylic acid anhydride.

The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride is reacted with a carboxylic anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortylene. Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydrate (HIMIC Anhydride) and the like. The amount of the carboxylic anhydride to be used is preferably from 1 to 1 mol per mol of the amount of (a).

The resin (B), specifically, for example, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricycloacrylic acid [5.2] .1.0 ^2.6 ]Resin such as oxime ester/(meth)acrylic copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (methyl) Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmalazone Amine copolymer, resin such as 3-methyl-3(meth)acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/ (Meth)acrylic acid copolymer, styrene/(meth)acrylic copolymer, etc. [K3]; benzyl (meth)acrylate/(meth)acrylic acid copolymer addition (meth)acrylic acid propylene Ester resin, resin of tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer addition to glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / Benzyl (meth)acrylate/(meth)acrylic acid copolymer addition (meth)acrylic acid a resin such as a propylene acrylate resin [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/glycidyl methacrylate with (meth)acrylic acid, (meth) Resin such as tricyclodecyl acrylate/styrene/glycidyl methacrylate and resin reacted with (meth)acrylic acid [K5]; tricyclodecyl (meth) acrylate / (methyl) a resin such as a resin obtained by reacting a copolymer of glycidyl acrylate with (meth)acrylic acid and a resin which is reacted with tetrahydrophthalic anhydride, etc. [K6].

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

Among them, the resin (B) is preferably a resin [K1] and a resin [K2].

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is increased, the residual film ratio is also high, the solubility of the unexposed portion to the developing solution is good, and the resolution of the color 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 from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. Here, 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, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component. When the content of the resin (B) is in the above range, the color pattern can be formed, and the resolution of the coloring pattern and the residual film ratio tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. A good (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tris(meth)acrylate, neopentyl glycol tri(meth)acrylate, neopentyl glycol tetra(meth)acrylate, and five (a) Di-n-pentaerythritol acrylate, di-n-pentaerythritol hexa(meth) acrylate, tricrostitol octa (meth) acrylate, tricrostitol hexa(meth) acrylate, ten Tetrakis pentaerythritol (meth)acrylate, tetrapentaerythritol hexa(meth)acrylate, tris(2-(methyl)propenyloxyethyl)isocyanate, ethylene glycol Modification of neopentyl glycol (meth)acrylate, ethylene glycol modified hexaerythritol hexa(meth) acrylate, propylene glycol modified tetrakis (meth) acrylate pentaerythritol ester, propylene Alcohol-modified dipentaerythritol hexa(meth)acrylate, modified caprolactone modified neopentyl glycol (meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate . The polymerizable compound may be used singly or in combination of two or more.

Among them, dineopentaerythritol penta(meth)acrylate and dineopentaerythritol hexa(meth)acrylate are preferred.

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

The content of the polymerizable compound (C) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the coloring 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 can generate a living radical, an acid or the like by the action of light or heat, and a known polymerization initiator can be used.

The polymerization initiator (D) preferably contains a compound selected from the group consisting of alkylphenones, three a polymerization initiator of at least one of the group consisting of a compound, a mercaptophosphine oxide compound, an O-merylxime compound, and a biimidazole compound, more preferably a polymerization initiator containing an O-mercaptopurine compound Agent.

The O-indenyl compound is a compound having a partial structure represented by the formula (d1).

Hereinafter, * indicates a keying key.

The O-indenyl hydrazine compound may, for example, be N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzyloxyl-1- (4-phenylthiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1 -keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]ethane-1-a Amine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethyloxy) Benzyl hydrazide}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)- 9H-carbazol-3-yl]-3-cyclopentylpropan-1-amine, N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H -oxazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, BASF Corporation, N-1919 (made by Adeka)) can also be used.

Wherein, the O-hydrazinolide compound is preferably selected from the group consisting of N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxyl 1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl At least one of the group consisting of propane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylthiophenyl)octane-1-one-2 - Imine. In the case of these O-indenyl ruthenium compounds, there is a tendency for a color filter having a high brightness to be obtained.

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

The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one, 2 -Dimethylamino-1-(4-(N-morpholinyl)phenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

The compound having a partial structure represented by the formula (d3) may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one or 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomer, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

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

three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The mercaptophosphine oxide compound may, for example, be 2,4,6-trimethylbenzylidenediphenylphosphine oxide, or a commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation).

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) linkage Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPS62-174204-A, etc.), 4, 4', 5, 5' An imidazole compound in which a phenyl group at the position is substituted with a carboalkoxy group (for example, refer to JPH07-10913-A, etc.) and the like.

Further, the polymerization initiator (D) may, for example, be a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether; diphenyl ketone or methyl phthalate; 4-phenyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tris-butylcarbonyl)diphenyl peroxide a diphenyl ketone compound such as a ketone or 2,4,6-trimethyldiphenyl ketone; a quinone compound such as phenanthrenequinone, 2-ethyl hydrazine or camphor quinone; 10-butyl- 2-chloroacridone, benzil, methyl phenylglyoxylate, titanium titanocene, and the like. These are used in combination with a polymerization starting aid (D1) (especially an amine) described later. Preferably.

The acid generator may, for example, be 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate or 4-ethoxymethoxyphenyldimethylhydrazine. Tosylate, 4-ethyloxyphenyl. methyl. Benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate Equivalent salts, or nitrobenzyl toluenesulfonates, benzoin tosylate salts, and the like.

The content of the polymerization initiator (D) 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 of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is in the above range, the sensitivity is high and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

Further, together with the polymerization initiator (D), a polymerization initiation aid (D1) may be further contained. The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound which initiates polymerization by a polymerization initiator.

The polymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy fluorene compound, a thioxanthone compound or a carboxylic acid compound, and is preferably a thioxanthone compound.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzylate, ethyl 4-dimethylaminobenzylate or 4-dimethylamine. Isoamyl benzylate, 2-dimethylaminoethyl benzylate, 2-ethylhexyl 4-dimethylaminobenzylate, N,N-dimethyl-p-toluidine, 4,4' - bis(dimethylamino)diphenyl ketone (commonly known as Michler's) Ketone)), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(ethylmethylamino)diphenyl ketone, etc., of which 4,4'- Bis(diethylamino)diphenyl ketone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The alkoxy ruthenium compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9. , 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

The thioxanthone compound may, for example, be 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone or 1-chloro -4-propoxythioxanthone and the like.

The carboxylic acid compound may, for example, be phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid or methoxy. Phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid , N-naphthylglycine, naphthyloxyacetic acid, and the like.

The polymerization initiator may be used singly or in combination of two or more.

When the polymerization initiator (D1) is used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). 1 to 20 parts by mass. When the amount of the polymerization starting aid (D1) is in this range, the color pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited and can be generally used in the field. Solvent. For example, an ester solvent (a solvent containing -COO- in the molecule, a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent containing no -COO-), an alcohol solvent (containing OH in the molecule, not containing -O-, -CO- And a solvent of -COO-), an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, etc. are selected and used.

The ester solvent may, for example, be methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate or isoamyl acetate. Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol acetate and γ-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, and diethyl ether. Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, phenyl methyl ether (anisole), benzene Ethyl ethyl ether, methyl phenyl methyl ether, and the like.

The ether ester solvent may, for example, be methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate or methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acid esters, etc.

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone, and the like.

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 1,3,5-trimethylbenzene.

The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

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

Among the above solvents, an organic solvent having a boiling point of 1 atm of from 120 ° C to 180 ° C is preferred from the viewpoint of coatability and drying properties. The solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 3 - Ethyl ethoxy propionate.

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

<Leveling agent (F)>

The leveling agent (F) may, for example, be a polyfluorene-based surfactant, a fluorine-based surfactant, or a polyfluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

The polyoxo-based surfactant may, for example, be a surfactant having a decane bond in the molecule. Specific examples include Toray silicone DC3PA, same SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade name: Toray DOW Corning). KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials) contract company system).

The above-mentioned fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), MEGAFAC (registered trademark) F142D, same with F171, same with F172, with F173, with F177, with F183, with F554, with R30, Same as RS-718-K (DIC system), Eftop (registered trademark) EF301, EF303, EF351, and EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, the same as S382, the same SC101, the same SC105 (asahi Glass), and E5844 (Daikin Fine-Chemical Institute).

The above-mentioned polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specifically, for example, MEGAFAC (registered trademark) R08, the same BL20, the same F475, the same F477, and the same F443 (DIC system) can be mentioned.

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

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably 0.01% based on the total amount of the coloring curable resin composition. The mass% or more is 0.05% by mass or less. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be made good.

<Other ingredients>

The colored curable resin composition of the present invention may contain various additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a photostabilizer, and a chain transfer agent, as needed.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention may, for example, be a mixture of a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (if necessary) ( E), leveling agent (F), polymerization starting aid (D1) and other ingredients to prepare.

Xanthene dye (Aa), anthraquinone dye (Ab) and dyes as needed (Ac) may be partially dissolved in a part or all of the solvent (E) in advance to prepare a solution.

The solution is preferably filtered through a filter having a pore diameter of about 0.01 to 1 μm.

When the pigment (Ad) is contained, it is preferred to mix the pigment (Ad) with a part or all of the solvent (E) in advance, and to disperse it by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. In the obtained pigment dispersion, the remaining coloring agent (A), the remaining resin (B), the polymerizable compound (C), the polymerization initiator (D), and the remaining solvent (E), and optionally The leveling agent (F), the polymerization starting aid (D1), and other components to be used are mixed so as to have a predetermined concentration, whereby the colored curable resin composition of the object can be prepared.

It is preferred to filter the color-setting resin composition after mixing with a filter having a pore diameter of about 0.01 to 10 μm.

<Color filter and method of manufacturing liquid crystal display device>

The method of forming a color filter by the colored curable resin composition of the present invention may, for example, be a photolithography method or a method using an ink jet apparatus. In the photolithography method, for example, the colored curable resin composition of the present invention is applied onto a substrate, and a volatile component such as a solvent is removed to form a colored composition layer, and the colored composition layer is exposed through a photomask. The method of imaging. After development, a colored pattern can be formed by heating as needed. In the method of forming the coloring pattern described above, the colored coating film of the cured product of the colored composition layer can be formed by not using a photomask and/or not developing the image during exposure. Such as Thus, the obtained color pattern and color coating film can be made into a color filter.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda-lime glass coated with cerium oxide, or polycarbonate or polymethacrylic acid can be used. A resin plate such as a methyl ester or polyethylene terephthalate is formed on the substrate, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Other color filter layers (for example, a color filter layer formed on a substrate by a colored curable resin composition), a resin layer, a transistor, a circuit, or the like may be formed on the substrates.

The film thickness of the color filter to be produced is not particularly limited, and may be appropriately adjusted depending on the intended use, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm.

Next, a method of patterning a glass substrate on which a thin film transistor (hereinafter referred to as "TFT") is formed will be described.

Specifically, a plurality of TFTs 22 are formed on each of the pixels on the glass substrate 21 by a well-known method such as photolithography (see FIG. 1). The TFT 22 is composed of, for example, a gate electrode 22a formed of molybdenum (Mo) and forming a part of a gate line on the glass substrate 21, and formed on the gate electrode 22a by, for example, nitridation. gate composed of the film (SiN _x) and the oxide film (SiO ₂₎ of the laminated film is a gate insulating film 22b, as much as crystalline silicon film 22c is formed on the gate insulating film 22b, and for example, an oxide film (SiO ₂₎ and A protective film 22d formed of a laminated film of a nitride film (SiN _x ). A region of the polycrystalline germanium film 22c opposed to the gate electrode 22a is a channel region of the TFT 22, and a region on both sides of the channel region is a source region or a drain region. The source region of the polycrystalline germanium film 22c is electrically connected to a signal line 27 formed of, for example, aluminum (Al) through a contact hole provided in the protective film 22d. Further, the drain region of the polycrystalline germanium film 22c is electrically connected to the pixel electrode 24 through a contact hole 201 which will be described later.

When a plurality of TFTs 22 are formed on each of the pixels on the glass substrate 21, an alignment mark (not shown) is formed on the glass substrate 21 together with the TFTs 22. This alignment mark is a reference for the alignment position in the forming step of the color filter layer 23 to be described later. Moreover, the alignment marks can also serve as a reference for the bonding of the drive substrate and the counter substrate. The alignment mark can be formed in at least one of the layers in the same process as the formation of a metal layer such as a wiring or a polycrystalline germanium layer in the manufacturing process of the TFT 22.

Next, the colored curable resin composition of the present invention is applied onto the glass substrate 21 on which the TFT 22 and the alignment mark are formed, and the volatile components such as a solvent are removed by heat drying (prebaking) and/or drying under reduced pressure to dry the composition. A coloring composition layer having a film thickness of 0.5 to 5.0 μm (for example, 1.0 μm) is formed.

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

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 60 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C at a pressure of from 50 to 150 Pa.

Then, the colored composition layer is irradiated with ultraviolet rays through a mask (not shown), and the unnecessary portion is selectively removed by the developing solution, thereby obtaining a connection hole formed in the drain region reaching the polycrystalline germanium film 22c. (contact The colored composition layer formed by the pixels of 201 is washed with water.

The unexposed portion of the colored composition layer was dissolved and removed by a developing solution by development. The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of the basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developing solution may also contain a surfactant.

The development method may be any of a puddle method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at any angle during development.

Thereafter, in order to reflow the colored composition layer on which the contact hole 201 is formed and/or to cure the polymerizable compound (C) or the like contained in the colored composition layer, for example, at 100 to 300 ° C Preferably, the temperature is from 150 to 230 ° C, and heating is, for example, from 1 to 120 minutes, preferably from 10 to 60 minutes. In this manner, the color-curable resin composition layer 23A of the color pattern is formed. The colored curable resin composition layer 23A corresponds to the color filter of the present invention.

In the same manner, each of the colored curable resin composition layers 23A is formed of a red colored curable resin composition, a green colored curable resin composition, and a blue colored curable resin composition, and each of the pixel columns is formed to contain red. The color filter layer 23 of the filter 23a, the green filter 23b, and the blue filter 23c (refer to Fig. 2). Although the area between the filters of the color filter layer 23 forms a mixed area with the adjacent color, since this area is a light-shielding area opposed to the signal line 27, it does not cause damage particularly in quality. Moreover, the area between the filters can also be made non-colored.

Next, for example, a method of coating the color filter layer 23 by spin coating is used. For example, a photosensitive resin film 29 as a protective film having a film thickness of 0.3 to 2.0 μm is formed. Then, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and the region corresponding to the connection hole 201 and the unnecessary portion are selectively removed by the developing liquid, thereby forming the polycrystalline ruthenium film 22c. After the contact hole 202 of the drain region, water washing is performed. Thereafter, in order to reflow the photosensitive resin film 29, heating is performed at a temperature (for example, 200 ° C) in the range of 100 to 300 °C. Next, in order to remove the residue such as a dye deposited in the connection hole 202 and the organic substance, etching is performed by oxygen plasma, and further, etching is performed by dilute hydrofluoric acid in order to remove the oxide film formed of the oxygen plasma.

Next, a transparent conductive material (for example, ITO (Indium-Tin Oxide)) is formed on the photosensitive resin film 29 by, for example, a sputtering method, and the ITO film is etched by photolithography and etching. Patterning is performed to form a transparent pixel electrode 24 (see Fig. 3). Further, the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) depending on the device to be fabricated. Thereafter, an alignment film is formed by a known method, and then the driving substrate and the counter substrate are bonded to each other, whereby a liquid crystal display device can be manufactured.

According to the colored curable resin composition of the present invention, in particular, a color filter excellent in contrast can be produced. The color filter includes color filters used as display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensing elements.

Example

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.

In the examples, "%" and "parts" are % by mass and part by mass unless otherwise specified.

In the following synthesis examples, the compounds were identified by elemental analysis (VARIO-EL; (manufactured by Elementar)).

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name: Chugai Aminol Fast PinkR; manufactured by Sino-foreign Chemical Co., Ltd.) was charged. 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were added dropwise while maintaining a temperature of 20 ° C or lower with stirring, 10.9 parts of sulfite chloride. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was carried out for 5 hours while maintaining the same temperature, followed by cooling to 20 ° C. The reaction solution after cooling was kept at 20 ° C or lower while stirring, and a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. After the resulting reaction mixture was distilled off by a rotary evaporator, a small amount of methanol was added and stirred vigorously. The mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystal was obtained by filtration, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a mixture of the dye (Aa-1) (the compound represented by the formula (A1-1) to the formula (A1-8). ) 11.3 copies.

[Synthesis Example 2]

20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under a light-shielding condition, and the resulting solution was stirred at 110 ° C for 6 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour, and then crystallized. The precipitated crystal was obtained as a residue by suction filtration, and dried to obtain 24 parts of the compound represented by the formula (1-30). The yield was 80%.

The structure of the compound represented by the formula (1-30) was confirmed by mass analysis (LC: Model 1200, manufactured by Agilent, MASS: LC/MSD type manufactured by Agilent).

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

Exact Mass: 602.2

[Synthesis Example 3]

A compound represented by the formula (1-38) was obtained in the same manner as in Synthesis Example 2 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by formula (1-38).

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.9

Exact Mass: 658.9

[Synthesis Example 4]

12 parts of the compound represented by the formula (1x), 60 parts of N-methyl-2-pyrrolidone and 12.6 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the resulting mixture was stirred at 60 ° C for 5 hours. After cooling the above reaction solution to room temperature, it is added to a mixture of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature. Mix for 1 hour. The precipitated crystal was obtained as a residue by suction filtration, and dried to obtain 12.4 parts of the compound represented by the formula (1-27). The yield was 83%.

Identification of the compound represented by formula (1-27).

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 503.4

Exact Mass: 502.2

[Synthesis Example 5]

15 parts of the compound represented by the formula (1x), 75 parts of N-methyl-2-pyrrolidone and 25.8 parts of decahydroquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the resulting mixture was stirred at 110 ° C. hour. After cooling the above reaction liquid to room temperature, it was added to a mixed liquid of 600 parts of water and 100 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The precipitated crystal was obtained as a residue by suction filtration, and dried to obtain 19.5 parts of the compound represented by the formula (1-29). The yield was 86%.

Identification of the compound represented by formula (1-29).

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 611.4

Exact Mass: 610.3

[Synthesis Example 6]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was passed through 0.02 L/min to form a nitrogen atmosphere, and ethyl lactate 305 was placed. The mass fraction was heated to 70 ° C with stirring.

Next, 46 parts by mass of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1), A solution was prepared by dissolving 240 parts by mass of a molar ratio of 50:50 in 185 parts by mass of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel.

On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts by mass of ethyl lactate, and another dropping funnel was used to 4 Drop into the flask every hour. After the completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9.1 × 10 ³ , a molecular weight distribution of 2.1, a solid content of 26% by mass, and a solid. A resin B1 solution having a component acid value of 120 mg-KOH/g. The resin B1 has the structural unit shown below.

[Synthesis Example 7]

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 182 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was replaced with nitrogen by air, and then the temperature was raised to 100 ° C. Will 22.0 g (70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) of tricyclodecane skeleton ( A mixture of 3.6 g of 2,2'-azobisisobutyronitrile was added to a mixture of 136 g of propylene glycol monomethyl ether acetate and 136 g of the mixture, and the mixture was further stirred at 100 °C.

Next, the atmosphere in the flask was replaced with air by nitrogen, and 35.5 g of propylene methacrylate (0.25 mol (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction)], 32 0.9 g of methylaminomethylphenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C to obtain a resin B2 solution having a solid content of 29% and a solid content of 79 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

[Synthesis Example 8]

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was passed through 0.02 L/min to form a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 70 ° C while stirring. Next, 60 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) are The molar ratio of 50:50 was 440 parts dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate, and another dropping funnel was used. It was dropped into the flask over 4 hours. After the completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9.1 × 10 ³ , a molecular weight distribution of 2.16, a solid content of 34.8%, and a solid content. The converted acid B3 solution was 81 mg-KOH/g. Resin B3 has the structural unit shown below.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example was carried out under the following conditions using a GPC method.

Device: K2479 (Shimadzu Corporation (stock) system)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (made by Tosoh)

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

[Example 1] (Modulation of coloring curable resin composition)

(A) Colorant: C.I. Pigment Blue 15:6 (pigment) 24 parts

Acrylic pigment dispersant 6.1 parts

Propylene glycol monomethyl ether acetate 163 parts

Mix the above, use a bead mill to fully disperse the pigment, and then mix the following

(A) Colorant: Dye (Aa-1) (xanthene dye) 1.8 parts

(A) Colorant: C.I. Solvent Blue 35 (Sudan blue II; manufactured by Aldrich; anthraquinone dye) 1.8 parts

(B) Resin: Resin B1 (converted in solid content) 60 parts

(C) Polymeric compound: dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts

(D) Polymerization initiator: N-benzyloxyl-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Corporation) 5 servings

(F) Leveling agent: Polyether modified polyoxygenated oil (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.08 parts

(E) Solvent: ethyl lactate 682 parts

(E) Solvent: propylene glycol monomethyl ether acetate 8 parts

A colored curable resin composition was obtained.

<Production of coloring pattern>

The colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then prebaked at 100 ° C for 3 minutes to obtain a colored composition layer. After leaving to cool, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK; TOPCON) was used at 150 mJ/cm ² in an atmospheric atmosphere. The amount of exposure (365 nm reference) was irradiated with light. The mask is formed using a line width and line and space pattern of 100 μm. The colored composition layer after the light irradiation was immersed and developed at 24 ° C for 60 seconds in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then placed in an oven. Post-baking at 230 ° C for 30 minutes gave a colored pattern.

<Measurement of film thickness>

The film thickness of the obtained color pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Color Evaluation>

For the obtained color pattern, the color separation is measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate (x, y) in the XYZ color system of CIE is measured using the characteristic function of the C light source. ) with a tristimulus value of Y. The greater the value of Y, the higher the brightness. The results are shown in Tables 3 and 4.

<Comparative evaluation>

A colored coating film was produced in the same manner as the production of the color pattern except that the mask was not used at the time of exposure. For the colored coating film produced, a comparison meter was used (CT-1: manufactured by Hosei Electric Co., Ltd., color difference meter BM-5A: TOPCON company, light source: F-10, polarizing film: pot kiln motor) ), the comparison was made with the blank value as 30,000. The higher the contrast of the colored coating film, the higher the contrast in the coloring pattern. The results are shown in Tables 3 and 4.

[Comparative Example 1]

(A) Colorant: C.I. Pigment Blue 15:6 (pigment) 20 parts

Acrylic pigment dispersant 5 parts

Propylene glycol monomethyl ether acetate 137 parts

Mix the above, use a bead mill to fully disperse the pigment, and then mix the following

(A) Colorant: Dye (Aa-1) (xanthene dye) 3.5 parts

(B) Resin: Resin B2 solution 157 parts

(C) Polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts

(D) Polymerization initiator: OXE01; manufactured by BASF) 15 parts

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 289 parts

A colored curable resin composition was obtained.

Examples 2 to 15

The same procedure as in Example 1 was carried out so as to have the compositions shown in Tables 1 and 2 to obtain a colored curable resin composition.

Further, in Tables 1 and 2, "Ad-1 ¹ "" is a mixture of acrylic acid pigment dispersant and propylene glycol monomethyl ether acetate in the column "E-1 ³ ", and is dispersed in advance. .

The column "E-1 ²⁾ " indicates the total content of propylene glycol monomethyl ether acetate.

In Tables 1 and 2, each component represents the following. Further, the resin (B) represents a part by mass in terms of solid content.

Xanthene dye (Aa): Aa-1: dye (Aa-1)

Xanthene dye (Aa): Aa-2: a compound represented by formula (1-30)

Xanthene dye (Aa): Aa-3: a compound represented by formula (1-38)

Xanthene dye (Aa): Aa-4: C.I. Acid red 52 (Tokyo Chemical Industry Co., Ltd.)

Xanthene dye (Aa): Aa-5: a compound represented by formula (1-27)

Xanthene dye (Aa): Aa-6: a compound represented by formula (1-29)

Anthraquinone dye (Ab): Ab-1: C.I. Solvent Blue 35 (Sudan blue II; manufactured by Aldrich)

Anthraquinone dye (Ab): Ab-2: C.I. Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant Co., Ltd.)

Anthraquinone dye (Ab): Ab-3: C.I. Acid Blue 80 (Coomassie (registered trademark) Blue B 150; manufactured by ICI)

Anthraquinone dye (Ab): Ab-4: C.I. Solvent Blue 104 (Polysynthren Blue RBL P; manufactured by Clariant Co., Ltd.)

Anthraquinone dye (Ab): Ab-5: C.I. Solvent Blue 122 (Polysynthren Blue R; manufactured by Clariant)

Pigment (Ad): Ad-1: C.I. Pigment Blue 15:6

Resin (B): B-1: Resin B1

Resin (B): B-2: Resin B2

Resin (B): B-3: Resin B3

Polymerizable compound (C): dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): D-1: N-benzyloxyl-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF company; O-mercaptopurine compound)

Polymerization initiator (D): D-2: 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF; alkyl benzophenone compound)

Polymerization initiation aid (D1): 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; Nippon Chemical Co., Ltd.; thioxanthone compound)

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

Solvent (E): E-2: ethyl lactate

Solvent (E): E-3: propylene glycol monomethyl ether

Solvent (E): E-4: 4-hydroxy-4-methyl-2-pentanone

Leveling agent (F): Polyether modified polyoxygenated oil (Toray silicone SH8400; Toray Dow Corning Co., Ltd.)

The colored curable resin compositions of Examples 2 to 15 and Comparative Example 1 obtained as described above were evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4.

According to the colored curable resin composition of the example, the obtained coating film was confirmed to exhibit high contrast. Therefore, it is understood that the coloring coating film or the coloring pattern obtained from the colored curable resin composition of the present invention is used as a high contrast color filter, and the liquid crystal display device including the color filter has excellent display characteristics.

By the colored curable resin composition of the present invention, a high contrast color filter can be formed.

21‧‧‧ glass substrate

22‧‧‧TFT (switching element)

22a‧‧‧Gate electrode

22b‧‧‧gate insulating film

22c‧‧‧Multi-crystalline enamel film

22d‧‧‧Protective film

23A‧‧‧Coloring curable resin composition layer (color filter)

27‧‧‧ Signal Line

201‧‧‧connection hole

Claims (6)

A colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant contains a xanthene dye and an anthraquinone dye, and the anthraquinone dye contains a formula (1b) a dye of the compound represented In the formula (1b), A represents -NH-R ⁵² , and R ⁵¹ and R ⁵² each independently represent a group represented by the formula (1b') [In the formula (1b'), R ⁵³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -CO ₂ H, -CO ₂ R ⁵⁴ , -NHCOR ⁵⁴ , -SO ₃ R ⁵⁴ or -SO ₂ NR ⁵⁴ R ⁵⁵ , R ⁵⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, a hydroxyl group or an amine group, R ⁵⁵ represents a hydrogen atom, and r represents an integer of 0 to 5, when r When it is 2 or more, a plurality of R ⁵³ may be the same or different, and X ⁵¹ represents a single bond or an alkylenediyl group having 1 to 6 carbon atoms; and when -CO ₂ H is present in the formula (1b), it may be formed. salt. The colored hardening resin composition according to claim 1, wherein the xanthene dye is a dye containing a compound represented by the formula (1a). In the formula (1a), R ¹ to R ⁴ independently of each other represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or may have a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO The carbon number of the substituent selected from ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ and -SO ₃ R ⁸ a monovalent aromatic hydrocarbon group to 10; the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may have a carbon number of 1 to Substituting 3 alkoxy, -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ -; R ¹ and R ² may together form a ring containing a nitrogen atom, R ³ And R ⁴ may form a ring containing a nitrogen atom; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ or -SO ₃ R ⁸ ; R ⁶ and R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is an integer of 2 or more, plural R ⁵ may be the same or different; A represents an integer of 0 or 1; X represents a halogen atom; R ⁸ is a C 1-20 monovalent saturated hydrocarbon group of 1, the saturated hydrocarbon Hydrogen atoms contained in it, which may be substituted by a halogen atom; Z ⁺ represents _{^{+ N (R 11) 4,}} Na + or K ^+; R ¹¹ each independently represent a hydrogen atom, a carbon number of 1 to 20 carbon monovalent saturated hydrocarbon group or A 7 to 10 aralkyl group. The colored curable resin composition according to the first or second aspect of the invention, wherein the content of the anthraquinone dye is 0.1% by mass or more and 70% by mass or less based on the total amount of the coloring agent. The colored curable resin composition according to claim 1 or 2, wherein the colorant further contains a pigment. A color filter formed of the colored curable resin composition according to any one of claims 1 to 4. A display device comprising the color filter of claim 5 of the patent application.