TW201335704A - Colored curable resin composition - Google Patents

Abstract

The present invention provides a colored curable resin composition comprising a coloring agent, a resin, a polymerizable compound, and a polymerizing initiator, wherein the coloring agent contains a xanthene dye, a triarylmethane dye and a pigment, and relative to 100 parts of the xanthene dye content by mass, the triarylmethane dye content is 1 to 100 parts and below by mass.

Description

Colored curable resin composition

The present invention relates to a color hardening resin composition.

The colored curable resin composition is produced by using a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. A coloring curable resin composition containing only a dibenzopyran dye as a coloring agent and C.I. Pigment Blue 15:6 (JP2010-32999-A) is known.

However, the conventional coloring curable resin composition described above may not completely satisfy the requirements of the color filter obtained by the coloring curable resin composition.

The present invention encompasses the following inventions.

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the coloring agent comprises a dibenzopyran dye, a triarylmethane dye, and a pigment, and the triarylmethane The content of the dye is from 1 part by mass to 100 parts by mass per 100 parts by mass of the dibenzopyran dye.

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

[3] A color filter formed of the colored curable resin composition as described in [1] or [2].

[4] A display device comprising the color filter according to [3].

A highly contrasting color filter can be formed by using the colored curable resin composition of the present invention.

21‧‧‧ glass substrate

22‧‧‧TFT (switching element)

22a‧‧‧Gate electrode

22b‧‧‧gate insulating film

22c‧‧‧ Polysilicon 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‧‧‧ contact holes

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

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

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

(Embodiment of the invention)

The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

The colorant (A) comprises a dibenzopyran dye (Aa), a triarylmethane dye (Ab), and a pigment (Ad). However, the coloring agent (A) may contain a dye different from the dibenzopyran dye (Aa) and the triarylmethane dye (Ab) (hereinafter sometimes referred to as "dye (Ac)").

The colored curable resin composition of the present invention is preferably a solvent (E) and/or a coating agent (F).

The colored curable resin composition of the present invention may further contain a polymerization initiation aid (D1).

In the color hardening resin composition of the present invention, the coloring agent (A) contains a dibenzopyran dye (Aa), a triarylmethane dye (Ab), and a pigment (Ad), so that a high contrast color filter can be produced.

<Colorant (A)>

The dibenzopyran dye (Aa) is a dye containing a compound having a dibenzopyran skeleton in the molecule. Examples of the dibenzopyran dye (Aa) include CI Acid Red No. 51 (hereinafter, the description of CI acid red is omitted, the number is described separately, and the others are the same.), No. 52, No. 87, No. 92, No. 94, No. 289, No. 388, CI Acid Violet No. 9, No. 30, No. 102, CI Alkaline Red No. 1 (Rose Red 6G), No. 2, No. 3, No. 4, No. 8, CI Alkaline Red 10 No. (Rhodamine B), No. 11, CI Alkaline Violet No. 10, No. 11, No. 25, CI Solvent Red No. 218, CI mordant red (Mordant Red) No. 27, CI Reactive Red No. 36 (Bangladesh Rose Red B) , sulforhodamine G, a dibenzopyran dye described in JP 2010-32999-A, and a dibenzopyran dye described in JP4492760-B. It is preferred to dissolve in an organic solvent.

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

[In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number of 6 to 10 which may have a substituent. An aromatic hydrocarbon group, and -CH ₂ - contained in the saturated hydrocarbon group may also be substituted with: -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 2 or more, a plurality of R ^{5 's} may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents: ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and 4 of R ¹¹ may be the same or different.

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.

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 -, R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing anthracene ring of 3 to 10 members together with a nitrogen atom.

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

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a propylphenyl group, a butylphenyl group and the like.

The aromatic hydrocarbon group may have a substituent, and may, for example, be 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 and -SO ₂ NR ⁹ R ¹⁰ . Among these, in terms of substituents, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ^{10 are} preferred, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ Better. In this case, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ⁴ are such a group, a color hardening resin composition of the present invention containing the compound (1a) can form a color filter having less foreign matter and excellent heat resistance.

The ring formed by the combination of R ¹ and R ² with a nitrogen atom and the ring formed by R ³ and R ⁴ together with a nitrogen atom may be exemplified below.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in 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 or a decyl group. a linear alkyl group such as decyl, dodecyl, hexadecyl or eicosyl; a branch of isopropyl, isobutyl, isopentyl, neopentyl or 2-ethylhexyl An alkyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

The hydrogen atom contained in the saturated hydrocarbon group may be substituted by, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Eicosyloxy and the like.

Examples of the -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, an eicosyloxycarbonyl group and the like.

Examples of the -SR ⁸ include a methyl group, an ethyl group, a butyl group, a hexyl group, a decyl group, an eicosyl group, and the like.

Examples of the -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butasulfonyl group, a hexylsulfonyl group, a sulfonyl group, an eicosylsulfonyl group, and the like.

Examples of -SO ₃ R ⁸ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexoxasulfonyl, eicosylsulfonate. Base.

Examples of -SO ₂ NR ⁹ R ^{10 include} , for example, amidoxime; N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropyl Amine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-butylbutylsulfonyl, N-t-butylamine sulfonyl, N-pentyl Amidoxime, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropane 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)hexyl N-1 substituted amine sulfonyl group such as sulfinyl 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-propyl Methylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-t-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N An N,N-2 substituted amine sulfonyl group such as bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may further contain a substituent. The substituent may, for example, be a hydroxyl group or 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 , -SO ₃ ^- -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ^{9 is more} preferred.

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

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ may, for example, be an alkyl group as described above and having a carbon number of 1 to 6.

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

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

In the above-mentioned ⁺ N(R ¹¹ ) ₄ , it is preferred that 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), and R ¹¹ 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 (1a).

The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter sometimes referred to as "compound (2a)"). Compound (2a) can be its tautomer.

[In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R 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 2 or more, a plurality of R ^{25 's} may be the same or different.

A1 represents an integer of 0 or 1.

X1 represents a halogen atom.

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

Z1 ⁺ represents: ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and four of R ²⁷ may be the same or different.

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

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

R ²¹ to R ^{24 are} a combination of R ²¹ and R ²³ as 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 preferably 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 a hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ replaced by.

When R ²¹ to R ²⁴ are such a group, 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, R ¹ and R ² together with a nitrogen atom The same as the ring. Among them, an aliphatic heterocyclic ring is preferred. Examples of the aliphatic heterocyclic ring are as follows.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ may be the same groups as the saturated hydrocarbon group exemplified in R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are -R ²⁶ , the -R ²⁶ groups are each independently a methyl group or an ethyl group. Again -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ in the R ^26, the carbon number of the branched alkyl group is preferably 3 to 20, carbon atoms, a branched alkyl group of more preferably 6 to 12, especially 2-ethyl The base is better. When R ²⁶ is such a group, a color filter which produces 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 ⁺ , and preferably ⁺ N(R ²⁷ ) ₄ .

The above ⁺ N(R ²⁷ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms in which at least two of the four R ²⁷ are used. 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), and R ²⁷ is such a group, a color filter which produces a small amount of foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).

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

Meanwhile, the compound (1a) is preferably a compound represented by the formula (3a) (hereinafter sometimes referred to as "compound (3a)"). Compound (3a) can be its tautomer.

[In the formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be 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 with 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 - is substituted.

R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkanoyl group having 1 to 4 carbon atoms or an alkanesulfonyl 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 are independent of each other and represent an integer from 0 to 5. When p is 2 or more, a plurality of R ³³ may be the same or different; when q is 2 or more, a plurality of R ³⁴ may be the same or different.

R ¹¹ represents the same meaning as described 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 the example of 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 .

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

R ³¹ and R ³² are independent of each other, and a saturated hydrocarbon group having a carbon number of 1 to 3 is preferred.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, second butyl group and tert-butyl group. Wait.

Examples of the alkylene group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ may, for example, be methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl or the like. Propylsulfonyl and the like.

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 the formula (1-1) to the formula (1-43). Further, in the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group.

Among the above compounds, the compound represented by the formula (1-1) to the formula (1-23) or the formula (1-37) to the formula (1-43) is equivalent to the compound (2a), and the formula (2) All of the compounds represented by the formula (1-24) to the formula (1-36) are equivalent to the compound (3a).

Among these, the sulfonamide of CI Acid Red No. 289, the fourth grade ammonium salt of CI Acid Red No. 289, the sulfonamide of CI Acid Violet No. 102 or the fourth grade ammonium salt of CI Acid Violet No. 102 good. Such a compound may, for example, be a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11) or the formula (1-12).

Further, the compound represented by any one of the formula (1-24) to the formula (1-33) is also preferable from the viewpoint of the solubility in the organic solvent.

As the dibenzopyran dye (Aa), a commercially available dibenzopyran dye can also be used (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., manufactured by Tajika Chemical Industry Co., Ltd. "Rhodamin 6G"). At the same time, the commercially available dibenzopyran dye can also be used as a starting material, and then synthesized by referring to JP2010-32999-A.

The triarylmethane dye (Ab) is a dye containing a compound having a triarylmethane skeleton in the molecule. Examples of the triarylmethane dye (Ab) include CI Acid Violet No. 15, No. 16, No. 17, No. 19, No. 21, No. 23, No. 24, No. 25, No. 38, No. 49, No. 72, CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 38, 48, 75 , 83, 84, 86, 88, 90, 90:1, 91, 93, 93:1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269, CI Acid Green 3, 5, 6, 7, 8, 9, 11 No. 13, No. 13, No. 14, No. 15, No. 16, No. 50, No. 50: No. 1, CI Alkaline Blue No. 7, No. 81, No. 83, No. 88, No. 89, CI Alkaline Violet No. 2 , CI Alkaline Red No. 9, CI Direct Blue No. 1, No. 3, No. 28, No. 29, No. 41, No. 42, No. 47, No. 52, No. 55, CI Edible Purple No. 3, CI Medicinal Red No. 29, No. 42, No. 52, No. 62, No. 76, No. 78, CI MG, No. 1, No. 1, No. 3, No. 6, No. 8, No. 10, No. 11, No. 15, No. 16, No. 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49, CI mord green 3, 13, 21, 23, 31, CI mord Brown 26 Wait. Meanwhile, when the triarylmethane dye is an acid dye or a basic dye, a salt may be formed with any cation or anion. The triarylmethane dye (Ab) is preferably dissolved in an organic solvent. In particular, when the colored curable resin composition of the present invention is prepared as a blue colored curable resin composition, the triarylmethane dye is at least one dye selected from the group consisting of blue, purple, and red. good.

Among these, the triarylmethane dye (Ab) is preferably a dye containing a compound represented by the formula (1b) (hereinafter sometimes referred to as "compound (1b)"). Compound (1b) may also be a tautomer thereof. When the compound (1b) is used, the content of the compound (1b) in the triarylmethane dye (Ab) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as a triarylmethane dye (Ab), it is preferred to use the compound (1b) alone.

[In the formula (1b), R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a phenyl group which may have a substituent or a benzene which may have a substituent methyl.

W ¹ represents a group represented by the formula (Z1) or the formula (Z2).

R ⁴⁷ to R ⁴⁹ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or a halogen atom.

Each of t1 to t3 independently represents an integer of 0 to 4. When t1 is 2 or more, a plurality of R ⁴⁷ may be the same or different; and when t2 is 2 or more, a plurality of R ⁴⁸ may be the same or different; and when t3 is 2 or more, plural R ⁴⁹ can be the same or different.

b represents an integer of 0 or 1.

Xb ^- represents a halide ion or an organometallic anion. ]

Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, neopentyl, An aliphatic saturated hydrocarbon group such as 2-ethylhexyl; an aliphatic unsaturated hydrocarbon group such as a propenyl group or a hexenyl group.

Examples of the halide ion include fluoride ion, chloride ion, bromide ion, and iodide ion.

Examples of the substituent which may be possessed in the aliphatic hydrocarbon group having 1 to 6 carbon atoms, the phenyl group and the benzyl group, and the aliphatic hydrocarbon group having 1 to 6 carbon atoms in R ⁴⁷ to R ⁴⁹ in R ⁴¹ to R ⁴⁶ Examples thereof include -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zb ⁺ and the like.

Further, Zb ⁺ represents: ⁺ N(R ⁵⁰ ) ₄ , Na ⁺ or K ⁺ . R ⁵⁰ 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; and ⁺ N(R ⁵⁰ ) ₄ is exemplified as ⁺ in the formula (1a) N(R ¹¹ ) _{4 is the} same group.

The aliphatic hydrocarbon group in R ⁴¹ to R ⁴⁶ is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

The aliphatic hydrocarbon group in R ⁴⁷ to R ⁴⁹ is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group.

T1 to t3 are independent of each other, and 0 or 1 is preferred.

The organometallic anion in Xb ^- has an anion having a structure in which a metal atom capable of forming a metal ion of two or more valences and an organic compound are bonded by an ionic bond or a coordinate bond.

Examples of the metal atom capable of forming a metal ion having two or more valences include Al, Cr, Co, Fe, Cu, Ni, Co, Zn, Mg, Ca, and Ba. Among them, Al, Cr and Co are preferred.

Examples of the organic compound include salicylic acid, diphenyl glycolic acid, phenylglycolic acid, picolinic acid, and a compound containing a plurality of carboxymethyl groups bonded to a nitrogen atom. Among them, salicylic acid is preferred.

Examples of the salicylic acid described above include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, and 4 - bromodelic acid, 3-methoxysalicylic acid, 2-hydroxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butyl water Salicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, and the like.

Examples of the above-mentioned diphenylglycolic acid include the following compounds.

Examples of the above-mentioned phenylglycolic acid include the following compounds.

Examples of the above-mentioned picolinic acid include the following compounds.

Examples of the compound having a plurality of carboxymethyl groups bonded to a nitrogen atom include the following compounds.

Examples of the above-mentioned organometallic anion include the following anions and the like.

Examples of the compound (1b) include compounds represented by the formula (2-1) to the formula (2-12).

As the triarylmethane dye (Ab), C.I. Acid Blue No. 90 (compound represented by the formula (2-1)) and C.I. Acid Blue No. 104 (compound represented by the formula (2-2)) are preferred. When it is such a triarylmethane dye, a highly contrasting coating film and pattern can be formed, and the occurrence of foreign matter is small.

The dye (Ac) is not particularly limited as long as it is a dye different from the dibenzopyran dye (Aa) and the triarylmethane dye (Ab), and examples thereof include an oil-soluble dye, an acid dye, and a base. Dyes such as dyes, direct dyes, mordant dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes, such as: colorimetric index (The Dyes in the Society of Dyers and Colourists, which are classified as compounds having a hue other than C.I. pigments, and generally known dyes as described in the dyeing guide (color dyeing company). Furthermore, according to the chemical structure, there are: azo dye, cyanine dye, anthraquinone dye, anthraquinone dye, naphthoquinone dye, quinone imine dye, methine dye, azo methine dye, squaric acid Cyanine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, an organic solvent-soluble dye is preferred.

Specific examples are as follows: CI Solvent Yellow No. 4, No. 14, No. 15, No. 23, No. 24, No. 38, No. 62, No. 63, No. 68, No. 82, No. 94, No. 98, No. 99, No. 162; CI Solvent Red 45, 49, 125, 130; CI Solvent Orange 2, 7, 11, 15, 26, 56; CI Solvent Blue 4, 5, 25 , No. 35, No. 37, No. 45, No. 67, No. 70, No. 90; CI Solvent Green No. 1, No. 4, No. 5, No. 7, No. 34, No. 35, etc. CI Solvent Dye, CI Acid Yellow No. 1 , 3, 7, 9, 11, 15, 17, 23, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73 No., 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, Nos. 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, 81, 82, 83, 88 No., 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, 356, 382, 383 No. 394, No. 401, No. 412, No. 417, No. 418, No. 422, No. 426; CI Acid Orange No. 6, No. 7, No. 8, No. 10, No. 12, No. 26, No. 50, No. 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7 , No. 17, No. 19, No. 29, No. 31, No. 33, No. 34, No. 36, No. 36:1, No. 39, No. 41, No. 42, No. 43, No. 47, No. 48, No. 51, No. 63 , 76, 103, 109, 118, 126; CI Acid Blue 2, 8, 14, 18, 23, 25, 27, 29, 35, 37, 41 No. 42, No. 42, No. 45, No. 47, No. 49, No. 50, No. 51, No. 52, No. 53, No. 55, No. 56, No. 57, No. 58, No. 59, No. 60, No. 62, No. 62, 62:1, 63, 64, 65, 68, 69 No. 70, 72, 74, 78, 79, 80, 81, 81:1, 82, 87, 92, 96, 102, 111, 113, 117 No., 120, 122, 124, 126, 127, 127:1, 129, 129:1, 130, 131, 137, 138, 140, 142, 143 , 145, 145:1, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 176, 182, 183 , 184, 187, 192, 198, 199, 203, 204, 205, 208, 210, 220, 229, 234, 236, 242, 243, 256 No. 259, No. 267, No. 285, No. 296, No. 315, No. 335; CI Acid Green No. 1, No. 58, No. 63, No. 65, No. 80, No. 104, No. 105, No. 106, No. 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 No., 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 , No. 246, No. 250; CI Direct Orange No. 34, No. 39, No. 41, No. 46, No. 50, No. 52, No. 56, No. 57, No. 61, No. 64, No. 65, No. 68, No. 70, No. 96, 96 No., No. 97, No. 106, No. 107; CI Direct Violet No. 47, No. 52, No. 54, No. 59, No. 60, 65 No., 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 2, 6 No. 8, No. 15, No. 22, No. 17, No. 57, No. 71, No. 76, No. 78, No. 80, No. 81, No. 84, No. 85, No. 86, No. 90, No. 93, No. 94, No. 95 , 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149 No., 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 No. 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77 , CI No. 79, No. 82, etc. CI Direct Dye, CI Alkaline Blue No. 1, No. 3, No. 5, No. 9, No. 19, No. 24, No. 25, No. 26, No. 28, No. 29, No. 40, No. 41, 41 No. 54, No. 54, No. 58, No. 59, No. 65, No. 65, No. 67, No. 68, No. 68; CI mediated yellow No. 5, No. 8, No. 10, No. 16, No. 20, No. 26, No. 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mor. 2, 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 No., No. 85, No. 86, No. 88, No. 90, No. 94, No. 95; CI mediated oranges No. 3, No. 4, No. 5, No. 8, No. 12, No. 13, No. 14, No. 20, No. 21, No. 23, No. 24, No. 28, No. 29, No. 32, No. 34, No. 35, No. 36, No. 37, No. 42, No. 43, No. 47, No. 48; CI MG, No. 1, No. 2, No. 4 , 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 No.; CI mord blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, No. 31, No. 39, No. 40, No. 41, No. 43, No. 44, No. 49, No. 53, No. 61, No. 74, No. 77, No. 83, No. 84; CI mediated green No. 1, No. 3, No. 4 , 5, 10, 15, 26, 29, 33, 34, 35 41, No. 43, No. 53, etc. of C.I. mordant dyes.

The pigment (Ad) is not particularly limited, and generally known pigments such as a pigment classified as a pigment in the color index (published by The Society of Dyers and Colourists) can be used.

Examples of pigments include: CI Pigment Yellow No. 1, No. 3, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17, No. 20, No. 31, No. 53, No. 83, No. 83, No. 86, No. 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194 Yellow pigments such as No. 214; CI Pigment Orange No. 13, No. 31, No. 36, No. 38, No. 40, No. 42, No., No. 51, No. 55, No. 59, No. 61, No. 64, No. 65, No. 65, Orange pigments such as No. 71 and No. 73; CI Pigment Red No. 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192 Red pigments such as No. 209, No. 215, No. 216, No. 224, No. 242, No. 254, No. 255, No. 264, No. 265; CI Pigment Blue No. 15, No. 15:3, No. 15:4, 15 : Blue pigments such as No. 6, No. 60; purple pigments such as CI Pigment Violet No. 1, No. 19, No. 23, No. 29, No. 32, No. 36, No. 38; CI Pigment Green No. 7, No. 36, No. 58 Green pigments such as No. 23, brown pigments such as CI Pigment Brown No. 23 and No. 25; black pigments such as CI Pigment Black No. 1, No. 7, and the like.

For pigments, blue pigments such as CI Pigment Blue No. 15, 15:3, 15:4, 15:6, No. 60; CI Pigment Violet No. 1, No. 19, No. 23, No. 29, No. 32 The purple pigments such as No. 36 and No. 38 are preferred, and CI Pigment Blue No. 15:3, No.15 and No.23 and CI Pigment Violet No.23 are preferred, and CI Pigment Blue No. 15:6 is even better. When the above-mentioned pigment is contained, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are also good.

Pigments, if necessary, can also be treated with turpentine and used to introduce acid Surface treatment of a pigment derivative such as a base or a basic group, graft treatment of a pigment surface by a polymer compound or the like, microparticulation treatment by a sulfuric acid micronization method, or an organic solvent for removing impurities Or a washing treatment such as water, or a removal treatment of an ionic impurity by an ion exchange method or the like.

The pigment is preferably one having a uniform particle size. When the dispersion treatment is carried out by including a pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include cationic dispersants such as cationic, anionic, nonionic, zwitterionic, polyester, polyamine, and polyacryl. These pigment dispersants may be used alone or in combination of two or more. For the pigment dispersant, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Astra Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), AJISPER (Azure) Manufactured by Seiko Co., Ltd., Disperbyk (manufactured by BYK-Chemie Co., Ltd.).

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

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

The content of the triarylmethane dye (Ab) is preferably 1 part by mass or more and 100 parts by mass or less based on 100 parts by mass of the dibenzopyran dye (Aa), and more preferably 20 parts by mass or more and 100 parts by mass or less.

The content of the pigment (Ad) is preferably 10% by mass or more and 99.9% by mass or less, and more preferably 30% by mass or more and 99% by mass or less based on the total amount of the coloring agent (A).

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 based on the total amount of the coloring agent (A), and 0.5% by mass or more and 30% by mass. % is better.

The coloring agent (A) is preferably a coloring agent containing a dibenzopyran dye (Aa), a triarylmethane dye (Ab), and a pigment (Ad). In this case, the content of each of these is a dibenzopyran dye (Aa): 0.1% by mass or more and 70% by mass or less of the triarylmethane dye (Ab) with respect to the total amount of the colorant (A): 0.1% by mass or more and 70% by mass or less of the pigment (Ad): preferably 29.9% by mass or more and 99.8% by mass or less, and the dibenzopyran dye (Aa): 0.5% by mass or more and 50% by mass or less of the triarylmethane dye (Ab): 0.5% by mass or more and 50% by mass or less of the pigment (Ad): more preferably 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 content. When the content of the coloring agent (A) is in the above range, the color density can be made sufficient as a color filter, and the necessary amount of the resin (B) and the polymerizable compound (C) can be contained in the composition, so that the machine can be formed. A pattern of sufficient strength. Here, the "total amount of solid content" as used herein means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the relative content of each component can be as follows: liquid chromatography or gas phase layer Analytical methods such as analysis are generally known.

<Resin (B)>

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

The resin "K1" is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a)"), and a cyclic ether having a carbon number of 2 to 4. a copolymer of a monomer (b) having a structure of an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); a resin "K2" (a) and (b), and a copolymerizable with (a) Monomer (c) (however, different from (a) and (b).) (hereinafter sometimes referred to as "(c)") copolymer; resin "K3" is a copolymer of (a) and (c) Resin "K4" is a copolymer of (a) and (c) and then reacted with (b); resin "K5" is a copolymer of (b) and (c) and then reacted with (a); resin "K6" is a resin in which the copolymer of (b) and (c) is further reacted with (a) and further reacted with a carboxylic anhydride.

(a), specifically, an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid; Diacid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3 , an unsaturated dicarboxylic acid such as 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-bornene-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] Geng-2- Alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6- a carboxyl group-containing bicyclic unsaturated compound such as ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-ethylene Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydration 5, Unsaturated dicarboxylic acid anhydride of 6-dicarboxybicyclo[2.2.1]hept-2-ene; succinic acid mono[2-(methyl)propenyloxyethyl]ester, phthalic acid mono [2] -Unsaturated mono[(meth)acryloxyalkyl]ester of a polyvalent carboxylic acid having two or more valences such as -(meth)acryloxyethyl]ester; α-(hydroxymethyl)acrylic acid An unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of the copolymerization reactivity and the solubility of the obtained resin to the aqueous alkali solution.

(b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). One type) and a polymerizable compound having an ethylenically unsaturated bond. In the aspect (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferred.

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

(b) Examples thereof include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), and having an oxetanyl group. a monomer (b2) having an (oxetanyl) group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)") and so on.

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

Examples of (b1-1) include, for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethylepoxypropyl (meth)acrylate. Ester, epoxypropyl vinyl ether, o-vinylbenzyloxypropyl ether, m-vinylbenzyloxypropyl ether, p-vinylbenzyloxypropyl ether, α -Methyl-o-vinylbenzyloxypropyl ether, α-methyl-m-vinylbenzyloxypropyl ether, α-methyl-p-vinylbenzyloxypropyl Ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-di(epoxypropyloxymethyl) ) styrene, 2,6-bis(goxypropyloxymethyl)styrene, 2,3,4-tris(oxiranoxymethyl)styrene, 2,3,5-tris(epoxy) Propyloxymethyl)styrene, 2,3,6-tris(epoxypropyloxymethyl)styrene, 3,4,5-tris(epoxypropyloxymethyl)styrene, 2,4 , 6-tris(epoxypropyloxymethyl)styrene, and the like.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel), (methyl) ) 3,4-epoxycyclohexylmethyl acrylate (eg Cyclomer A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg Cyclomer M100; manufactured by Daicel) A compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the general formula (I) and the general formula (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 bond base with O. ]

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

Examples of the alkyl group in which the hydrogen atom is a hydroxyl group may be hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl or 3-hydroxypropyl. 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

Preferred examples of R ^a and R ^b include a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1 group. 5-diyl, hexane-1,6-diyl and the like.

The preferred ones of X ^a and X ^b are as follows: single bond, methylene group, ethyl group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, preferably, single bond, *- More preferably CH ₂ CH ₂ -O- (* indicates a bond group 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). Further, the formula (I-1), the formula (I-3), the formula (I-5), and the formula (I-7), The compound represented by the formula (I-9) or the formula (I-11) to the formula (I-15) is preferred. The compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) is more preferable.

The compound represented by the formula (II) may, for example, be a compound represented by the formula (II-1) to the formula (II-15). By the general formula (II-1), the general formula (II-3), the general formula (II-5), the general formula (II-7), the general formula (II-9) or the general formula (II-11) The compound represented by the formula (II-15) is preferred. The compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly. Moreover, these can also be mixed in any ratio. When mixing, the mixing ratio is in molar ratio, preferably from the formula (I): the formula (II) is from 5:95 to 95:5, more preferably from 10:90 to 90:10, at 20:80. It is even better at 80:20.

(b2), more preferably a monomer having an oxetanyl group and a (meth) acryloxy group. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3 -ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3- Methyl-3-methylpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropene oxime Ethyl oxetane, 3-ethyl-3-propenyloxyethyloxetane, and the like.

(b3), more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. In the aspect of (b3), specifically, tetrahydrofuran methyl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuranmethyl methacrylate or the like can be exemplified.

In the case of (b), it is preferable that (b1) is preferable in that the reliability of the obtained color filter is higher in heat resistance and chemical resistance. At the same time, (b1-2) is more preferable because the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2.6 ]decane-8-ester (in the technical field) The conventional name is "dicyclopentanyl (meth) acrylate." Also, it is sometimes called "tricyclodecyl (meth) acrylate".), tricyclo(meth) acrylate [5.2.1.0 ^2.6 Terpene-8-ester (in the technical field, the customary name is "dicyclopentenyl (meth)acrylate".), dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (methyl) (meth)acrylates such as benzyl acrylate; 2-hydroxyl (meth)acrylate a hydroxyl group-containing (meth) acrylate such as ethyl ester or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and diethyl itaconate a dicarboxylic acid diester of an ester or the like; a bicyclo[2.2.1]hept-2-ene, a 5-methylbicyclo[2.2.1]hept-2-ene, a 5-ethylbicyclo[2.2.1] Hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-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-di(2'- Hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2 .1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene , 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy Alkylcarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[ 2.2.1] Hept-2-ene, 5 a bicyclic unsaturated compound of 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylm-butyleneimine, N-cyclohexyl cis-butyl Iridylimine, N-benzylmethyleneimine, N-succinimido-3-methyleneimine benzoate, N-succinimide-4 - maleimide butyrate, N-succinimide-6-methyleneimide hexanoate, N-succinimide-3-oxetimine Dicarbonyl quinone imine derivatives such as propionate, N-(9-acridinyl) maleimide, styrene, α-methylstyrene, m-methylstyrene, p-methyl Styrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butyl Alkene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, benzene is used in terms of copolymerization reactivity and heat resistance. Ethylene, vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] Hept-2-ene and the like are preferred.

In the resin "K1", the ratio derived from each structural unit is derived from the structural unit derived from (a) in the total structural unit constituting the resin "K1": 2 to 60 mol% derived from the structural unit of (b) 40 to 98 mol% is preferred, and the structural unit derived from (a): 10 to 50 mol% is derived from the structural unit of (b): preferably 50 to 90 mol%.

When the ratio of the structural unit of the resin "K1" is in the above range, for example, the storage stability of the colored curable resin composition, the development property when a coloring pattern is formed, and the solvent resistance of the obtained color filter are further improved. Good tendency.

Resin "K1" can be referred to in the document "Polymer Synthesis Experiment Method" (Dazu Takashi, Publisher, Chemicals, Co., Ltd., 1st Edition, 1st, 1st, 1972, March 1, 1972) and the documents described in the literature. Manufactured by citing literature.

Specifically, a method may be mentioned in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, nitrogen is substituted for oxygen to remove oxygen gas. , stirring, and heating and heat preservation at the same time. Further, the polymerization initiator, the solvent and the like used therein are not particularly limited, and those generally used in the category can be used. For example, a polymerization initiator may, for example, be an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic The peroxide (such as benzamidine peroxide); the solvent may be any solvent that can dissolve the monomer, and the solvent (E) of the colored curable resin composition of the present invention may be dissolved as described later. Agents, etc.

Further, the copolymer obtained may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) obtained by reprecipitation or the like may be used. In particular, in the solvent at the time of polymerization, by using the solvent contained in the colored curable resin composition of the present invention, the solution after the reaction can be directly used in the preparation of the color-curable resin composition of the present invention. The production steps of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio derived from each structural unit, in the total structural unit constituting the resin [K2], is a structural unit derived from (a): 2 to 45 mol% derived from the structural unit of (b) : 2 to 95 mol% derived from the structural unit of (c): preferably from 1 to 65 mol%, from the structural unit derived from (a): 5 to 40 mol% derived from the structural unit of (b): 5 to 80 mol% is derived from the structural unit of (c): 5 to 60 mol% is more preferable.

When the ratio of the structural unit of the resin [K2] is in the above range, for example, the storage stability of the colored curable resin composition, the development property when a color pattern is formed, and the solvent resistance and heat resistance of the obtained color filter are obtained. Sexual and mechanical strength has a better tendency.

The resin [K2] can be produced in the same manner as described in the production method of the resin [K1].

In the resin [K3], the ratio derived from each structural unit is in the composition of the resin. In the total structural unit of [K3], the structural unit derived from (a): 2 to 60 mol% is derived from the structural unit of (c): preferably 40 to 98 mol%, derived from the structure of (a) Unit: 10 to 50 mol% The structural unit derived from (c): 50 to 90 mol% is more preferable.

The resin [K3] can be produced in the same manner as described in the production method of the resin [K1].

In the resin [K4], the copolymer of (a) and (c) may be obtained first, and the carboxylic acid and/or carboxylic anhydride having (a) may be added by (b) a cyclic ether having a carbon number of 2 to 4; Made into.

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

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

After the copolymer of (a) and (c) is produced, the gas in the flask is replaced by nitrogen to air, and then the catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (such as tris(dimethyl) The resin [K4] can be produced by adding a polymerization inhibitor (such as hydroquinone) and a polymerization inhibitor (such as hydroquinone) to a flask, and reacting 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. In this range, the colored curable resin can be composed The stability of the object, the development of the color pattern, and the balance of solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tend to be better. The reactivity from the cyclic ether is high and the unreacted (b) remains, and the (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total 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 addition method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the heat generation amount of the polymerization, and the like. At the same time, as with the polymerization conditions, the addition method and the reaction temperature can be appropriately adjusted in consideration of the manufacturing equipment and the calorific value of the polymerization.

The resin [K5] was obtained in the same manner as in the above-described production method of the resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer can be used as it is, and a concentrated or diluted solution can be used, and a solid (powder) obtained by reprecipitation or the like can also be used.

The ratio of the structural units derived from (b) and (c), relative to the total number of moles constituting the total structural unit of the aforementioned copolymer, is derived from the structural unit derived from (b): 5 to 95 mol% (from The structural unit of c) is preferably from 5 to 95 mol%, and the structural unit derived from (b): from 10 to 90 mol%, from the structural unit of (c): more preferably from 10 to 90 mol%.

At the same time, the carboxylic acid of (a) is obtained by the cyclic ether derived from (b) of the copolymer of (b) and (c) under the same conditions as the method for producing the resin [K4]. The resin [K5] can be obtained by reacting with a carboxylic anhydride.

The amount of (a) used in the reaction with the aforementioned copolymer is preferably from 5 to 80 moles per 100 moles of (b). The reactivity from the cyclic ether is better and the unreacted (b) remains, and the (b) used for the resin [K5] is preferably (b1), more preferably (b1-1).

The resin [K6] is a resin in which the resin [K5] is further reacted with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted by a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3, 4, 5, 6-four. Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydrated 5,6-dicarboxybicyclo[2.2.1]heptan-2- Alkene (Himic anhydride) or 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).

Resin (B), specifically, (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, acrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2.6 ] resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, (methyl) Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricycloacrylate [5.2.1.0 ^2.6 ] decyl ester / (meth)acrylic acid / N-cyclohexyl cis-butene a resin such as a quinone imine copolymer, a 3-methyl-3-(meth) propylene methoxymethyl oxetane/(meth)acrylic acid/styrene copolymer [K2]; (methyl) Resin of benzyl methacrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic copolymer, etc. [K3]; benzyl (meth) acrylate/(meth)acrylic acid copolymer (meth)acrylic acid propyl acrylate addition resin, trimethyl decyl (meth) acrylate / styrene / (meth) acrylate copolymer and then (meth) acrylate propyl acrylate resin, (a Base) tricyclodecyl acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer a resin such as a resin of glycidyl acrylate-added resin [K4]; a copolymer of trimethyl decyl (meth) acrylate / glycidyl (meth) acrylate and a resin reacted with (meth) acrylate a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate and a resin such as a resin reacted with (meth)acrylic acid [K5]; tricyclo(meth)acrylate A copolymer of decyl ester/glycidyl methacrylate and a resin such as a resin which is reacted with (meth)acrylic acid and further reacted with tetrahydrophthalic anhydride, etc. [K6].

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

The weight average molecular weight of the resin (B) to polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is increased, the film residual ratio is also high, the solubility of the unexposed portion to the developing solution is better, and the resolution of the colored pattern tends to be higher.

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. The acid value refers to a value measured by neutralizing the amount (mg) of potassium hydroxide necessary for 1 g of the resin (B), and can be determined by titration with 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 within the above range, a coloring pattern can be formed, and the resolution of the coloring pattern and the film residual ratio tend to be improved.

<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, and the like. A (meth) acrylate compound is preferred.

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 tri(meth)acrylate, neopentyl glycol tri(meth)acrylate, neopentyl glycol tetra(meth)acrylate, and five. Dipentaerythritol (meth)acrylate, dineopentyl hexa(meth)acrylate, tricobalt octa(meth)acrylate, tricrostitol hexa(meth)acrylate , tetrapentaerythritol decyl (meth) acrylate, tetrane pentaerythritol penta(meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isopropyl cyanide, B Glycol-modified neopentyl glycol (meth)acrylate, ethylene glycol modified pentatyl hexa(meth) acrylate, propylene glycol modified neopentyl glycol (meth) acrylate, propylene glycol Modification of dipentaerythritol hexa(meth)acrylate, modification of caprolactone to neopentyl glycol (meth)acrylate, caprolactone modification of dipentaerythritol hexa(meth)acrylate, etc. .

Among them, dineopentaerythritol penta(meth)acrylate and dipentaerythritol 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 7 to 65 mass%, more preferably 13 to 60 mass%, still more preferably 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 film residual ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be better.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid or the like by the action of light and heat, and a generally known polymerization initiator can be used.

a polymerization initiator (D) containing a compound selected from the group consisting of alkyl phenones, three At least one polymerization initiator which is a group of the compound, the fluorenylphosphonium compound, the o-nonyl ruthenium compound and the biimidazole compound is preferred, and the polymerization initiator containing the o-nonyl ruthenium compound is more preferable.

The above o-nonyl fluorene compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * denotes a bonding group.

Examples of the above-mentioned ortho-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine and N-benzylformamide 1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylmercaptophenyl)-3-cyclopentyl Propane-1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxancyclopentyl) Methoxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2-methyl) Benzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Products such as Irgacure OXE 01, OXE 02 (above, manufactured by BASF Corporation), N-1919 (made by ADEKA Corporation), and the like can also be used. Wherein the ortho-indenyl hydrazine compound is selected from the group consisting of N-benzylideneoxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzylideneoxy- 1-(4-phenylmercaptophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylmercaptobenzene At least one selected from the group consisting of -3-cyclopentylpropan-1-one-2-imine, N-benzylideneoxy-1-(4-phenylmercaptophenyl) octyl Alkan-1-one-2-imine is more preferred. Such ortho-quinone-based compounds have a tendency to obtain high-density color filters.

The above alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure as shown in the formula (d3). In such partial configurations, the phenyl ring may contain a substituent.

The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-N-morpholinyl-1-(4-methylindenylphenyl)propan-1-one, 2-Dimethylamino-1-(4-N-morpholinylphenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) may 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)propane An oligomer of 1-ketone, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

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

The above triterpene compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-di(trichloro) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-di(trichloromethyl)-6-piperidin-1,3,5-triazine 2,4-di(trichloromethane) 6-(4-methoxystyryl)-1,3,5-triazine, 2,4-di(trichloromethyl)-6-[2-(5-methylfuran-2 -yl)vinyl]-1,3,5-triazine, 2,4-di(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5- Triterpenoid, 2,4-di(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2 , 4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

The cerium phosphinylphosphine compound may, for example, be oxidized-2,4,6-trimethylbenzhydryldiphenylphosphine. A product such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-di(2, 3-Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to, for example, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-di ( 2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis Oxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-di (2-Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to, for example, JPS48-38403-B, JPS62-174204-A, etc.), 4 The phenyl group at the 4', 5, 5'-position is an imidazole compound substituted with an alkoxycarbonyl group (refer to, for example, JPH07-10913-A, etc.) and the like.

At the same time, the polymerization initiator (D) may also be exemplified by benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like. Affinity compound; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4 a benzophenone compound such as 4'-tetrakis(t-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylidene An anthraquinone compound such as hydrazine or camphor; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compound, and the like. These It is preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

Examples of the acid generator include p-toluenesulfonic acid-4-hydroxyphenyldimethylhydrazine, hexafluoroantimonic acid-4-hydroxyphenyldimethylhydrazine, p-toluenesulfonic acid-4-ethoxime Benzo dimethyl hydrazine, hexafluoroantimonic acid-4-ethenyloxyphenyl/methyl/benzyl hydrazine, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, p-toluenesulfonate An anthracene salt such as diphenyl sulfonium acid or diphenyl sulfonium hexafluoroantimonate; nitrobenzyl methyl tomate sulfonate; benzoin toluene sulfonate;

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 within the above range, the sensitivity can be increased and the exposure time can be shortened, so that the productivity of the color filter can be further improved.

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer which can be used for the polymerization of a polymerizable compound which starts polymerization by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it is generally used in combination with the polymerization initiator (D).

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

Examples of the aforementioned amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-methyl Aniline, 4,4'-bis(dimethylamino)benzophenone (commonly known as mickleone), 4,4'-di(diethylamino)benzophenone, 4,4' -Bis(ethylmethylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.), etc. The goods can also be used.

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

Examples of the aforementioned thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, and 2,4-di. Chlorothione, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the carboxylic acid compound include phenylmercaptoacetic acid, methylphenylmercaptoacetic acid, ethylphenylmercaptoacetic acid, methylethylphenylmercaptoacetic acid, dimethylphenylsulfanylacetic acid, and A. Oxyphenylthioalkylacetic acid, dimethoxyphenyl-mercaptoacetic acid, methoxyphenyl-mercaptoacetic acid, dimethoxyphenyl-mercaptoacetic acid, chlorophenyl-mercaptoacetic acid, dichlorophenyl-mercaptoacetic acid, N- Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

When such a polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, and 1 to 20 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Better. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and there is a tendency to improve the productivity of the color filter.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in this category can be used. For example, an ester solvent (a solvent containing -COO-, a solvent containing no -O-), an ether solvent (a solvent containing -O-, a solvent containing no -COO-), an ether ester solvent (molecular inclusion) -COO- and -O-solvent), ketone solvent (molecular-CO-, solvent free of -COO-), alcohol solvent (molecular OH, no -O-, -CO- and -COO - the solvent), aromatic Hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and acetic acid. Amyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate , cyclohexanol acetate, γ-butyrolactone, and the like.

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, and diethylene glycol monoethyl ether. , diethylene 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-methylbutyl Alcohol, 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, anisole, phenyl ether, methyl Anisole 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, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ester, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 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.

The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.

The aromatic hydrocarbon solvent may, for example, be benzene, toluene, xylene or trimethylbenzene.

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

Among the above solvents, an organic solvent having a boiling point of at least 1 atm of from 120 ° C to 180 ° C is preferred from the viewpoint of coatability and dryness. The solvent is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol single Ethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 3-ethyl Ethyl oxypropionate is more preferred.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of 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 coating can be improved, and the color filter is not formed when the color filter is formed, so that the display property tends to be better.

<Painting agent (F)>

Examples of the coating agent (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may contain a polymerizable group on the side chain.

The polyoxo-based surfactant may have a decane bond in the molecule. Surfactant and the like. Specific examples are: Toray Silicone DC3PA, the same series SH7PA, the same series DC11PA, the same series SH21PA, the same series SH28PA, the same series SH29PA, the same series SH30PA, the same series SH8400 (trade name: Dow Corning Toray company), KP321 KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials, Japan).

The fluorine-based surfactant may, for example, be a surfactant of a fluorine-containing carbon chain in the molecule. Specific examples include: Fluorad (registered trademark) FC430, the same series FC431 (manufactured by Sumitomo 3M), MEGAFAC (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177, the same series F183 , the same series F554, the same series R30, the same series RS-718-K (made by DIC company), EFTOP (registered trademark) EF301, the same series EF303, the same series EF351, the same series EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, the same series S382, the same series SC101, the same series SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Corporation Daikin Precision Research Institute), etc.

The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a decane bond or a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, the same series BL20, the same series F475, the same series F477, and the same series F443 (manufactured by DIC Corporation).

The content of the coating 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 more preferably 0.01% by mass or more and 0.05% by mass based on the total amount of the coloring curable resin composition. % is better and below. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made better.

<Other ingredients>

The color-curable resin composition of the present invention may further contain a filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, etc., if necessary, and additives generally known in the technical field. .

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention may be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a solvent (E). The agent (F), the polymerization starting aid (D1) and other components are mixed and prepared.

However, a dibenzopyran dye (Aa), a triarylmethane dye (Ab), and optionally a dye (Ac) may be previously dissolved in a part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a membrane having a pore diameter of about 0.01 to 1 μm.

In the case of the pigment (Ad), it is preferred to mix it with a part or all of the solvent (E) in advance, and then use a bead mill or the like to disperse it until the average particle diameter of the pigment is about 0.2 μm or less. In some cases, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as necessary. By mixing the remaining components in the pigment dispersion obtained in this manner and setting the concentration, the intended color-curable resin composition can be prepared.

It is preferred that the colored curable resin composition after mixing is filtered with a filter having a pore diameter of about 0.01 to 10 μm.

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

Examples of the method of forming a color filter using the colored curable resin composition of the present invention include a photolithography method and a method using an ink jet apparatus. The photoetching method is, for example, applying the colored curable resin composition of the present invention to a substrate, and then A method in which a volatile component such as a solvent is removed to form a colored composition layer, and then the colored composition layer is exposed through a photomask to be developed. After the image is developed, a colored pattern can be formed by heating as necessary. In the method of forming the coloring pattern, the colored coating film of the cured product of the colored composition layer can be formed by not using a photomask during exposure and/or when no image is formed. The obtained coloring pattern and coloring coating film are color filters.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with cerium oxide, and polycarbonate, polymethyl methacrylate, and poly A resin plate or the like of ethylene terephthalate or the like is used after forming an aluminum, silver, silver/copper/palladium alloy thin film or the like on the substrate. On the substrate, other color filter layers, resin layers, transistors, circuits, and the like may be formed.

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

Next, a method of forming a pattern on 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 generally known method such as photolithography (see Fig. 1). The TFT 22 is composed of, for example, a gate electrode 22a formed of molybdenum (Mo) on the glass substrate 21 and forming a part of the gate line, and a nitride film (SiN _X ) formed on the gate electrode 22a. a gate insulating film 22b of a build-up film of an oxide film (SiO ₂ ), a polysilicon film 22c formed on the gate insulating film 22b, and a film such as an oxide film (SiO ₂ ) and a nitride film (SiN _X ) The protective film 22d formed by the laminated film is composed of a film. The region of the polysilicon film 22c opposed to the gate electrode 22a is a channel region of the TFT 22. Further, the region on both sides of the channel region becomes a source region or a drain region. The source region of the polysilicon film 22c is in contact with a contact hole provided on the protective film 22d, and is electrically connected to a signal line 27 formed of, for example, aluminum (Al). Further, the drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 as will be described later.

When a plurality of TFTs 22 are formed on each of the pixels on the glass substrate 21, alignment marks (not shown) are formed on the glass substrate 21 simultaneously with the TFTs 22. This alignment mark is used as a reference for positional alignment in the formation step of the color filter layer 23 as will be described later. Furthermore, these alignment marks can also serve as a mark for bonding the drive substrate and the counter substrate. The alignment mark can be formed in the same step by at least one layer when a metal layer such as a wiring or a polysilicon layer is formed in the process of manufacturing 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 (prebake) and/or drying under reduced pressure. Drying is carried out to form a colored composition layer having a film thickness of 0.5 to 5.0 μm, such as 1.0 μm.

The coating method may be, for example, a spin coating method, a slit coating method, a slit type spin coating method, or the like.

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

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

Next, the colored composition layer is irradiated with ultraviolet rays through a photomask (not shown), and the developing liquid is selectively removed without being required to be formed. The colored composition layer formed on the pixel of the contact hole 201 on the drain region of the polysilicon film 22c is then washed with water.

Thereafter, the unexposed portion of the colored composition layer is dissolved and removed in the developing solution by development. As an example of the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration of such a basic compound in an aqueous solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Furthermore, in terms of a developing solution, a surfactant may be further included.

The method of development can be any paddle method, dipping method, or spray method. The substrate can be tilted at any angle during development.

Thereafter, in order to reflow the colored composition layer forming the contact hole 201, and/or to harden the polymerizable compound (C) or the like contained in the colored composition layer, it may be 100 to 300. °C, preferably at a temperature of from 150 to 230 ° C, for from 1 to 120 minutes, preferably from 10 to 60 minutes. In this way, the colored curable resin composition layer 23A of the colored pattern can be formed. The colored curable resin composition layer 23A corresponds to the color filter of the present invention.

By repeating this operation, each colored curable resin composition layer 23A is formed from the red colored curable resin composition, the green colored curable resin composition, and the blue colored curable resin composition, and can be formed on each pixel column. Corresponding to the color filter layer 23 including the red color filter 23a, the green color filter 23b, and the blue color filter 23c (refer to Fig. 2). The area between the color filters of the color filter layer 23 is a mixed area of adjacent colors, which is a light-shielding area opposed to the signal line 27, and has no particular influence on the quality. Furthermore, the area between the color filters may not be colored.

Next, the color filter layer 23 is covered by a spin coating method to form a photosensitive resin film 29 such as a protective film having a film thickness of 0.3 to 2.0 μm. Second, through the mask (not shown), the photosensitive resin film 29 is irradiated with ultraviolet rays, and the region corresponding to the contact hole 201 and the unnecessary portion are selectively removed by the developing liquid, and then contact is formed on the drain region which reaches the polysilicon film 22c. The contact hole 202 is then washed with water. Thereafter, in order to reflow the photosensitive resin film 29, it is heated at, for example, 200 ° C at a temperature in the range of 100 to 300 ° C. Next, in order to remove the residue and organic matter of the dye or the like deposited in the contact hole 202, etching is performed by oxygen plasma, and in order to remove the oxide film formed by the oxygen plasma, it is performed by, for example, dilute hydrofluoric acid. Etching.

Then, the transparent conductive material is formed on the photosensitive resin film 29 by, for example, spin coating, such as ITO (Indium-Tin Oxide: oxide mixed film of indium and tin), and the ITO film is further photoetched. The pattern is formed by etching 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 to manufacture a liquid crystal display device.

According to the colored curable resin composition of the present invention, a color filter which is particularly excellent in comparison can be produced. The color filter can be used as a color filter in a display device (such as a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image element.

Example

Hereinafter, the colored curable resin composition of the present invention will be described in more detail with reference to examples. "%" and "parts" in the examples are % by mass and parts by mass unless otherwise stated.

In the following synthesis examples, the compounds were identified by mass analysis (LC: Agilent 1200, MASS: Agilent LC/MSD) or elemental analysis (VARIO-EL: manufactured by ELEMENTAL).

[Synthesis Example 1]

20 parts of the compound of the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was further stirred at 110 ° C for 6 hours. Thereafter, the obtained reaction liquid was cooled to room temperature, and then 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 to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain a residue, followed by drying to obtain 24 parts of a compound represented by the formula (1-24) (hereinafter referred to as "dibenzopyran dye 1"). The yield was 80%.

Identification of the compound of the formula (1-24): (mass analysis) ionization morphology = ESI +: m / z = [M + H] ⁺ 603.4 Exact Mass: 602.2

[Synthesis Example 2]

In a flask containing 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 Pink R; 15 parts, 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were added, and the mixture was kept at 20 ° C or lower with stirring, and 10.9 parts of sulfite chloride was added dropwise. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was carried out at the same temperature for 5 hours, followed by cooling to 20 ° C. The cooled reaction solution was maintained at 20 ° C or lower with stirring, and a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. After that, stir at the same temperature for 5 hours. Reaction. Next, after the obtained reaction mixture was distilled off in a rotary distiller, a small amount of methanol was added and vigorously stirred. The mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. Thereafter, the precipitated crystals are separated by filtration, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dibenzopyran dye 2 (general formula (Aa-1-1) to formula (Aa- 1-8) A mixture of the compounds shown) 11.3 parts.

[Synthesis Example 3]

1.0 part of a compound represented by the formula (f-1) (BONTRON (registered trademark) E-108, manufactured by Orient Chemical Industry Co., Ltd.) was dissolved in 70 parts of N,N-dimethylformamide to prepare a solution (s1). ). Further, 3.92 parts of a compound represented by the formula (2-5) (Victoria Pure Blue BO, manufactured by Sigma-Aldrich Co., Ltd.) was dissolved in 90 parts of N,N-dimethylformamide to prepare a solution (t1). . Thereafter, the solution (t1) was added to the solution (s1) at 25 ° C, and then the temperature was further raised to 80 ° C and stirred for 8 hours. After the mixture was cooled to room temperature, 100 parts of saturated brine was added thereto, and then 1000 parts of ion-exchanged water was added thereto, and the mixture was further stirred for 1 hour. After that, the precipitate was collected by suction filtration, and washed with 100 parts of ion-exchanged water and 100 parts of hexane to obtain a compound represented by the formula (2-9) (hereinafter referred to as "triarylmethane dye 1"). 1.70 servings.

Identification of the compound of the formula (2-9): (elemental analysis) C: 75.6 H: 7.9 N: 4.2

[Synthesis Example 4]

3.30 parts of 3-bromofluorobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.00 parts of diethylamine, 0.064 parts of copper powder (manufactured by Kanto Chemical Co., Ltd.), 0.19 parts of copper (I) iodide, and tripotassium phosphate n-hydrate (manufactured by Kanto Chemical Co., Ltd.) 2.20 parts and 2 (dimethylamino)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.0 parts were mixed at room temperature, and the mixture was further heated to 80 ° C and stirred for 72 hours. After the mixture was cooled to room temperature, 200 parts of water and 150 parts of chloroform were added, and the mixture was separated to obtain a chloroform layer, which was then dried over magnesium sulfate. Further, the solution obtained by removing magnesium sulfate was distilled off under reduced pressure to give chloroform, and the compound of the formula (gx-1) was obtained.

16.30 parts of N,N-diethyl-3-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 19.00 parts of dimethoxymethane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 100 parts of acetic acid were mixed. Thereafter, 300 parts of a mixture of acetic acid/98% sulfuric acid (1/1) was added dropwise to the mixed solution, and stirred at room temperature for 10 minutes. Thereafter, the precipitate was collected by suction filtration, and washed with 1000 parts of ion-exchanged water to obtain 10.04 parts of a compound represented by the following formula (gx-2).

6.70 parts of the compound represented by the formula (gx-2), 20 parts of potassium permanganate (manufactured by Kanto Chemical Co., Ltd.), copper (II) sulfate and a mixture (manufactured by Kanto Chemical Co., Ltd.) were mixed and placed in a room. Stir for 6 hours at room temperature. Then, 200 parts of chloroform was added to the reaction, and the chloroform extraction solution was separated by filtration. The chloroform was distilled off under reduced pressure to give 6.20 parts of the compound of the formula (gx-3).

14.10 parts of the compound represented by the formula (gx-3), 34.50 parts of the compound represented by the formula (gx-1), and 50 parts of phosphorous oxychloride (manufactured by Kanto Chemical Co., Ltd.) were mixed at room temperature. The temperature was raised to 100 ° C and stirred for 3 hours. After the mixture was cooled to room temperature, a mixed solvent of 120 parts of ethyl acetate / 10 parts of perchloric acid was added, and the mixture was further stirred for 1 hour. Then, the precipitate was obtained by suction filtration, and washed with 200 parts of ethyl acetate to obtain 8.64 parts of a salt represented by the following formula (g-1).

1.54 parts of a compound represented by the formula (f-1) (BONTRON (registered trademark) E-108, manufactured by Orient Chemical Industry Co., Ltd.) was dissolved in 61 parts of N,N-dimethylformamide to prepare a solution (s2). ). Further, 1.50 parts of the salt represented by the formula (g-1) was dissolved in 15 parts of N,N-dimethylformamide to prepare a solution (t2). Then, a solution of (t2) was added to the solution (s2) at 25 ° C, and stirred for 2 hours. Further, 382 parts of ion-exchanged water was added to the mixture, and the mixture was further stirred for 1 hour. Then, the precipitate was collected by suction filtration, and washed with 127 parts of ion-exchanged water to obtain 1.78 parts of a compound represented by the formula (2-10) (hereinafter referred to as "triarylmethane dye 2").

Identification of the compound of the formula (2-10): (elemental analysis) C: 73.7 H: 8.4 N: 4.1

[Synthesis Example 5]

Nitrogen gas was introduced into a nitrogen atmosphere at 0.02 L/min in a triangular flask equipped with a circulation condenser, a dropping funnel, and a stirrer, and then 305 parts by mass of ethyl lactate was added, and heated to 70 ° C while 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)) The mixture was mixed at a molar ratio of 50:50. 240 parts by mass and 185 parts by mass of ethyl lactate were dissolved to prepare a solution, and the solution was added dropwise to a flask at 70 ° C for 4 hours in 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. Into the flask in 4 hours. 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, and a solid content of 26 % by mass. The solid solution was a resin B1 solution having an acid value of 120 mg-KOH/g. This resin B1 has the structural unit shown below.

[Synthesis Example 6]

In a triangular flask equipped with a stirrer, a thermometer, a circulating condenser, a dropping funnel, and a nitrogen introduction tube, 182 g of propylene glycol monomethyl ether acetate was introduced, and the gas in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. Thereafter, it is a monomethacrylate (dicyclopentyl methacrylate) containing 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and a tricyclodecane skeleton; Hitachi A solution of 2,2'-azobisisobutyronitrile (3.6 g) was added dropwise to a mixture of 22.0 g (0.10 mol) and propylene glycol monomethyl ether acetate 136 g of FA-513M manufactured by Huacheng Co., Ltd. at 100 ° C. Continue to stir.

Next, the gas in the flask was changed from nitrogen to air, and 35.5 g [0.25 mol of propylene glycol methacrylate (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction) ], tris-dimethylaminomethylphenol 0.9 g and hydroquinone 0.145 g were placed in a triangular flask, and then the reaction was continued at 110 ° C to obtain a resin having a solid content of 29% and a solid content of 79 mg-KOH/g. B2 solution. The weight average molecular weight of the converted polystyrene by GPC measurement was 30,000.

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

Device; K2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

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

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

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

First, (A) colorant: CI Pigment Blue 15: No. 6 (pigment) 16 parts of acrylic pigment dispersant 3.9 parts of propylene glycol monomethyl ether acetate 130 parts were mixed, and the pigment was completely dispersed by a bead mill. Next, (A) Colorant: Dibenzopyran dye 1 2.2 parts (A) Colorant: CI Acid Blue No. 104 (Daiwa BLUE 300: manufactured by Daiwa Chemical Co., Ltd.: Triarylmethane dye) 0.9 part (B) Resin: Resin B1 (converted solid content) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA: manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzylideneoxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01: manufactured by BASF Corporation) 10 parts (F) Agent: Polyether modified polyoxygenated oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.1 part (E) Solvent: ethyl lactate 556 parts (E) Solvent: propylene glycol monomethyl ether acetate 8 parts were mixed A colored curable resin composition.

<Production of coloring pattern>

First on a 5cm square glass substrate (EAGLE 2000: Corning In the production, the colored curable resin composition was applied by a spin coating method, and then prebaked at 100 ° C for 3 minutes to obtain a colored layer.

Thereafter, after cooling, the distance between the substrate on which the coloring layer was formed and the mask made of quartz glass was 100 μm, and the exposure amount (150E-150RSK; manufactured by TOPCON Co., Ltd.) was exposed to the atmosphere at 150 mJ/cm ² ( The 365 nm reference) illuminates the light. For the mask, a pattern that can form a line/pitch of 100 μm is used. After the light was irradiated, the colored layer was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C for 60 seconds, and after washing with water, in an oven. After post-baking at 230 ° C for 30 minutes, a colored pattern was obtained.

<Measurement of film thickness>

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

<Colorimetric evaluation>

For the obtained coloring pattern, the color separation was measured by a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate (x, in the XYZ color system of CIE) was measured using the characteristic coefficient of the C light source. y) and tristimulus value Y. The larger the value of Y, the higher the brightness. The results are shown in Table 1.

<Comparative assessment>

A colored coating film was produced in the same manner as the production of the coloring pattern except that the mask was not used for the exposure. Then, the color coating film obtained was used, and a contrast meter (CT-1: manufactured by Husui Electric Co., Ltd., color difference meter BM-5A: TOPCON, light source: F-10, polarizer: manufactured by Husui Electric Co., Ltd.) was used. The comparison was made with a blank test value of 30,000. The higher the contrast in the coating film, the higher the contrast in the color pattern.

The results are shown in Table 1.

[Embodiment 2]

The same procedure as in Example 1 was carried out except that C.I. Acid Blue No. 104 was replaced by C.I. Acid Blue No. 90 to obtain a colored curable resin composition. Further, the colored curable resin composition was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[Example 3] (Modulation of coloring curable resin composition)

First, (A) colorant: CI Pigment Blue 15: No. 6 (pigment) 17 parts of acrylic pigment dispersant, 4.2 parts of propylene glycol monomethyl ether acetate 141 parts were mixed, and the pigment was completely dispersed by a bead mill. Next, (A) Colorant: CI Acid Red No. 52 (manufactured by Tokyo Chemical Industry Co., Ltd.: dibenzopyran dye) 2.5 parts (A) Colorant: Triphenylmethane dye 1 1.0 part (B) Resin: Resin B1 (converted solid content) 50 parts (C) Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA: manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N- Benzyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01: manufactured by BASF Corporation) 10 parts (F) coating agent: Polyether modified polyoxygenated oil (Toray Silicone SH8400: manufactured by Dow Corning Toray) 0.1 part (E) Solvent: 559 parts of ethyl lactate (E) Solvent: propylene glycol monomethyl ether acetate 8 parts were mixed to obtain a colored curable resin composition.

The same operation as in Example 1 was carried out for the colored curable resin composition, and the same evaluation was carried out. The results are shown in Table 1.

[Example 4]

The same operation as in Example 3 was carried out except that the triphenylmethane dye 1 was substituted with the triphenylmethane dye 2 to obtain a colored curable resin composition. Further, the colored curable resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]

First, (A) colorant: CI Pigment Blue 15: No. 6 (pigment) 20 parts of acrylic pigment dispersant 5 parts of propylene glycol monomethyl ether acetate 137 parts are mixed, and the pigment is completely dispersed by a bead mill. Next, (A) Colorant: Dibenzopyran dye 2 3.5 parts (B) Resin: Resin B2 solution 157 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) of a polymerization initiator: OXE 01 (manufactured by BASF Corporation) 15 parts of (E) solvent: 289 parts of 4-hydroxy-4-methyl-2-pentanone were mixed to obtain a colored curable resin composition. Thereafter, the colored curable resin composition was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[Example 5] (Modulation of coloring curable resin composition)

First, (A) colorant: CI Pigment Blue 15: No. 6 (pigment) 24 parts of acrylic pigment dispersant 6.1 parts of propylene glycol monomethyl ether acetate 163 parts were mixed, and the pigment was completely dispersed by a bead mill. Next, (A) Colorant: Dibenzopyran dye 2 1.8 parts (A) Colorant: CI Acid Blue No. 104 (Daiwa BLUE 300: manufactured by Daiwa Chemical Co., Ltd.: Triarylmethane dye) 1.8 parts (B) Resin: Resin B1 (converted solid content) 60 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA: manufactured by Nippon Kayaku Co., Ltd.) 40 parts (D) Polymerization initiator: N-benzylideneoxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01: manufactured by BASF) 5 parts (F) Agent: Polyether modified polyoxygenated oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.08 parts (E) Solvent: 852 parts of ethyl lactate (E) Solvent: propylene glycol monomethyl ether acetate 8 parts were mixed to obtain a colored curable resin composition.

Thereafter, the colored curable resin composition was subjected to the same evaluation as in Example 1 to determine a color filter which gave a high contrast.

From the color hardening resin composition of the example, it was confirmed that the obtained colored coating film showed high contrast. From this, it is understood that the coloring coating film and the coloring pattern obtained by the colored curable resin composition of the present invention can be used as a high contrast color filter, and the liquid crystal display device including the color filter exhibits excellent characteristics.

Therefore, with 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‧‧‧ Polysilicon film

22d‧‧‧Protective film

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

27‧‧‧ Signal Line

201‧‧‧Contact hole

Claims (4)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant comprises a dibenzopyran dye, a triarylmethane dye, and a pigment, and the content of the triarylmethane dye The content is 1 part by mass or more and 100 parts by mass or less based on 100 parts by mass of the dibenzopyran dye. The colored hardening resin composition according to the first aspect of the invention, wherein the content of the dibenzopyran dye is 0.1% by mass or more and 70% by mass or less based on the total amount of the coloring agent. A color filter formed of the color hardening resin composition as described in claim 1 or 2. A display device comprising the color filter of claim 3 of the patent application.