TWI675068B - Dye and colored curable resin composition - Google Patents

Abstract

The present invention is a dye having a group containing a silicon atom and a squaraine skeleton.

Description

Dyes and colored hardening resin composition

The present invention relates to a dye and a coloring curable resin composition.

Squaric acid dyes are used in fields such as photoreceptors. In Japanese Patent Application Laid-Open No. 60-248652, the squarylium dye is a compound represented by the formula (II-0).

The present invention includes the following inventions.

[1] A dye comprising a group containing a silicon atom and a squarocyanine skeleton.

[2] The dye as described in [1], wherein the group containing a silicon atom is a group containing -Si (R ¹⁴ ) ₃

[R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and three R ¹⁴ may be the same or different, respectively].

[3] The dye according to [1] or [2], wherein the group containing a silicon atom is a group represented by formula (iia) [In formula (iia), R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The three R ¹⁴ may be the same or different. L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. -CH ₂ -contained in the alkanediyl group may be substituted by an oxygen atom. * Indicates a bonding group].

[4] The dye according to any one of [1] to [3], which is a compound represented by the formula (IIa) [In the formula (IIa), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms (which may constitute the saturated hydrocarbon group) Between carbon atoms, oxygen or sulfur atoms can also be inserted).

R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxyl group.

R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a silicon atom-containing group, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between the carbon atoms constituting the saturated hydrocarbon group, also An oxygen atom or a sulfur atom may be inserted) or a phenyl group which may have a substituent. However, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a silicon atom].

[5] The dye according to item [4], wherein the group containing a silicon atom is a group represented by formula (iia) [In formula (iia), R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The three R ¹⁴ may be the same or different. L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. -CH ₂ -contained in the alkanediyl group may be substituted by an oxygen atom. * Indicates a bonding group].

[6] The dye according to any one of [4] or [5], wherein the phenyl group which may have a substituent is a group represented by formula (i): (In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5. When m is 2 or more, The plural R ¹² may be the same as or different from each other. * Represents a group bonded to a nitrogen atom).

[7] The dye according to any one of [1] to [6], which is a compound represented by the formula (II): [In formula (II), R ^1a and R ^2a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting the saturated hydrocarbon group, also An oxygen atom or a sulfur atom can be inserted).

R ^3a and R ^4a each independently represent a hydrogen atom or a hydroxyl group.

One of R ^5a and R ^6a is a group represented by formula (ii), and the other is a hydrogen atom, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting a saturated hydrocarbon group) (You can also insert an oxygen atom or a sulfur atom) or a group represented by formula (i).

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5. When m is 2 or more, The plural R ¹² may be the same as or different from each other. * Represents a group bonded to a nitrogen atom.)

(In formula (ii), n represents an integer of 1 to 8; R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; * represents a bond with a nitrogen atom Base. The three R ¹⁴ may be the same or different.)]

[8] A coloring agent containing the dye according to any one of [1] to [7].

[9] The coloring agent according to item [8], which further contains a yellow pigment.

[10] The coloring agent according to item [9], wherein the yellow pigment is at least one pigment selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185.

[11] A coloring curable resin composition containing the coloring agent according to any one of [8] to [10], a resin, a polymerizable compound, and a polymerization initiator.

[12] A coating film formed from the colored curable resin composition according to [11].

[13] A color filter formed of the color-hardening resin composition according to [11].

[14] A display device comprising the color filter described in [13].

The dye of the present invention is excellent in solubility in an organic solvent, and a color filter formed of a coloring curable resin composition containing the dye is also excellent in heat resistance.

The present invention is a dye having a group containing a silicon atom and a squaraine skeleton.

Examples of the group containing a silicon atom include a substituent having a siloxy group such as a trialkylsiloxy group and a trialkoxysilyl group.

Examples of the trialkylsiloxy group include trimethylsiloxy group, triethylsiloxy group, and the like, and trialkylsiloxy groups having an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 are preferred).

Trialkoxysilyl groups include trimethoxysilyl groups, triethoxysilyl groups, and the like, and trialkylsilyl groups having an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 are preferred).

It has a siloxy group, for example: an alicyclic ring having 3 to 10 carbon atoms A group of a hydrocarbon and a siloxy group, and a group having an oxygen atom and a sulfur atom and a group of a siloxy group inserted into a saturated hydrocarbon group having a carbon number of 1 to 20 to be described later. Such a group may further include a halogen atom and an alkyl group. Amino groups and dialkylamino groups (hereinafter, such substituted amine groups are collectively referred to as "(di) alkylamino groups") and the like.

Among the dyes of the present invention, a group containing a silicon atom is preferably a group containing -Si (R ¹⁴ ) ₃ , and a group represented by formula (iia) is more preferred:

In -Si (R ¹⁴ ) ₃ , R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The three R ¹⁴ may be the same or different.

Examples of the alkyl group represented by R ¹⁴ include methyl, ethyl, propyl, and butyl.

Examples of the alkoxy group represented by R ¹⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

R ^{14 is} preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, methyl, ethyl, propyl, methoxy, ethoxy, or propoxy Preferably, a hydrogen atom, methyl, ethyl, methoxy or ethoxy is more preferred.

The three R ¹⁴ are preferably the same.

In formula (iia), R ¹⁴⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. -CH ₂ -contained in the alkanediyl group may be substituted by an oxygen atom. * Indicates a bonding group with a nitrogen atom.

Examples of the alkyl group represented by R ¹⁴⁴ include methyl, ethyl, propyl, and butyl.

Examples of the alkoxy group represented by R ¹⁴⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

R ^{144 is} preferably a hydrogen atom, methyl, ethyl, propyl, methoxy, ethoxy or propoxy, and more preferably a hydrogen atom, methyl, ethyl, methoxy or ethoxy. The three R ¹⁴⁴ are preferably the same.

Examples of the alkanediyl group represented by L ¹ include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, and butane- 1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, and the like.

L ¹ is preferably an alkanediyl group having 1 to 4 carbon atoms.

Examples of the group represented by the formula (iia) include the groups shown below. Among them, the base represented by the formula (ii-1) to the base represented by the formula (ii-6) is preferable.

(* Represents a bonding group with a nitrogen atom or a carbon atom).

Examples of the dye of the present invention include trimethyl Siloxane, triethylsilyl, trimethoxysilyl, triethoxysilyl, and other siloxy dyes with a squarylium skeleton.

The dye of the present invention contains a compound represented by formula (IIa) (Hereinafter, it is also described as a compound (IIa)), and it is more preferable that it contains the compound represented by Formula (II) (henceforth, also described as a compound (II)). Compound (IIa) and compound (II) also include their tautomers, respectively.

[In the formula (II), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms (which constitutes the saturated hydrocarbon group) Between carbon atoms, oxygen or sulfur atoms can also be inserted).

R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxyl group.

R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a silicon atom-containing group, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between the carbon atoms constituting the saturated hydrocarbon group, also An oxygen atom or a sulfur atom may be inserted) or a phenyl group which may have a substituent. However, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a silicon atom. ]

[In formula (II), R ^1a and R ^2a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting the saturated hydrocarbon group, also An oxygen atom or a sulfur atom can be inserted).

R ^3a and R ^4a each independently represent a hydrogen atom or a hydroxyl group.

One of R ^5a and R ^6a is a group represented by formula (ii), and the other is a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting a saturated hydrocarbon group, An oxygen atom or a sulfur atom may be inserted) or a group represented by formula (i).

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5. When m is 2 or more, The plural R ¹² may be the same as or different from each other. * Represents a group bonded to a nitrogen atom.)

(n, R ¹⁴ and * are the same as defined above.)]

In the present specification, 2 ^♁ represents a bivalent positive charge of a ring system.

Examples of the halogen atom of the formula (IIa) and the formula (II) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of monovalent saturated hydrocarbon groups in formula (IIa) and formula (II) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl Alkyl, hexadecyl and icosyl alkyl linear alkyl groups having 1 to 20 carbons; isopropyl, isobutyl, second butyl, third butyl, isopentyl, neo 3 to 20 carbon chain branches such as pentyl and 2-ethylhexyl; 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecyl 20 alicyclic saturated hydrocarbon group.

Examples of the substituent of the monovalent saturated hydrocarbon group in the formula (IIa) and the formula (II) include a halogen atom, a hydroxyl group, and a (di) alkylamino group having 1 to 8 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the (di) alkylamino group include methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, dimethylamino, and diethylamino , Dipropylamino, ethylmethylamino, and the like.

Examples of the saturated hydrocarbon group which may have a substituent include a group represented by the following formula (* Indicates the basis of bonding).

In formula (IIa) and formula (II), a carbon atom constituting the above-mentioned monovalent saturated hydrocarbon group may also have an oxygen atom or a sulfur atom, and examples thereof include the following: (* Indicates the basis of bonding).

R ¹ , R ² , R ^1a , R ^2a , R ¹¹¹ and R ^{112 are} each independent, preferably a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 4 carbon atoms; a hydrogen atom, a hydroxyl group, and a methyl group are more preferred; hydrogen Atoms are even better.

In the compound (IIa), at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ represents a group containing a silicon atom. It is preferable that at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a base represented by formula (iia); at least one of R ⁵ and R ⁶ is a base represented by formula (iia), R ^It is more preferable that at least one of ¹⁵ and R ¹⁶ is a base represented by formula (iia).

In the compound (IIa), a group containing a silicon atom is preferably a group represented by formula (iia), and a group represented by formula (ii) is more preferred.

In the compound (IIa), a phenyl group which may have a substituent is preferably a group represented by formula (i).

Compound (IIa) is a compound of formula (IIa) in which a group containing a silicon atom is a group represented by formula (iia), and a phenyl group which may have a substituent is a group represented by formula (i) (Referred to as "compound (IIb)").

In the compound (II), one of R ^5a and R ^6a is a group represented by formula (iia), the other is a hydrogen atom, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( Among carbon atoms constituting a saturated hydrocarbon group, an oxygen atom or a sulfur atom may also be inserted) or a group represented by formula (i); Among R ^5a and R ^6a , one is a group represented by formula (ii), The other is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the saturated hydrocarbon group) or the group represented by formula (i) is Better.

R ⁵ , R ⁶ , R ^5a , R ^6a , R ¹⁵ and R ¹⁶ may have a phenyl substituent, and examples thereof include a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a monovalent group having 2 to 20 carbon atoms. Saturated hydrocarbyl.

The monovalent saturated hydrocarbon group in this substituent is: methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, n-hexyl, n-heptyl, 2 -Ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and other alkyl groups having 1 to 20 carbon atoms are preferred.

Examples of the monovalent unsaturated hydrocarbon group in the substituent include carbons such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl. Alkenyl groups of 2 to 20.

Examples of the monovalent unsaturated hydrocarbon group represented by R ¹² in formula (i) include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene Alkenyl groups having 2 to 20 carbon atoms, such as alkyl, decenyl, and the like.

Examples of the monovalent saturated hydrocarbon group represented by R ¹² include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, n-hexyl, Alkyl groups having 1 to 20 carbons such as n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.

R ¹² is preferably a hydrogen atom or a carbon number of 1 to 4, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

The base represented by formula (i) may be exemplified as follows: (* Represents a group bonded to a nitrogen atom).

In formula (II), n is preferably an integer of 1 to 6, and 1 to 4 Integers are better.

When the groups represented by R ⁵ , R ⁶ , R ^5a and R ^6a represent groups other than the groups represented by formula (iia) and formula (ii), respectively, a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, The group represented by formula (i) is preferred, and a hydrogen atom is more preferred.

The base shown in the following formula (R ⁵ and R ⁶ respectively have the same meanings as above, and * represents a bonding group with a carbon atom), and The radicals shown (R ^5a and R ^6a respectively have the same meanings as above, and * represents a bonding group with a carbon atom), and the following radicals can be enumerated:

Dyestuffs containing a group containing silicon atoms and a squarine skeleton Examples of the material include a compound represented by the formula (AII-1) to a compound represented by the formula (AII-75).

In the present invention, from the point that raw materials are easily available, The compound represented by the formula (AII-4) to the compound represented by the formula (AII-6), and the compound represented by the formula (AII-31) to the compound represented by the formula (AII-33) are preferable.

Compound (II), according to Japanese Patent Application Laid-Open No. 2002-363434 It can be produced by the method described in the publication No. 1, specifically, by using the compound represented by the formula (IV-1) and a cubic acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) ( 3,4-dihydroxy-3-cyclobutene-1,2-dione).

(Wherein R ^1a to R ^6a each have the same meaning as described above).

Relative to 1 mole of the compound represented by formula (IV-1) The amount used is preferably from 0.5 mol to 0.8 mol, more preferably from 0.55 mol to 0.6 mol.

The reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 80 ° C to 140 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

In terms of productivity, the reaction is in organic solvents Perform better. Examples of organic solvents include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; Ketone solvents, such as methyl isobutyl ketone; amine solvents, such as 1-methyl-2-pyrrolidone, etc., may be used in combination. Among them, a mixed solvent of butanol and toluene is preferred. The amount of the organic solvent used is preferably 30 parts by mass or more and 200 parts by mass or less, and more preferably 50 parts by mass or more and 150 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (IV-1).

The method for obtaining the target compound (II) from the reaction mixture is not particularly limited, and various conventional methods can be adopted. For example, after cooling, the precipitated crystals can be collected by filtration. The crystals collected by filtration are preferably washed with water and then dried. If necessary, it can be further refined by conventional methods such as recrystallization.

<Colorant>

The coloring agent of the present invention contains a dye having a group containing a silicon atom and a squarylium skeleton (hereinafter, this colorant is referred to as "colorant (A)").

The colorant (A), in addition to the dye of the present invention, may further contain other dyes (A2), pigments (P), or a mixture thereof in order to adjust the color, that is, to adjust the spectral characteristics.

Examples of the dye (A2) include oil-soluble dyes, acid dyes, and acid dyes. Dyes such as amine salts and sulfonamide derivatives of acid dyes, such as those classified as dyes in the colour index (published by The Society of Dyers and Colourists), and contained in dyeing notes (color dyeing society) The conventional dye. Furthermore, depending on the chemical structure, coumarin dyes, gold-containing azo dyes, pyridone azo dyes, barbituran azo dyes, quinoline yellow dyes, methine dyes, anthocyanin dyes, and anthracene Quinone dyes, triphenylmethane dyes, xanthene dyes, and phthalocyanin dyes. These dyes may be used alone or in combination of two or more.

Specific examples include: CI Solvent Yellow No. 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is recorded), 14, 15, 23, 24, 38, 62, 63, and 68 No. 82, No. 94, No. 98, No. 99, No. 162; CI Solvent Orange No. 2, No. 7, No. 11, No. 15, No. 26, No. 56; etc. CI solvent dyes; CI Acid Yellow No. 1, No. 3 , 7, 9, 9, 17, 23, 25, 29, 34, 36, 38, 40, 42, 42, 54, 65, 72, 73, 76 No. 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196 , 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240 No. 242, 243, 251 No .; CI Acid Orange No. 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; etc. CI acid dyes, CI Direct Yellow No. 2, 33, 34, 35, 38, 39, 43, 47, Numbers 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136 , 138, 141; CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96 No. 97, 106, 107; etc. CI direct dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43 No. 45, 56, No. 61, No. 62, No. 65; CI Mordant Orange No. 3, No. 4, No. 5, No. 8, No. 12, No. 13, No. 14, 20, 21, 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 mordant dyes, etc.

For dyes (A2), yellow dyes such as coumarin dyes, gold-containing azo dyes, pyridone azo dyes, barbituric azo dyes, quinoline yellow dyes, methine dyes, and anthocyanin dyes are used. Better.

The content of the dye of the present invention is generally preferably 3 to 99.9% by mass, and more preferably 4 to 50% by mass relative to the total amount of the colorant. 5 It is more preferable to be 30% by mass. When the content of the dye of the present invention is within the aforementioned range, it is preferable that the brightness is high when the color filter is manufactured.

The pigment (P) is not particularly limited, and it can be used conventionally. Pigments, for example, pigments classified as pigments in The Society of Dyers and Colourists.

Examples of the pigment (P) include CI Pigment Yellow No. 1, No. 3, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17, No. 20, No. 24, No. 31, No. 53, No. 83 No. 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, Yellow pigments such as No. 166, No. 173, No. 194, No. 214; CI Pigment Orange No. 13, No. 31, No. 36, No. 38, No. 40, No. 42, No. 43, No. 51, No. 55, No. 59, No. 61 , 64, 65, 71, 73 and other orange pigments; CI Pigment Green No. 7, 36, 58 and other green pigments.

Pigment (P): CI Pigment Yellow No. 1, 3, 12, 13, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86 , 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 Yellow pigments such as No. 194, No. 214, etc .; and green pigments such as CI Pigment Green No. 7, 36, and 58 are preferred, CI Pigment Yellow No. 138, 150, 185, and CI Pigment Green No. 36, 58 For the better, CI Pigment Yellow 138, CI Pigment Yellow 150 and CI Pigment Yellow 185 is even better. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter can be improved.

<Colored curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). It may also contain a solvent (E).

In the present specification, the compounds of the respective components are exemplified, and if not particularly limited, they may be used alone or in combination.

In the colored curable resin composition of the present invention, The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass based on the total solid content. When the content of the colorant (A) is within the foregoing range, the color density when the color filter is made is sufficient, and the required amount of the resin (B) and the polymerizable compound (C) can be contained in the composition. A pattern with sufficient mechanical strength. Here, the "total amount of solid components" in the present specification refers to an amount in which the solvent content is removed from the total amount of the coloring curable resin composition. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

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

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Ba) (hereinafter sometimes referred to as "(Ba)") and a cyclic ether structure having 2 to 4 carbon atoms And ethylenically unsaturated bond monomer (Bb) (hereinafter sometimes referred to as "(Bb)") copolymer; resin [K2]: (Ba), (Bb), and monomer (Bc) copolymerizable with (Ba) (however, (Ba) and (Bb) are different) ( (Hereinafter sometimes referred to as "(Bc)") copolymer; resin [K3]: copolymer of (Ba) and (Bc); resin [K4]: copolymer of (Ba) and (Bc) and (Bb) ) Resin; Resin [K5]: Resin that reacts the copolymer of (Bb) and (Bc) with (Ba); Resin [K6]: Reacts the copolymer of (Bb) and (Bc) with (Ba) Resin that reacts with carboxylic anhydride.

(Ba) Examples include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, and citraconic acid Acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydro Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxyl Bicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2 -Ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6 -Ethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4- Vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydrated 5, 6-Dicarboxybicyclo [2.2.1] hept-2-ene and other unsaturated dicarboxylic anhydrides; succinate mono [2- (methyl) propane Acyl oxy ethyl] phthalate, mono Unsaturated mono [(meth) acryloxyalkyl] esters of two- or more-valent polycarboxylic acids, such as [2- (meth) acryloxyethyl] esters; α- (hydroxymethyl) acrylic acid and the like, unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(Bb) means, for example, a cyclic ether structure having 2 to 4 carbon atoms A polymerizable compound (for example, at least one selected from the group consisting of an oxetane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond.

(Bb) A monomer having a cyclic ether and a (meth) acryloxy group having 2 to 4 carbon atoms 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) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

(Bb) Examples include oxetanyl group and ethylenic property. A monomer having a saturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.

In terms of making the obtained color filter more reliable in terms of heat resistance, chemical resistance, and the like, (Bb) is preferably a monomer containing an oxetanyl group and an ethylenically unsaturated bond.

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and third butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, dodecane (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ester (meth) , The common name is "dicyclopentyl (meth) acrylate". Also, it is sometimes called "tricyclodecyl (meth) acrylate"), tricyclic (meth) acrylate [5.2.1.0 ^2,6 ] Decene-8-ester (in its technical field, the common name is "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, isopropyl (meth) acrylate Fluorenyl ester, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) (Meth) acrylates such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as 2-hydroxypropyl (meth) acrylate; dicarboxylic acids such as diethyl maleate, diethyl fumarate, and diethyl iconate Diesters; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] 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-dihydroxydiene Cyclic [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (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-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2 .1] hept-2-ene, 5-benzyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] heptane -2-ene, 5,6-bis (cyclohexyl Carbonyl) bicyclic unsaturated compounds such as bicyclo [2.2.1] hept-2-ene; N-phenylcis-butenedifluoreneimine, N-cyclohexylcisbutenedifluoreneimine, N-benzyl N-succinimide diimide, N-succinimide imido-3-cis butemodiimide benzoate, N-succinimide 4-cis butimide diimide butyric acid Ester, N-succinimide-6-cis-butenediimidehexanoate, N-succinimide-3-cis-butenediimidepropionate, N- (9-propylene Fluorenyl) dicarbonyl fluorenimine derivatives such as cis-butene difluorenimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxybenzene Ethylene, acrylonitrile, methacrylonitrile, ethylene chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3- Dimethyl-1,3-butadiene and the like.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylcis butylenediimide, N-cyclohexylcisbutenediimide, N -Benzyl cis butene diamidine, bicyclo [2.2.1] hept-2-ene and the like are preferred.

Examples of the resin (B) include (meth) acrylic acid-3,4-epoxycyclohexylmethyl ester / (meth) acrylic acid copolymer, acrylic acid-3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] Decyl ester / (meth) acrylic copolymer [K1]; Glycidyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid ring Oxypropyl ester / styrene / (meth) acrylic acid copolymer, acrylic acid-3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleic diene Resins such as fluorene imine copolymer, 3-methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; (meth) acrylic acid Resins such as benzyl / (meth) acrylic copolymer, styrene / (meth) acrylic copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic copolymer addition (meth) Glycidyl Acrylate Resin, Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer addition Glycidyl (meth) acrylate Resin, Tricyclodecyl (meth) acrylate Esters / benzyl (meth) acrylate / (meth) acrylic acid copolymers added with glycidyl (meth) acrylate Resins and other resins [K4]; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid, Tricyclodecyl (meth) acrylate / benzene Copolymers of ethylene / glycidyl (meth) acrylic acid copolymer and (meth) acrylic acid-reactive resins [K5]; Tricyclodecyl (meth) acrylic acid / glycidyl (meth) acrylate copolymer Resins reacted with (meth) acrylic acid and resins reacted with tetrahydrophthalic anhydride [K6] and the like.

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

Resin [K1], refer to the method contained in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki, Issuer, Chemical Dojin Co., Ltd., 1st Edition, 1st Issue, March 1, 1972) and the document Manufactured by reference.

The prepared copolymer may be used directly after the reaction, or may be a concentrated or diluted solution, or a solid (powder) removed by a method such as reprecipitation. In particular, as for 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 to prepare the colored curable resin composition of the present invention. The manufacturing process of the colored curable resin composition of this invention can be simplified.

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

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

The acid value of the resin (B) is preferably from 50 to 170 mg-KOH / g, more preferably from 60 to 150 mg-KOH / g, and even more preferably from 70 to 135 mg-KOH / g. The measured value of the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B) with an acid value can be determined by, for example, titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of solid components. When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution of the colored pattern and the film residual rate tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, etc. ) Acrylate compounds are preferred.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dipentaerythritol. Alcohol five (a Base) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol ten (Meth) acrylate, Tetranepentaerythritol nona (meth) acrylate, Trimeric isocyanate (2- (meth) acryloxyethyl), Ethylene glycol modified neopentyl Alcohol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol Hexa (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc.

Of these, dipentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.

Weight average molecular weight of polymerizable compound (C), 150 It is preferably 2,900, and more preferably 250 to 1,500.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of solid components. When the content of the polymerizable compound (C) is within the above-mentioned range, there is a tendency that the film residual rate at the time of forming a colored pattern and the chemical resistance of the color filter are increased.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that generates living radicals, acids, and the like by the action of light and heat, and a conventional polymerization initiator can be used. Examples of the polymerization initiator that generates living radicals include, for example, O-fluorenyl oxime compounds, alkyl phenone compounds, Compounds, fluorenylphosphine oxides and biimidazole compounds.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, and N-benzyl Ethoxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylsulfanylphenyl) 3-Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazole- 3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4- Dioxycyclopentaminylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxymethyl-1- [9-ethyl- 6- (2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl -6- (2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE 01, OXE 02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Among them, the O-fluorenyl oxime compound is selected from the group consisting of: N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, and N-benzyl Ethoxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylsulfanylphenyl) At least one of the groups formed by -3-cyclopentylpropane-1-one-2-imine is preferred, and N-benzyloxy-1- (4-phenylsulfanylphenyl) octyl Alkan-1-one-2-imine is more preferred. In the case of these O-fluorenyl oxime compounds, a color filter with a high brightness tends to be obtained.

Examples of the alkyl phenone compound include 2-methyl-2-N-morpholinyl-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamine 2- (4-N-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) formyl Group] -1- [4- (4-morpholinyl) phenyl] butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2- Methyl-1- [4- (2-hydroxyethoxy) Phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomer, α, α-diethoxyacetophenone, benzylformaldehyde and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above manufactured by BASF) can also be used.

Aforementioned three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

As the fluorenylphosphine oxide, 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide or the like can also be used. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF).

Examples of the aforementioned biimidazole compound include: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro (Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy) Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204 Etc.), imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted with a carboalkoxy group (see Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Examples of the polymerization initiator (D) include benzoin and benzene. Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; benzophenone, o-benzoyl methyl benzoate, 4 -Phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacryl Pyridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc.

Examples of the acid-generating polymerization initiator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethylfluorenylbenzene Dimethylpyridine p-toluenesulfonate, 4-Ethyloxyphenylmethylbenzylpyrene hexafluoroantimonate, triphenylpyrene p-toluenesulfonate, triphenylpyrene hexafluoroantimonate , Onium salts such as diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, and nitrobenzyl tosylate, benzoin tosylate, and the like.

The polymerization initiator (D) is selected from the group consisting of: O-fluorenyl oxime compound, alkyl phenone compound, A polymerization initiator of at least one of the group consisting of a compound, a fluorenylphosphine oxide, and a biimidazole compound is preferable, and a polymerization initiator containing an O-fluorenyl oxime compound is more preferable.

Relative to the total of resin (B) and polymerizable compound (C) The amount is 100 parts by mass, and the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass. Prior to the content of the polymerization initiator (D) When it is within the above range, the sensitivity can be increased and the exposure time tends to be shortened, so that the productivity of the color filter can be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the technical field can be used. Examples include: ester solvents (solvents containing -COO-, -O-free solvents), ether solvents (solvents containing -O-, -COO-free solvents), ether-ester solvents (molecules containing -COO- and -O-solvents), ketone solvents (solvents with -CO- in the molecule, but without -COO-), alcohol solvents (with OH in the molecule, -O-, -CO-, and -COO) -Solvents), aromatic hydrocarbon solvents, amine solvents, dimethyl sulfene 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, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexane Alcohol acetate and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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-methylbutanol , Tetrahydrofuran, tetrahydropyran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and methyl Anisole and so on.

Examples of the ether-ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Esters, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropionate, 2-ethyl Ethyloxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, etc. .

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

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

Examples of the amidine solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 210 ° C. or lower at 1 atm in terms of coatability and drying properties is preferred. In terms of solvents, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol Monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide More preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the coloring curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the aforementioned range, the flatness at the time of coating can be made good, and since the color density is not insufficient when forming a color filter, the display characteristics tend to be good.

<Other ingredients>

The coloring curable resin composition of the present invention may optionally include, for example, a polymerization initiation aid, a leveling agent, a filler, other polymer compounds, a tackifier, an antioxidant, a light stabilizer, and a chain transfer agent. Wait for additives known in this technical field.

<Manufacturing method of colored curable resin composition>

The colored curable resin composition of the present invention can be obtained by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and optionally The leveling agent, polymerization initiation aid and other ingredients used are mixed and prepared.

The pigment (P) is preferably partially or completely mixed with a part of the solvent (E) in advance, and then dispersed with a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be prepared as required. Then, in the pigment dispersion liquid prepared in this way, the remaining ingredients are mixed so as to have a predetermined concentration, so that the intended color hardening property can be adjusted. Resin composition.

The dye may be dissolved in part or all of the solvent (E) in advance to prepare a solution. This solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

The mixed coloring curable resin composition is preferably filtered through a filter having a pore size of about 0.1 to 10 μm.

<Manufacturing method of coating film>

The coating film of the present invention is formed from the colored curable resin composition of the present invention. The coating film can be formed by curing the colored curable resin composition. The coating film of the present invention may include a coloring pattern described later. The method of hardening this coloring curable resin composition is mentioned later.

<Manufacturing Method of Color Filter>

The color filter of the present invention is formed of the coloring curable resin composition of the present invention. The color filter can be formed by curing the colored curable resin composition. The color filter can be obtained, for example, by coating the colored curable resin composition on a substrate, and then drying to form a colored composition layer, and exposing the colored composition layer through a photomask. The color filter of the present invention may include a coloring pattern on the coating film.

Examples of the method for producing a colored pattern using the colored curable resin composition of the present invention include a photoetching method, an inkjet method, and a printing method. Among them, a photoetching method is preferable. The photo-etching method is a method in which the colored curable resin composition is coated on a substrate, dried to form a colored composition layer, and then the colored composition layer is exposed and developed through a photomask. In the photoetching method, the above-mentioned formation can be performed by using no photomask and / or no development during exposure. Coating film of color composition layer hardened material. The coloring pattern and coating film formed in this way are the color filters of the present invention.

The film thickness of the color filter is not particularly limited, and may be appropriately adjusted depending on the purpose and application. For example, it is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, and even more preferably 0.5 to 6 μm.

For the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass with silica coated on the surface, as well as polycarbonate, polymethyl methacrylate carbonate, and polyethylene pairs can be used. Resin plates such as phthalate, silicon, and the like are formed of aluminum, silver, silver / copper / palladium alloy films, and the like on the substrate. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. may also be formed.

The formation of pixels of various colors by the photo-etching method can be performed by a conventional or conventional device and conditions. For example, it can be manufactured as follows.

First, a colored curable resin composition is coated on a substrate, and then volatile components such as solvents are removed by drying under heat (pre-baking) and / or reduced pressure drying, and dried to obtain a smooth colored composition layer.

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

The temperature during heating and drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When performing the drying under reduced pressure, it is preferably performed at a temperature ranging from 20 to 25 ° C under a pressure of 50 to 150 Pa.

The film thickness of the coloring composition layer is not particularly limited, and color can be filtered according to the purpose The film thickness of the device is appropriately selected.

Next, the colored composition layer is exposed through a mask for forming the intended colored pattern. The pattern on the reticle is not particularly limited, and the pattern may be used depending on the purpose of use.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, filters that block light in the wavelength range up to 350 nm can be used to block light in these wavelength ranges; band-pass filters that take out light in the wavelength range near 436 nm, 408 nm, and 365 nm can also be used The device selectively extracts light in these wavelength ranges. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

In order to illuminate the entire exposure surface uniformly with parallel rays, and to align the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a photomask aligner and a stepper.

By contacting the coloring composition layer after exposure with the developing solution, Touch development, you can form a colored pattern on the substrate. By development, the unexposed part of the coloring composition layer can be dissolved in a developing solution and removed. As the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferably used. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Moreover, the developing solution may contain a surfactant.

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

After development, washing with water is preferred.

Furthermore, the coloring pattern obtained is preferably post-baked. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

(Example)

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples. In the examples, the percentages and parts indicating the content and even the usage amount are mass standards unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by mass analysis (LC; Model 1200 manufactured by Agilent, MASS; Model LC / MSD manufactured by Agilent).

Example 1: Synthesis of a compound represented by formula (AII-32)

First, to 10.9 parts of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 19 parts of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 parts of acetic acid were added, and refluxed in 200 parts of tetrahydrofuran for 8 hours. After completion of the reaction, tetrahydrofuran was distilled off to obtain 29.8 parts of a compound represented by the formula (AII-32-1).

2.9 parts of the compound represented by the formula (AII-32-1), 0.6 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 parts of 1-butanol and 60 parts of toluene were mixed. The resulting mixture was dewatered using a Dean-Stark tube while at 125 Stir at 3 ° C for 3 hours. After the reaction, the solvent was distilled off, and 15 parts of acetic acid was added, and then 18% saline was added dropwise, and the precipitated solid was collected by filtration. The filtered solid was washed with hexane. The obtained solid was dried under reduced pressure to obtain 3.4 parts of a compound represented by the formula (AII-32).

Identification of the compound represented by formula (AII-32)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = 680.4 [M + 1] ⁺

Exact Mass: 679.3

Example 2: Synthesis of a compound represented by formula (AII-5)

A compound represented by the formula (AII-5) was prepared in the same manner as in Example 1 except that aniline was used instead of the 3-aminophenol in Example 1.

Identification of compounds represented by formula (AII-5)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = 650.0 [M + 1] ⁺ exact mass: 648.9

Example 3: Synthesis of a compound represented by formula (AII-31)

A trimethoxysilane was used in place of the triethoxysilane in Example 1, and was synthesized in the same manner as in Example 1 to obtain the formula (AII-31). Of compounds.

Identification of compounds represented by formula (AII-31)

(Mass analysis) Ionization mode = ESI ⁺ : m / z = 597.8 [M + 1] ⁺

Exact mass: 596.8

0.35 parts of the compound represented by the formula (AII-32), the compound represented by the formula (AII-5) and the compound represented by the formula (AII-31) were each dissolved in chloroform to make the volume 250 cm ³ , and then 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and the absorption spectrum was measured with a spectrophotometer (quartz tube, light transmission distance: 1 cm). The maximum absorption wavelengths of the compound: λ _max are 688 nm, 680 nm, and 687 nm, respectively.

(Measurement of solubility)

For the compounds obtained in Examples 1 to 3 and the compound represented by formula (II-0), p-propylene glycol monomethyl ether (hereinafter, simply referred to as PGME), ethyl lactate (hereinafter, simply referred to as EL ), The solubility of propylene glycol monomethyl ether acetate (hereinafter, referred to as PGMEA).

In a 50 mL sample tube, the compound was mixed with the above-mentioned solvent in the following ratio, and then the sample tube was screwed tightly and shaken in an ultrasonic shaker at 30 ° C for 3 minutes. After standing at room temperature for 30 minutes, it was suction-filtered, and the residue was visually observed. When insoluble matter is not confirmed, it is judged as good solubility and ○, when insoluble matter is confirmed, it is judged as insoluble matter Good and ×. The results are shown in Table 1.

[Synthesis of Resin]

First, in a flask equipped with a circulating cooler, a dropping funnel, and a stirrer, pass an appropriate amount of nitrogen to a nitrogen gas environment, add 100 parts of propylene glycol monomethyl ether acetate, and heat to 85 ° C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ester, and acrylic acid-3 will be dissolved in 40 parts of propylene glycol monomethyl ether acetate. , 4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ester mixture (contains a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel) 171 Part of the solution was dropped into the flask using a drip pump over about 5 hours. On the other hand, another solution was prepared by dissolving 26 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate. The pump was dropped into the flask over a period of about 5 hours. After the addition of the polymerization initiator was completed, the solution was kept at the same temperature for 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH / g.

[Preparation of colored curable resin composition] Example 7

The following components are mixed to prepare a colored curable resin composition:

Example 8

The following components are mixed to prepare a colored curable resin composition:

Leveling agent (F): polyether modified silicone oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.)

0.1 serving. Example 9

The following components are mixed to prepare a colored curable resin composition:

Comparative Example 2

The following components are mixed to prepare a colored curable resin composition:

[Formation of pattern]

A 2 inch square glass substrate (EAGLE XG, manufactured by Corning Corporation) was coated with a colored photosensitive resin composition by a spin coating method, and then prebaked at 100 ° C for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK, manufactured by TOPCON Co., Ltd.) was used in an atmosphere of 150 mJ / cm ² The exposure amount (based on 365 nm) is irradiated with light. For the photomask, a 100 μm line / space pattern is used.

After the above light was irradiated, the obtained coating film was dipped in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds for development. After washing with water, It was then post-baked in an oven at 200 ° C for 20 minutes to obtain a pattern.

[Evaluation of heat resistance]

The coating film of the colored photosensitive resin composition was heated at 200 ° C. for 20 minutes, and the color difference (ΔEab *) before and after the coating film was heated was measured using a color measuring machine (OSP-SP-200, manufactured by OLYMPUS). The coating films prepared in Examples 7, 8, and 9 were subjected to the above-mentioned heat resistance evaluation, respectively. As a result, the color difference (ΔEab *) was 12.6 (Example 7), 10.2 (Example 8), and 11.1 (Implementation). Example 9). Comparative Example 2 was also evaluated for heat resistance in the same manner. As a result, the color difference (ΔEab *) was 20.5, and it was found that the heat resistance of the dye in this case was excellent.

(Industrial availability)

The dye of the present invention has excellent solubility in an organic solvent. Therefore, since the colored curable resin composition of the present invention contains the dye of the present invention, foreign matter is less generated, and a high-quality color filter can be produced, and a color filter excellent in heat resistance can be provided.

Claims (10)

A dye having a group containing a silicon atom and a squarylium skeleton, wherein the dye is a compound represented by formula (IIa); In formula (IIa), R ¹ , R ² , R ^111, and R ¹¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Between carbon atoms, an oxygen atom or a sulfur atom can be inserted; R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxyl group; R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, A group represented by formula (iia), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the saturated carbon group ; However, at least one of R ⁵ , R ⁶ , R ^15, and R ¹⁶ is a group represented by formula (iia). * -L ¹ -Si (R ¹⁴ ) ₃ (iia) In formula (iia), R ¹⁴ Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; the three R ¹⁴ may be the same or different; L ¹ represents an alkanediyl group having 1 to 8 carbon atoms; the -CH ₂ -contained in the alkanediyl group may be substituted by an oxygen atom; * indicates a bonding end. The dye according to item 1 of the scope of patent application, wherein the phenyl group which may have a substituent is a group represented by formula (i) In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5; and when m is 2 or more, a plural number R ¹² may be the same as or different from each other; * represents a group bonded to a nitrogen atom. The dye according to item 1 or 2 of the scope of patent application, which is a compound represented by formula (II); In formula (II), R ^1a and R ^2a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (the carbon atoms constituting the saturated hydrocarbon group may also be inserted Oxygen atom or sulfur atom); R ^3a and R ^4a each independently represent a hydrogen atom or a hydroxyl group; when one of R ^5a and R ^6a is a group represented by formula (ii), the other is a hydrogen atom, A monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the saturated hydrocarbon group) or a group represented by formula (i); In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5; and when m is 2 or more, a plural number R ¹² may be the same or different; * represents a group bonded to a nitrogen atom; In formula (ii), n represents an integer of 1 to 8; R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; * represents a group bonded to a nitrogen atom ; Three R ¹⁴ may be the same or different. A coloring agent, which contains the dyes described in claims 1, 2 or 3 of the scope of patent application. The coloring agent according to item 4 of the patent application scope, which further contains a yellow pigment. The coloring agent described in item 5 of the scope of the patent application, wherein the yellow pigment is at least one pigment selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 150 and C.I. Pigment Yellow 185. A coloring curable resin composition containing a coloring agent, a resin, a polymerizable compound, and a polymerization initiator as described in item 4 or 5 of the scope of patent application. A coating film is formed from the coloring curable resin composition described in claim 7 of the scope of patent application. A color filter is formed of the color-hardening resin composition described in item 7 of the scope of patent application. A display device includes the color filter described in item 9 of the scope of patent application.