TWI664240B - Compound and colored curable resin composition - Google Patents

Abstract

A compound represented by the formula (A-VI).

[In the formula (A-VI), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (can be inserted between the carbon atoms constituting the alkyl group) Oxygen atom).

R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R ^9A to R ^12A includes a silicon atom.

G ^g- represents a relative anion.

g represents an arbitrary natural number.

D represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]

Description

Compound and colored hardening resin composition

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

As a dye used in the field of color filters, Japanese Patent Application Publication No. 2010-520508 describes a di (tri) -aryl (hetero) pigment and a tri-aryl (hetero) -carbocation pigment.

The present invention includes the following inventions.

[1] A compound which is a compound represented by the formula (A-VI).

[In the formula (A-VI), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (can be inserted between the carbon atoms constituting the alkyl group) Oxygen atom).

R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R ^9A to R ^12A includes a silicon atom.

G ^g- represents a relative anion.

g represents an arbitrary natural number.

D represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]

[2] The compound according to [1], wherein at least one of R ^9A to R ^12A is a group represented by formula (iia).

* -L ¹ -Si (R ¹⁴⁴⁾ in ₃ (iia) [formula (iia), L ¹ represents a C alkyl group two 1 to 12, -CH alkanediyl group which contains ₂ - may be -O- , -CO- or -NR ^111- .

R ¹¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

The three R ¹⁴⁴ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

* Indicates a bond with a nitrogen atom. ]

[3] The compound according to [2], wherein at least one of R ^9A to R ^12A is a group represented by formula (ii).

[In formula (ii), n represents an integer of 1 to 8, and three R ¹⁴ each independently represent 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 * represents an Bonding of nitrogen atoms. ]

[4] The compound according to [1], wherein the compound represented by the formula (A-VI) is a compound represented by the formula (A-II).

[In the formula (A-II), X represents an oxygen atom or a sulfur atom.

R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R ⁴¹ to R ⁴⁴ is a group represented by formula (iia).

* -L ¹ -Si (R ¹⁴⁴⁾ in ₃ (iia) [formula (iia), L ¹ represents a C alkyl group two 1 to 12, -CH alkanediyl group which contains ₂ - may be -O- , -CO- or -NR ^111- .

R ¹¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

The three R ¹⁴⁴ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons.

* Indicates a bond with a nitrogen atom. ]

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group).

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.

G ^g- represents a relative anion.

g represents an arbitrary natural number. ]

[5] The compound according to [4], wherein at least one of R ⁴¹ to R ⁴⁴ is a group represented by formula (ii).

(In formula (ii), n represents an integer of 1 to 8, three R ¹⁴ each independently represent 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 * represents an Bonding of nitrogen atoms.)

[6] A coloring agent containing the compound according to any one of [1] to [5].

[7] The coloring agent according to [6], which further contains a blue pigment.

[8] The coloring agent according to [7], wherein the blue pigment is C.I. Pigment Blue 15: 6.

[9] A coloring curable resin composition containing the coloring agent according to any one of [6] to [8], a resin, a polymerizable compound, and a polymerization initiator.

[10] A coating film formed from the colored hardening resin composition according to [9].

[11] A color filter formed of the color hardening resin composition according to [9].

[12] A display device comprising the color filter according to [11].

The compound system of the present invention is excellent in solubility in an organic solvent.

The compound of the present invention is a compound represented by formula (A-VI) (hereinafter sometimes referred to as "compound (A-VI)"), and compound (A-VI) also includes tautomers thereof.

In the formula (A-VI), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (oxygen may be inserted between the carbon atoms constituting the alkyl group atom).

R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R ^9A to R ^12A includes a silicon atom.

G ^g- represents a relative anion.

g represents an arbitrary natural number.

D represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

The compound represented by the formula (A-VI) is preferably a compound represented by the formula (A-II) (hereinafter sometimes referred to as "compound (A-II)").

The compound (A-II) also includes its tautomer.

In the formula (A-II), X represents an oxygen atom or a sulfur atom.

R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R ⁴¹ to R ⁴⁴ is a group represented by formula (iia).

* -L ¹ -Si (R ¹⁴⁴⁾ in ₃ (iia) [formula (iia), L ¹ represents a C alkyl group two 1 to 12, -CH alkanediyl group which contains ₂ - may be -O- , -CO- or -NR ^111- .

R ¹¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

The three R ¹⁴⁴ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

* Indicates a bond with a nitrogen atom. ]

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbons, or an aryl group which may have a substituent.

G ^g- represents a relative anion.

g represents an arbitrary natural number.

In the formula (A-VI) and the formula (A-II), the alkyl group having 1 to 20 carbon atoms represented by R ^1A to R ^12A , R ⁴¹ to R ^46, and R ⁵⁵ may be a chain, branched chain, or ring As a specific example of any one of these states, a group represented by the following formula is mentioned. Among them, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

(* Indicates a bond with a carbon atom or a nitrogen atom.)

Examples of the group in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group include a group represented by the following formula. Among them, a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 1 to 10 carbon atoms is more preferable, and a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 1 to 6 carbon atoms is more preferable.

(* Indicates a bond with a carbon atom or a nitrogen atom.)

Examples of the substituents of the alkyl group represented by R ^9A to R ^12A and R ⁴¹ to R ⁴⁶ include a group containing a silicon atom, an amino group, an alkylamino group, and a halogen atom.

Examples of the silicon atom-containing radicals include: trimethylsilyl, triethylsilyl, and the like; trimethoxysilyl, triethoxysilyl, and other tri (alkoxy) silyl Base etc. Specific examples of the group containing a silicon atom include a group represented by formula (iia).

Examples of the alkylamino group include alkylamino groups having an alkyl group having 1 to 12 carbon atoms.

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

Examples of the alkyl group having 1 to 20 carbon atoms having such a substituent include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

^Among the aryl groups represented by R ^9A to R ^12A , R ⁴¹ to R ⁴⁶ and R ⁵⁵ , examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine; chloromethyl, trifluoromethyl Haloalkyl groups having 1 to 6 carbon atoms; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; sulfamoyl groups; Base etc.

Examples of the aryl system include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl.

Specific examples of the aryl group which may have a substituent include a group represented by the following formula.

(In the formula, * represents a bond with a nitrogen atom.)

In terms of ease of synthesis, R ^1A to R ^8A and R ⁴⁷ to R ⁵⁴ are each preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and each independently a hydrogen atom. A methyl, fluorine, or chlorine atom is more preferred.

At least one of R ^9A , R ^10A , R ^11A and R ^12A includes a silicon atom. "Containing a silicon atom" means that a silicon atom is included in all the substituents of the alkyl group or aryl group represented by R ^9A , R ^10A , R ^11A and R ^12A . That is, at least one of R ^9A , R ^10A , R ^11A and R ^12A is an alkyl group having a substituent or an aryl group having a substituent, and the substituent in the alkyl group and the aryl group contains a silicon atom .

At least one of R ^9A , R ^10A , R ^11A and R ^12A is preferably a group having a group containing a silicon atom as a substituent.

R ^9A to R ^12A are system to at least one of formula (IIa) as shown in the preferred group, R ^9A to R ^12A in at least one line in formula (ii) the group shown better.

* -L ¹ -Si (R ¹⁴⁴ ) ₃ (iia) [wherein L ¹ represents an alkanediyl group having 1 to 12 carbon atoms, and -CH ₂ -which is contained in the alkanediyl group may be passed through -O-, -CO -Or -NR ¹¹¹ -substituted.

R ¹¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

The three R ¹⁴⁴ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

* Indicates a bond with a nitrogen atom. ]

In formula (ii), n represents an integer of 1 to 8, and three R ¹⁴ each independently represent 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 * represents a nitrogen atom. Atomic bond.

Two of R ^9A to R ^12A are preferably based on the formula (iia), one selected by R ^9A and R ^10A , and one selected by R ^11A and R ^12A are expressed by the formula ( The base shown by iia) is better.

R ^9A and R ^12A are each preferably a group represented by the formula (iia), and more preferably each independently represented by the formula (ii).

Examples of the alkanediyl system represented by L ¹ include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, Hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, Undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1, 15-diyl, hexadecane-1,16-diyl and heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1, 2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, Pentane-1,4-diyl, 2-methylbutane-1,4-diyl, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane- 1,4-Diyl, cyclooctane-1,5-diyl and other cycloalkanediyl, norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1 , 5-diyl, adamantane-2,6-diyl, etc.

L ¹ is preferably an alkyldiyl group having 1 to 8 carbon atoms.

Examples of the saturated hydrocarbon group represented by R ¹¹¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and hexadecyl , Eicosyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl and 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclo Heptyl, cyclooctyl and tricyclodecyl.

Examples of the alkyl system represented by R ¹⁴⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, Neopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl, alkyl having 1 to 4 carbon atoms Better.

Examples of the alkoxy system represented by R ¹⁴⁴ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, tertiary butoxy, and n-pentyl. Oxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonoxy, n-decoxy, n-undecyloxy and n-dodecyloxy Alkoxy having 1 to 4 carbon atoms is preferred.

Examples of the alkyl system represented by R ¹⁴ in formula (ii) include methyl, ethyl, propyl, and butyl.

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

R ¹⁴ is preferably a hydrogen atom, methyl, ethyl, propyl, methoxy, ethoxy or propoxy, more preferably a hydrogen atom, methyl, ethyl, methoxy or ethoxy, Methoxy or ethoxy is more preferred.

The three R ¹⁴ series are preferably the same.

n is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

At least one of R ⁴¹ to R ⁴⁴ is preferably a base represented by formula (iia), and more preferably a base represented by formula (ii). R ⁴¹ and R ^{44 are} preferably each independently a base represented by formula (iia), and more preferably each independently a base represented by formula (ii).

Examples of the group represented by the formula (iia) include the groups shown below. Among them, the bases represented by the formulae (ii-1) to (ii-6) are preferred.

(In each chemical formula, * represents a bond with a nitrogen atom or a carbon atom.)

When R ^9A to R ^12A and R ⁴¹ to R ^{44 are} not a group represented by formula (iia), an alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent, which is each independently a hydrogen atom, is preferred. Each is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom, a fluoromethyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms An aryl group (for example, an aryl group represented by the following formula) as a substituent is more preferred.

(In each formula, * represents a bond with a nitrogen atom.)

Examples of the alkyl group represented by R ⁴⁷ to R ⁵⁴ (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) include a group represented by the following formula.

(In each formula, * represents a bond with a carbon atom.)

From the viewpoint of the ease of synthesis, R ⁴⁵ , R ⁴⁶ and R ⁵⁵ are each preferably an alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent, and each independently having a carbon number of 1 to An alkyl group of 8 or an aryl group represented by the following formula is more preferred.

(In each formula, * represents a bond with a nitrogen atom.)

Of formula (A-VI) and of formula (A-II), the relative anionic shown as the G ^{g- include: F -, Cl -, Br} -, I - and other halides, and the formula (Y1), formula (y2) and an anion represented by formula (y3).

In the formula (y1), R ^B1 represents a halogenated hydrocarbon group. The halogenated hydrocarbon group is preferably a group substituted with a fluorine atom, and examples thereof include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , and -C (CF ₃ ) ₃ .

In formula (y2), R ^B2 and R ^B3 represent a halogen atom or a halogenated hydrocarbon group.

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

The halogenated hydrocarbon group is preferably a group substituted with a fluorine atom, and examples thereof include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ).

R ^B2 and R ^B3 may be bonded to each other to form a ring including -SO ₂ -N ^-- SO _2- .

In formula (y3), R ^B4 and R ^B5 represent a group having a divalent aromatic ring. The divalent aromatic ring system is preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms such as phenylene and naphthyl. The group represented by R ^B4 and R ^{B5 is} preferably an alkenyl group having 2 to 4 carbon atoms such as a vinyl group and an allyl group. Examples of R ^B4 and R ^B5 include the following groups.

In formula (y3), M represents an aluminum atom or a boron atom.

G ^g- is preferably a halide ion or an anion represented by the formula (y2), and more preferably an anion represented by the formula (y2).

The ^g in G ^g- is preferably 1.

Examples of the aryl group which may have a substituent in D of the formula (A-VI) include a phenyl group which may have a substituent such as a group represented by the following formula, or a naphthyl group which may have a substituent. Examples of the substituent of the phenyl or naphthyl group include a halogen atom, an alkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms or A phenyl group having 1 to 4 carbon atoms.

(In each formula, * represents a bond with a carbon atom.)

Among the aryl groups, those represented by the formula (A1-2) and the formula (A1-6) are preferred.

Examples of the heteroaryl group which may have a substituent in D of the formula (A-VI) include a group represented by the following formula having a phenyl group and R ^X1 R ^X2 N (R ^X1 and R ^X2 are each independently A thiazolyl group representing an alkyl group having 1 to 4 carbons or a phenyl group which may have an alkyl group having 1 to 4 carbons as a substituent.

(In each formula, * represents a bond with a carbon atom.)

Among the heteroaryl groups, those represented by the formula (A1-12) and the formula (A1-13) are preferred.

In the formula (A-VI), D is preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a 5-membered heteroaryl group which may have a substituent, and a naphthyl group which may have a substituent. Or a thiazolyl group which may have a substituent is more preferable.

Examples of the cation system in the compound (A-VI) include cations represented by the formulae (A-VI-1) to (A-VI-28).

Among them, the formulas (A-VI-1), (A-VI-2), (A-VI-5), (A-VI-6), (A-VI-9), and ( A-VI-10) is preferably a cation.

Examples of the compound (A-VI) include compounds represented by the formulae (A-VI-1a) to (A-VI-28a) and the formulae (A-VI-1b) to (A-VI-28b). among them In particular, formula (A-VI-1b), formula (A-VI-2b), formula (A-VI-5b), formula (A-VI-6b), formula (A-VI-9b), and formula (A -VI-10b) is preferably a compound.

Examples of the cation system in the compound (A-II) include cations represented by the formulae (A-I-a1) to (A-I-a24). Among them, the cations represented by the formula (A-I-a1) to (A-I-a6) are particularly preferable.

Examples of the compound (A-II) include compounds represented by the formulae (A-I-a1a) to (A-I-a24a) and the formulae (A-I-a1b) to (A-I-a24b). Where especially The compounds represented by the formulae (A-I-a1a) to (A-I-a6a) and the formulae (A-I-a1b) to (A-I-a6b) are preferred.

The compound (A-VI) can be produced, for example, by reacting a compound represented by the formula D-H (D is the same as defined above) with a compound represented by the formula (C-II).

This reaction can be performed in the presence of an organic solvent or without a solvent.

In the formula (C-II), R ^1A to R ^12A each have the same meaning as described above.

The amount of the compound represented by formula (C-II) relative to D-H The compounds shown are 1 mole, preferably 0.5 moles to 8 moles, more preferably 1 mole to 3 moles.

The reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

Either reaction is preferably carried out in an organic solvent from the viewpoint of yield. Examples of organic solvents include: hydrocarbon solvents such as toluene and xylene; halogen hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitrocarbons such as nitrobenzene Solvents; ketone solvents such as methyl isobutyl ketone; ammonium solvents such as 1-methyl-2-pyrrolidone. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 1 part by mass of the compound represented by Formula D-H, and more preferably 2 parts by mass or more and 10 parts by mass or less.

The above reaction is preferably carried out in the presence of a condensing agent from the viewpoint of yield. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorous trichloride, sulfuric acid, and thionyl chloride.

The amount of the condensing agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less based on 1 part by mass of the compound represented by Formula D-H.

The method for obtaining the target compound (A-VI) from the reaction mixture is not particularly limited, and various known methods can be used. Examples thereof include a method of mixing a reaction mixture with an alcohol (for example, methanol), and filtering the precipitated crystals. The reaction mixture is preferably added to the aforementioned alcohol. The temperature at which the reaction mixture is added is preferably -100 ° C to 50 ° C. -80 ° C to 0 ° C is more preferred. After that, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like and then dried. It can also be further refined by conventional methods such as recrystallization.

Examples of the compound represented by D-H include the following compounds, and the formula (A1-2D), the formula (A1-6D), the formula (A1-12D), and the formula (A1-13D) are preferable. The compounds represented by the formulae (A1-2D) to (A1-6D) can be obtained from commercially available reagents. The compounds represented by the formulae (A1-12D) to (A1-17D) can be obtained by conventional methods. Various methods are prepared, for example, the method described in West German Patent Application No. P3928243.0.

The coloring agent of the present invention (hereinafter, this colorant may be referred to as "colorant (A)") contains the compound (A-VI). The colorant (A) may further contain other dyes (that is, dyes other than the compound (A-VI)), pigments, or a mixture of these.

The coloring curable resin composition of the present invention contains a coloring agent (A) containing a compound (A-VI) such as a compound (A-II), a resin (B), a polymerizable compound (C), and a polymerization initiator (D ). It may further contain a solvent (E).

In the present specification, the exemplified compounds of each component may be used alone or in combination unless otherwise specified.

<Colorant (A)>

In addition to the compound of the present invention, the colorant (A) may further contain other dyes (A2), pigments (P), or a mixture thereof for the purpose of toning, that is, to adjust the spectral characteristics.

The dyes (A2) are dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and examples thereof include: Color Index, The Society of Dyers and Colourists publishes) compounds classified by dyes, and the conventional dyes described in Dyeing Notes (Color Dye Co.).

According to the chemical structure, examples include: coumarin dyes, metal-containing azo dyes, pyridone azo dyes, barbitur azo dyes, quinophthalone dyes, methine dyes, cyanine dyes, Anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes. These dyes can be used alone or in combination of two or more.

Specific examples of the dye (A2) include CI solvent yellow 4 (hereinafter, the description of CI solvent yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, and 94, 98, 99, 162; CI solvent dyes such as CI solvent orange 2, 7, 11, 15, 26, 56, etc., CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34 , 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140 , 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212 , 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI acid dyes such as CI Acid Red 52, 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 Orange 34, 39, 41, 46, 50 , 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc. CI direct dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30 , 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, CI mordant dyes such as 34, 35, 36, 37, 42, 43, 47, 48 and so on.

The content of the compound (A-VI) such as the compound (A-II) in the colorant (A) is preferably 3 to 99.9% by mass, and 4 to 80% by mass relative to the total amount of the colorant. More preferably, 5 to 30% by mass is more preferable. When the content of the compound (A-VI) is within the aforementioned range, it is preferable because the brightness when the color filter is made is high.

The pigment (P) is not particularly limited, and conventional pigments can be used, and examples thereof include pigments classified by color index (published by The Society of Dyers and Colourists) pigments.

For example, CI Pigment Yellow 1, 3, 12, 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, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments.

Pigment (P) is CI Pigment Yellow 1, 3, 12, 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, 194, 214 and other yellow pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Blue 15, 15: 3 Blue pigments such as 15: 4, 15: 6, etc. are preferred, with CI Pigment Yellow 150, 185; CI Pigment Green 58 and CI Pigment Blue 15: 6 are more preferred, and CI Pigment Blue 15: 6 is particularly preferred. Since the colorant (A) contains the aforementioned pigment, the transmission spectrum is easily optimized, and the heat resistance and chemical resistance of the color filter are improved.

The content of the pigment (P) in the colorant (A) is preferably 0.1 to 60% by mass, and more preferably 8 to 55% by mass, with respect to the total amount of the colorant (A). When the pigment is contained in the above ratio, the transmission spectrum is easily optimized, and the heat resistance and chemical resistance of the color filter are improved.

The content of the colorant (A) in the colored curable resin composition is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and 10 to 50% by mass based on the total solid content. Better. When the content of the colorant (A) is within the aforementioned range, the color density when the color filter is made is sufficient, and the resin (B) and the polymerizable amount can be contained in the composition in a necessary amount. Compound (C) can form a pattern with sufficient mechanical strength.

Here, the "total solid content" in this specification means the total amount of the colored curable resin composition minus the content of the solvent. The total amount of the solid content and the content of each component with respect to the total amount can be measured by a conventional analysis means such as liquid chromatography or gas chromatography.

<Resin (B)>

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

Resin [K1]; at least one (Ba) (hereinafter sometimes referred to as "(Ba)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and a ring having 2 to 4 carbon atoms Copolymer of monomers (Bb) (hereinafter sometimes referred to as "(Bb)"), which are ether-like structures and ethylenically unsaturated bonds; resins [K2]; (Ba), (Bb), and copolymerizable with (Ba) (Bc) (but different from (Ba) and (Bb).) (Hereinafter sometimes referred to as "(Bc)"); copolymer of resin [K3]; (Ba) and (Bc) Resin [K4]; resin that reacts the copolymer of (Ba) and (Bc) with (Bb); resin [K5]; resin that reacts the copolymer of (Bb) and (Bc) with (Ba); Resin [K6]; A resin in which a copolymer of (Bb) and (Bc) is reacted with (Ba) and then reacted with a carboxylic anhydride.

(Ba) Specific examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-ethylene benzoic acid; maleic acid, fumaric acid, Pyrocitric acid, methyl fumaric acid, itaconic acid, 3-vinylphthalein Acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene di Unsaturated dicarboxylic acids such as carboxylic acids; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclic [ 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; Diene anhydride, pyrocitric anhydride, methylene succinic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydro Unsaturated dicarboxylic anhydrides such as phthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] heptan-2-ene anhydride; succinate mono [2- (meth) acrylic acid Unsaturated mono [(meth) acryloxyalkyl] esters of polyvalent polycarboxylic acids such as ethyl] esters, phthalic acid mono [2- (meth) acryloxyethyl] esters; such as The α- (hydroxymethyl) acrylic acid contains unsaturated acrylates such as a hydroxyl group and a carboxyl group in the same molecule.

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the point that copolymerization reactivity is obtained and the solubility of the obtained resin to an alkali aqueous solution.

Examples of the (Bb) system include a cyclic ether structure having 2 to 4 carbon atoms (for example, a group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). At least one selected) a polymerizable compound having an ethylenically unsaturated bond. The (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group.

In this specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The designations of "(meth) acrylfluorenyl" and "(meth) acrylate" are also synonymous.

Examples of (Bb) include a monomer having an epoxy ethyl group and an ethylenically unsaturated bond, a monomer having an epoxy butyl group and an ethylenically unsaturated bond, and a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond.体 等。 Body and so on.

(Bb) From the viewpoint of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance, a monomer having an epoxyethyl group and an ethylenically unsaturated bond is preferred.

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, secondary butyl (meth) acrylate, and trimethyl (meth) acrylate. Butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester (in this industry In the technical field, it is called by the common name of "dicyclopentyl (meth) acrylate." It is also sometimes called "tricyclodecyl (meth) acrylate."), Tricyclic (meth) acrylate [5.2. 1.0 ^2,6 ] decene-8-yl ester (in the technical field of this industry, it is called by the common name of "dicyclopentenyl (meth) acrylate."), Dicyclopentyloxyethyl (meth) acrylate Ester, isoamyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (meth) (Meth) acrylates such as naphthyl acrylate, benzyl (meth) acrylate, etc .; ) Hydroxy-containing (meth) acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, methylene Dicarboxylic acid diesters such as diethyl succinate; 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- Dihydroxybicyclo [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-methyl Bicyclo [2.2.1] hept-2-ene, 5-tertiary butoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene Ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (tertiary butoxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclic unsaturated compounds such as 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene; N-phenyl-cis-butenediimidine, N-cyclohexyl-cis-butenedi Sulfenimide, N-benzylcis butylenediimide, N-succinimidylimide-3-cis butylenediimideamine benzoate, N-succinimidylimide-4-cisbutyl Arylene diimide butyrate, N-succinimide imino-6-cis butylene diimide hexanoate, N-succinimide 3-maleimide dipropionate , N- (9-acridyl) maleimide derivatives such as maleimide, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, Isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the point of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylcis butylenediimide, N-cyclohexylcis butylenediimide, and N-benzyl Preference is given to maleimide and bicyclo [2.2.1] hept-2-ene.

Specific examples of the resin (B) include: 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic copolymer, 3,4-epoxy tricyclic [5.2.1.0 ^2,6 ] resins such as decyl acrylate / (meth) acrylic copolymer [K1]; propylene oxide (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic copolymer, ( Glycidyl acrylate / styrene / (meth) acrylic copolymer, 3,4-epoxy tricyclic [5.2.1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid / N-ring Resin such as hexyl cis butene diimide copolymer, 3-methyl-3- (meth) acryl fluorenyloxymethyloxycyclobutane / (meth) acrylic acid / styrene copolymer, etc. [K2]; Resin [K3] such as benzyl (meth) acrylate / (meth) acrylic copolymer, styrene / (meth) acrylic copolymer; add benzyl (meth) acrylate / (meth) acrylic copolymer (Meth) acrylic acid propylene oxide resin, (meth) acrylic acid tricyclodecyl ester / styrene / (meth) acrylic acid copolymer addition (meth) acrylic acid propylene oxide resin, (Meth) acrylate tricyclodecyl ester / benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin [K4] into (meth) acrylic acid propylene resin; etc .; a resin obtained by reacting (meth) acrylic acid tricyclodecyl / (meth) acrylic acid propylene copolymer with (meth) acrylic acid Resins, resins such as (meth) acrylic acid tricyclodecyl ester / styrene / (meth) acrylic acid propylene copolymers and (meth) acrylic acid-reacted resins [K5]; (meth) Resin [K6] and the like, such as a resin in which a copolymer of acrylate tricyclodecyl / glycidyl (meth) acrylate reacts with (meth) acrylic acid, and a resin with tetrahydrophthalic anhydride.

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

Resin [K1] can be referred to the method described in the document "The Practical Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., the first edition of the first edition of the Chemical Doctrine, March 1, 1972) and the method described in the document It is manufactured by citations.

The obtained copolymer can be used as it is after the reaction, or it can be used as a concentrated or diluted solution, or it can be used as a solid (powder) by a method such as re-sinking. The solvent at the time of polymerization can be used directly for the preparation of the colored curable resin composition of the present invention by using the solvent contained in the colored curable resin composition of the present invention. The manufacturing process of the coloring curable resin composition of this invention is simplified.

The polystyrene equivalent weight average molecular weight of the resin (B) 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 above range, the hardness of the color filter is increased, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.

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

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B). For example, the acid value can be determined by 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 even more preferably 17 to 55% by mass with respect to the total solid content. When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized from living radicals and / or acids generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and ( A meth) acrylate compound is preferred.

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 penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, tetraxin Pentaerythritol deca (meth) acrylate, tetranepentaerythritol nona (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanate, ethylene glycol modification Quality new Pentaerythritol tetra (meth) acrylate, ethylene glycol modified dinepentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dipentyl Tetraol hexa (meth) acrylate, γ-caprolactone modified neopentaerythritol tetra (meth) acrylate, γ-caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like.

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

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

The content of the polymerizable compound (C) in the colored curable resin composition is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and 17 to 55% by mass with respect to the total solid content. Even better. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of starting polymerization by generating active radicals, acids, and the like through the action of light or heat, and a conventional polymerization initiator can be used.

Examples of polymerization initiators that generate living radicals include: O-acyl oxime compounds, benzoyl ketone compounds, triazine compounds, acylphosphine oxide, and biimidazole Compound.

Examples of the O-fluorenyl oxime compound system include: N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzyloxy-1 -(4- Phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2- Imine, N-Ethyloxy-1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazol-3-yl] ethane-1-imine, N-ethyl Methoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolylmethoxy) benzylfluorenyl}- 9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1--1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazole-3 -Yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazole-3- Group] -3-cyclopentylpropane-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (all of which are manufactured by BASF), and N-1919 (made by ADEKA) can be used. Among them, O-fluorenyl oxime compounds are composed of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one Preferably at least one selected from the group consisting of -2-imines, more preferably N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine . Such an O-fluorenyl oxime compound tends to obtain a color filter with high brightness.

Examples of the benzoyl ketone compound system include 2-methyl-2-N-morpholinyl-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamino- 1- (4-N-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamine) -2-[(4-methylphenyl) methyl] -1 -[4- (4-N-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-isopropenylbenzene Oligomers of propane-1-one, α, α-diethoxyacetophenone, benzyldimethylketal, and the like. Irgacure (registered trademark) 369, Commercial products such as 907, 379 (all of which are manufactured by BASF).

Examples of the triazine compound system are: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro (Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5 -Triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2 -Yl) vinyl] -1,3,5-triazine, 2,4-bis (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 so on.

Examples of the aforementioned fluorenylphosphine compound system include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine compound and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

Examples of the aforementioned biimidazole compound system are: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -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 ( Alkoxyphenyl) 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 (see Japanese Patent Application Publication No. 48-38403, Japanese Patent Application 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.).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; diphenyl ketone, o-benzylidene benzoate methyl ester, 4-phenyldiphenylketone, 4-benzylfluorenyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (tertiarybutylperoxycarbonyl) diphenylketone, Diphenyl ketone compounds such as 2,4,6-trimethyldiphenyl ketone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloro Acridinone, diphenylethylene dione, methyl phenylglyoxylate, titanocene compound, and the like.

Examples of the acid-generating polymerization initiator are: 4-hydroxyphenyldimethylfluorene p-toluenesulfonate, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, 4-ethoxyfluorenylbenzene Dimethylpyridine p-toluenesulfonate, 4-Ethyloxyphenylmethylbenzylpyrene hexafluoroantimonate, triphenylpyrene p-toluenesulfonate, triphenylpyrene hexafluoroantimonate Salts, onium salts such as diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, and the like, as well as nitrobenzyltoluenesulfonate, benzoin tosylate, and the like.

The polymerization initiator (D) is obtained by polymerizing at least one selected from the group consisting of an O-fluorenyl oxime compound, an phenalkyl ketone compound, a triazine compound, a fluorenyl phosphino compound, and a biimidazole compound. The initiator is preferred, and a polymerization initiator containing an O-fluorenyl oxime compound is more preferred.

The content of the polymerization initiator (D) in the colored curable resin composition is preferably from 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), and is preferably 1 to 30 parts by mass. It is more preferably 20 parts by mass. When the content of the polymerization initiator (D) is within the aforementioned range, the high sensitivity will tend to shorten the exposure time, so the productivity of the color filter will be improved. high.

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but -COO- not in the molecule), and ether ester solvents (molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (containing OH in the molecule but -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amidine solvents and dimethyl sulfene.

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

Examples of the ether solvent system include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two Ethylene 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-dioxane, 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.

Examples of the ether ester solvent system include: methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, acetic acid 3 -Methoxybutyl, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

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

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

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

Among the solvents mentioned above, organic solvents having a boiling point of 1 ° C or higher and 210 ° C or lower at 1 atmosphere are preferred from the viewpoints of coating properties and drying properties. Examples of the solvent system include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether. Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide is preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone and 3-ethoxy Ethyl propionate is 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 colored 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 is improved, and the color density is not insufficient when forming a color filter, so the display characteristics tend to be improved.

<Other ingredients>

The colored curable resin composition of the present invention may contain a polymerization initiation aid, a leveling agent, a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, and the like, as required. Conventional additives in the technical field of the industry.

<Manufacturing method of colored curable resin composition>

The colored curable resin composition of the present invention can be mixed with a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and as needed. It is prepared by using a leveling agent, a polymerization initiator, and other ingredients.

The pigment (P) is preferably mixed with a part or all of the solvent (E) in advance so that the average particle diameter of the pigment is about 0.2 μm or less. It is preferably dispersed using a bead mill or the like. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. In this way In the material dispersion, the intended coloring curable resin composition can be prepared by mixing the remaining components to a predetermined concentration.

To the colorant (A), as the dye, a solution containing a dye obtained by dissolving a part or all of the solvent (E) in advance may be added. This solution is preferably filtered through a filter with a pore size of about 0.01 to 1 μm before being mixed with other ingredients.

The coloring curable resin composition obtained by the above-mentioned mixing 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 of 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 this invention may contain the coloring pattern mentioned later. A method for curing the colored curable resin composition is described 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 is obtained by, for example, coating the colored curable resin composition on a substrate, and drying the colored curable resin composition to form a colored composition layer, and exposing the colored composition layer through a photomask. The color filter of the present invention usually has a colored pattern on a coating film.

Examples of a method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is particularly preferred. The photolithography method is based on the aforementioned curable resin composition. A method of coating on a substrate and drying it to form a colored composition layer, and then exposing and developing the composition layer through a photomask.

In the photolithography method, a coating film of the cured product of the coloring composition layer described above can be formed without using a mask and / or without development during exposure. The coloring pattern and the coloring coating film thus formed 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, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

The substrate can be glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silicon oxide; polycarbonate, polymethyl methacrylate, and polyethylene terephthalate Resin plates such as diesters; silicon; aluminum, silver, silver / copper / palladium alloy films, and the like are formed on the substrate. On such substrates, other color filter layers, resin layers, transistors, and circuits can be formed.

The formation of pixels of various colors by photolithography can be performed using known or customary devices and conditions. For example, it can be produced as follows.

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

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

The temperature for 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 drying under reduced pressure, it is preferably performed at a temperature in the range of 20 to 25 ° C under a pressure of 50 to 150 Pa.

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the intended color filter.

Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the purpose of use can be used.

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, you can remove the light below 350nm by using a filter cut out of this wavelength range, or you can select the bandpass filter in the wavelength range of 436nm, 408nm, and 365nm. . Specific examples include: mercury lamps, light-emitting diodes, metal halogen lamps, halogen lamps, and the like.

Since the parallel light can be irradiated uniformly on the entire exposure surface or at the correct alignment position of the substrate on which the photomask and the coloring composition layer are formed, an exposure device using a photomask aligner and a stepper is preferred.

A colored pattern is formed on the substrate by developing the colored composition layer after exposure by contacting with a developing solution. The unexposed portion of the colored composition layer is dissolved and removed by the developing solution through development.

The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

The developing method may be a paddle method or a dipping method. And spray method. Furthermore, the substrate can be tilted at an arbitrary angle during development.

After development, washing with water is preferred.

Furthermore, post-baking is preferably performed with the obtained colored pattern. 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 to these examples. In the examples, the representative content and even the usage% and parts are based on quality 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 (A-I-a6a)

After adding 36.3 parts of potassium thiocyanate and 160 parts of acetone, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts of benzamidine chloride (manufactured by Tokyo Kasei Co., Ltd.) was dropped over 10 minutes. After the addition was completed, the mixture was stirred at room temperature for another 2 hours. Then, after cooling the reaction mixture under ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the addition was completed, the mixture was stirred at room temperature for another 30 minutes. Then, after the reaction mixture was ice-cooled, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After the addition was completed, the mixture was stirred at room temperature for another 30 minutes. Then, 35.3 parts of chloroacetic acid was added dropwise at room temperature. After the dropping was completed, the mixture was stirred under reflux for 7 hours. Next, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120 parts of tap water, and then 200 parts of toluene was added and stirred for 30 minutes. minute. Then, the stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded in a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then 200 parts of tap water, and finally 200 parts of saturated saline.

An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which water was removed. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure to obtain 52 parts of a compound represented by the formula (B-I-1).

21.2 parts of 4,4-diaminodiphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.), 38.6 parts of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 parts of acetic acid are added to 200 parts of tetrahydrofuran , Reflux for 8 hours. After the reaction was completed, tetrahydrofuran was distilled off to obtain 60 parts of a compound represented by the formula (A-I-a6-1).

The compound represented by the formula (A-I-a6-1) obtained above After 29.6 parts, 14.7 parts of the compound represented by the formula (B-I-1) and 20 parts of toluene were added, 23 parts of phosphorus trichloride was added, and the mixture was stirred at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction solution into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The stirring was stopped, and the mixture was allowed to stand for 30 minutes, and separated into an organic layer and an aqueous layer. After the aqueous layer was discarded in a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which water was removed. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a blue-violet solid. The blue-violet solid was dried under reduced pressure to obtain 42.1 parts of a compound represented by the formula (A-I-a6a).

Identification of the compound represented by formula (A-I-a6a)

(Mass analysis) Ionization mode = ESI +: m / z = 855.4 [M-Cl] ⁺ Exact mass: 890.4

Example 2: Synthesis of a compound represented by formula (A-I-a6b)

4.2 parts of a compound represented by formula (AI-a6-2), 2.8 parts of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and N, N-dimethylformamide After 30 parts were added, the mixture was stirred at 40 ° C for 3 hours. The reaction mixture is then cooled After reaching room temperature, 500 parts of tap water was added dropwise with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a turquoise solid. The blue-green solid was dried under reduced pressure to obtain 11.2 parts of a compound represented by the formula (A-I-a6b).

The compound of formula (AI-a6a) and formula (AI-a6b) 0.35 parts of FIG was dissolved in chloroform so that the volume becomes 250cm ^3, 2cm ³ wherein the ion exchanged water so that the volume becomes 100cm ³ (concentration: 0.028 g / L), and the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). The maximum absorption wavelength of this compound: λ max is 638 nm and 639 nm, respectively.

Example 3: Synthesis of a compound represented by formula (A-VI-2a)

In Example 1, except that N-1-ethyl-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of formula (BI-1), the same synthesis was performed as in Example 1 to obtain formula (A-VI- 2a).

Identification of the compound represented by formula (A-VI-2a)

(Mass analysis) ionization mode = ESI +: m / z = 719.0 [M-Cl] ⁺ exact mass: 754.5

Example 4: Synthesis of a compound represented by formula (A-VI-2b)

In Example 2, a compound represented by the formula (A-VI-2b) was obtained in the same manner as in Example 2 except that the compound represented by the formula (A-VI-2a) was used instead of the formula (A-I-a6a).

The compound of formula (A-VI-2a) and of formula (A-VI-2b) 0.35 parts of FIG dissolved in chloroform so that the volume becomes 250cm ^3, 2cm ³ wherein the ion exchanged water so that the volume becomes 100cm ³ (Concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). The maximum absorption wavelength of this compound: λ max is 615 nm and 617 nm, respectively.

<Measurement of solubility>

For the compounds obtained in Examples 1 to 4 and the compound represented by formula (II-0), propylene glycol monomethyl ether (hereinafter, referred to as PGME), ethyl lactate (hereinafter, referred to as EL), and propylene glycol monomethyl ether The solubility of an acid ester (hereinafter, simply referred to as PGMEA) was determined as follows.

The compound was mixed with the solvent in a 50 mL sample tube at the following ratio, and then the sample tube was sealed and shaken at 30 ° C. for 3 minutes with an ultrasonic vibration machine. After 30 minutes at room temperature, suction filtration was performed. Visually observe the residue. When insoluble matter cannot be confirmed, the solubility is judged to be good and recorded as ○, and when insoluble matter is confirmed, it is judged to be poor in solubility and recorded as x. The results are shown in Table 1.

[Synthesis of resin]

A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with an appropriate amount of nitrogen to create a nitrogen atmosphere. 100 parts of propylene glycol monomethyl ether acetate was fed, and heated to 85 ° C. while stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] A mixture of decane-9-yl acrylate (containing a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) was dissolved in propylene glycol monomethyl ether ethyl A solution of 40 parts of the acid ester was dripped in for about 5 hours using a dripping pump. On the other hand, a solution in which 26 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 120 parts of propylene glycol monomethyl ether acetate was used with another dropping pump. It was dropped into the flask in about 5 hours. After the dripping of the polymerization initiator was completed, the temperature was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of the 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 5

Colorant (A): 2.5 parts of dye represented by formula (AI-a6a); Resin (B): Resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): dioxin Tetraol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; And 380 parts of 4-hydroxy-4-methyl-2-pentanone; Leveling agent (H): 0.12 part of polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); mixed to obtain a colored hardening resin composition.

Example 6

Colorant (A): 2.5 parts of dye represented by formula (AI-a6b); Resin (B): Resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): dioxin Tetraol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; And 380 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H): 0.12 parts of polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); A colored curable resin composition was obtained.

Example 7

The colorant (A): 2.5 parts of the dye represented by the formula (A-VI-2a); the resin (B): the resin (B-1) (solid content conversion) 50 parts; the polymerizable compound (C): two 16 parts of neopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylsulfide) Phenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; and 380 parts of 4-hydroxy-4-methyl-2-pentanone; Leveling agent (H): Polyether modified polysiloxane (TORAY SILICONE SH8400; Toray Dow Corning Co., Ltd.) 0.12 parts ; Mixed to obtain a colored curable resin composition.

Example 8

Colorant (A): 2.5 parts of the dye represented by the formula (A-VI-2b); Resin (B): Resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): 2 16 parts of neopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylthiobenzene) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 380 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H): 0.12 parts of polyether modified polysiloxane (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); They were mixed to obtain a colored curable resin composition.

Example 9

Will: C.I. Pigment Blue 15: 6 (Pigment) 4.48 parts Acrylic pigment dispersant 1.76 parts of propylene glycol monomethyl ether acetate 29.8 parts were mixed, the pigment was sufficiently dispersed using a bead mill, and then, the colorant (A): 2.5 parts of the dye represented by the formula (AI-a6a); resin (B): 50 parts of resin (B-1) (converted by solid content); polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 Parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Made by the company; 4.1 parts of O-fluorenyl oxime compound); solvent (E): 100 parts of propylene glycol monomethyl ether acetate; and 450 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H ): 0.12 parts of polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); mixed to obtain a colored hardening resin composition.

Example 10

CI Pigment Blue 15: 6 (pigment) 2.2 parts of acrylic pigment dispersant 1.0 part of propylene glycol monomethyl ether acetate 14.1 parts were mixed, the pigment was sufficiently dispersed using a bead mill, and then the colorant (A): Formula ( 8.4 parts of the dye shown by AI-a6a); CI acid red 52 0.1 parts; resin (B): resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1 -(4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): 100 parts of propylene glycol monomethyl ether acetate; and 50 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H): polyether modified silicone oil (TORAY SILICONE SH8400; Toray Dow Corning (Manufactured by the company) 0.12 parts; mixed to obtain a colored curable resin composition.

Comparative Example 2

Dye: 2.5 parts of the dye represented by the formula (II-0); Resin (B): 50 parts of the resin (B-1) (in terms of solid content); polymerizable compound (C): dipentaerythritol hexaacrylic acid Esters (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) octane-1 -Keto-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): 100 parts of propylene glycol monomethyl ether acetate; and 4-hydroxyl 450 parts of 4-methyl-2-pentanone; leveling agent (H): 0.12 parts of polyether modified polysiloxane (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); coloring and hardening Resin composition.

[Formation of pattern]

The colored curable resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Corporation) 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 set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon) was used at 150 mJ / cm ² in an atmospheric environment. Exposure (365 nm reference) light irradiation. The photomask is a photomask in which 100 μm line and space patterns are formed. After light irradiation, the coating film (thickness: 2.8 μm) was immersed and developed at 23 ° C. for 80 seconds using an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide. After washing with water, it was placed in an oven. After 20 minutes at 220 ° C, a pattern was obtained.

[Heat resistance evaluation]

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 heating of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The coating film obtained in each example was subjected to the above-mentioned heat resistance evaluation results. The color difference (ΔEab *) was 10.0 (Example 5), 10.1 (Example 6), 11.2 (Example 7), 12.0. (Example 8), 7.3 (Example 9), and 8.5 (Example 10). The heat resistance evaluation was performed in the same manner as in Comparative Example 2. The color difference (ΔEab *) was 40.1.

The colored curable resin composition containing the compound of the formula (A-IV) can produce a color filter having good heat resistance.

[Industrial availability]

The compound of the present invention is excellent in solubility in an organic solvent. Since the colored curable resin composition of the present invention contains the compound of the present invention, a high-quality color filter with less generation of foreign matter can be produced from the colored curable resin composition.

Claims (11)

A compound represented by the formula (A-VI), In the formula (A-VI), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (an oxygen may be inserted between the carbon atoms constituting the alkyl group Atom), R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aromatic group which may have a substituent However, at least one of R ^9A to R ^12A is a group represented by the following formula (iia), G ^g- represents a relative anion, g represents an arbitrary natural number, and D represents an aryl group which may have a substituent, Or a heteroaryl group which may have a substituent, * -L ¹ -Si (R ¹⁴⁴ ) ₃ (iia) In the formula (iia), L ¹ represents an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group contains -CH ₂ -may be substituted by -O-, -CO-, or -NR ^111- , R ¹¹¹ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms, and three R ¹⁴⁴ each independently represent an alkyl group having 1 to 12 carbon atoms Oxygen, * represents a bond with a nitrogen atom. The compound according to item 1 of the scope of patent application, wherein at least one of R ^9A to R ^12A is a base represented by formula (ii), In formula (ii), n represents an integer of 1 to 8, three R ¹⁴ each independently represent an alkoxy group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. The compound described in item 1 of the scope of patent application, wherein the compound represented by the formula (A-VI) is a compound represented by the formula (A-II), In the formula (A-II), X represents an oxygen atom or a sulfur atom, and R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms which may have a substituent (at the carbon atom constituting the alkyl group) An oxygen atom may be inserted in between) or an aryl group which may have a substituent. However, at least one of R ⁴¹ to R ⁴⁴ is a group represented by formula (iia), * -L ¹ -Si (R ¹⁴⁴ ) ₃ (iia ) In the formula (iia), L ¹ represents an alkanediyl group having 1 to 12 carbon atoms, and -CH ₂ -contained in the alkanediyl group may be substituted with -O-, -CO-, or -NR ^111- , and R ¹¹¹ represents A hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, three R ¹⁴⁴ each independently represent an alkoxy group having 1 to 12 carbon atoms, * represents a bond with a nitrogen atom, and R ⁴⁷ to R ⁵⁴ each independently represent A hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms (an oxygen atom can be inserted between the carbon atoms constituting the alkyl group), and R ⁵⁵ represents a hydrogen atom and an alkyl group having 1 to 20 carbon atoms Or an aryl group which may have a substituent, G ^g- represents a relative anion, and g represents an arbitrary natural number. The compound according to item 3 of the scope of patent application, wherein at least one of R ⁴¹ to R ⁴⁴ is a group represented by formula (ii), In formula (ii), n represents an integer of 1 to 8, three R ¹⁴ each independently represent an alkoxy group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. A coloring agent, which contains the compound as described in item 1 of the scope of patent application. The coloring agent according to item 5 of the patent application scope, which further contains a blue pigment. The coloring agent according to item 6 of the scope of patent application, wherein the blue pigment is C.I. Pigment Blue 15: 6. A coloring curable resin composition containing a coloring agent, a resin, a polymerizable compound, and a polymerization initiator as described in item 5 of the scope of patent application. A coating film is formed by the colored hardening resin composition as described in item 8 of the scope of patent application. A color filter is formed of a color-hardening resin composition as described in item 8 of the scope of patent application. A display device includes a color filter as described in item 10 of the scope of patent application.