TW201332986A - Colored curable resin composition - Google Patents

Abstract

The present invention provides a colored curable resin composition comprising a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and an organometal compound, the coloring agent comprises a compound of the formula (1) below, and the maximum molal absorptivity value of the organometallic compound in visible light area is smaller than the maximum molal absorptivity value of the compound of the formula (1) in visible light. Wherein R1 and R2 each independently represent a phenyl group optionally having a substituent; R3 and R4 each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms; R5 represents -OH, -SO3H, etc. R6 and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of from 0 to 4.

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used in the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As such a color-curable resin composition, a color-curable resin composition is known, and a compound represented by the formula (A2-1a) and a compound represented by the formula (A2-1b) are contained as a coloring agent by 2- Ethylhexylamine and sulfoximine dye, and CIPigment blue, and bis(dibutyldithiocarbamic acid) zinc (JP2011-118365-A).

In the above-described colored curable resin composition, the brightness of the color filter obtained by the colored curable resin composition is not necessarily sufficient.

The present invention contains the following invention.

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an organometallic compound, wherein the colorant contains a compound represented by the formula (1), and the visible light region of the organometallic compound The maximum value of the Mohr absorption coefficient is smaller than the maximum value of the Mohr absorption coefficient in the visible light region of the compound represented by the formula (1).

In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent.

R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon group The hydrogen atom may be substituted by an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ - contained in the above saturated hydrocarbon group may be -O-, -CO- or -NR ¹¹ - replaced.

R ¹ and R ³ may form a ring containing a nitrogen atom together with a nitrogen atom, and R ² and R ⁴ may form a ring together with a nitrogen atom.

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

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

m represents an integer from 0 to 4. When m is 2 or more, a plurality of R ^{5 's} may be the same or different.

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

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

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other and form a 3 to 10 member nitrogen-containing heterocyclic ring together with the nitrogen atom.

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

[2] The colored curable resin composition according to [1], wherein the organometallic compound is selected from the group consisting of a compound represented by the formula (F1), a compound represented by the formula (F2), and a hydrate thereof. At least one of them.

In the formula (F1), W ¹ and W ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, the aliphatic hydrocarbon group and the aromatic hydrocarbon group. The hydrogen atom contained may be substituted with a hydroxyl group.

M ¹ represents a metal atom.

x represents an integer of 1 to 3, and when x is 2 or more, a plurality of W ¹ and W ² may be the same or different from each other].

[In the formula (F2), W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom.

M ² represents a metal atom.

y represents an integer of 1 to 3, and when y is 2 or more, a plurality of W ³ and W ⁴ are the same or different from each other.

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

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

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

According to the colored curable resin composition of the present invention, a high-density color filter can be formed.

21‧‧‧ glass substrate

22‧‧‧TFT (switching element)

22a‧‧‧Gate electrode

22b‧‧‧gate insulating film

22c‧‧‧Multi-crystalline enamel film

22d‧‧‧Protective film

23‧‧‧Color filter layer

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

23a‧‧‧Red Filter

23b‧‧‧Green Filter

23c‧‧‧Blue filter

24‧‧‧ pixel electrodes

27‧‧‧ signal line

29‧‧‧Photosensitive resin film (protective film)

201, 202‧‧‧ connection holes

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

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

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

The colored curable resin composition of the present invention contains: a coloring agent (A), Resin (B), polymerizable compound (C), polymerization initiator (D), and organometallic compound (M).

The coloring agent (A) is preferably a compound containing the above formula (1) (hereinafter referred to as "compound (1)"), and further contains a pigment (A1).

The colored curable resin composition of the present invention is preferably a solvent (E).

In addition, the coloring-curable resin composition of the present invention may contain a dye different from the compound (1) (hereinafter referred to as "dye (A2)") or a polymerization initiator (option) as needed. At least one of the group of D1) and the surfactant (F).

Further, in the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

<compound (1)>

In the colored curable resin composition of the present invention, a high-density color filter can be produced by containing the compound (1) as a coloring agent. As the compound (1), it may be a tautomer thereof.

[In the formula (1), R ¹ to R ⁷ and m each have the same meaning as described above].

In the case of R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ , examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group. a linear alkyl group having 1 to 20 carbon atoms such as an octyl group, a decyl group, a decyl group, a dodecyl group, a hexadecyl group or an eicosyl group; an isopropyl group, an isobutyl group, a secondary butyl group, a branched alkyl group having a carbon number of 3 to 20 such as a tertiary butyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group; a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a tricyclic fluorenyl group.

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

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

Examples of the -SR ⁸ include a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a mercaptothio group, an eicosylthio group and the like.

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

Examples of the -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tertiary butoxysulfonyl group, a hexyloxysulfonyl group, and the like. Eicosyloxysulfonyl and the like.

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

R ⁹ and R ¹⁰ may be bonded to each other and together with a nitrogen atom form a 3 to 10 member nitrogen-containing heterocyclic ring. That is, an atom constituting a monovalent saturated hydrocarbon group in R ⁹ may be bonded to an atom constituting a monovalent saturated hydrocarbon group in R ¹⁰ and a 3 to 10 member nitrogen-containing hetero ring may be formed together with the nitrogen atom. As the heterocyclic ring, for example, the following may be mentioned.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³ and R ⁴ include those having 1 to 10 carbon atoms among the saturated hydrocarbon groups of R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted. The alkyl group having 1 to 3 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group.

a saturated hydrocarbon group substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms For example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, toluylmethyl, tolylethyl, tolylpropyl, tolylbutyl, methoxy Phenylmethyl, methoxyphenylethyl, methoxyphenylpropyl, methoxyphenylbutyl and the like.

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

Examples of the saturated hydrocarbon group substituted by a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

As R ³ and R ⁴ , an unsubstituted saturated hydrocarbon group having 1 to 10 carbon atoms is preferred, and a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is preferred, and 1 is a carbon number of 1 to 3. A saturated hydrocarbon group is more preferred.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a secondary butyl group. Base, tertiary butyl, isopentyl, neopentyl and the like.

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

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

The above-mentioned ⁺ N(R ¹¹ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms in at least two of the four R ¹¹ groups. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these substituents, -R ^{8 is} preferred, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred. As the case of -SO ₃ ^- Z ⁺ in this case, -SO ₃ ^-+ N(R ¹¹ ) _{4 is} preferred.

Examples of the phenyl group having a substituent include toluyl, dimethylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, methylthiophenyl, and methylsulfonate. Nonylphenyl and the like. Among them, a phenyl group having a substituent in the ortho position relative to a bond bond with nitrogen is preferred.

R ¹ and R ^{2 are} each independently a phenyl group having a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, preferably a tolyl group or a dimethylphenyl group, and an o-tolyl group or 2,6. - Dimethylphenyl is more preferred.

R ¹ and R ³ together with the nitrogen atom form a ring containing a nitrogen atom. That is, a carbon atom on the benzene ring constituting the phenyl group which may have a substituent in R ¹ may be bonded to an atom constituting the monovalent saturated hydrocarbon group in R ³ and form a ring containing a nitrogen atom together with the nitrogen atom. R ² and R ⁴ may form a ring containing a nitrogen atom together with a nitrogen atom. That is, a carbon atom on the benzene ring constituting the phenyl group which may have a substituent in R ² may be bonded to an atom constituting the monovalent saturated hydrocarbon group in R ⁴ and form a ring containing a nitrogen atom together with the nitrogen atom. As the formed ring, for example, the following may be mentioned.

As R ⁵ , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ^{10 are} preferred.

As R ⁶ and R ⁷ , a hydrogen atom, a methyl group and an ethyl group are preferred, and a hydrogen atom is more preferred.

m is preferably an integer of 0 to 2, more preferably 1 or 2.

As the compound (1), a compound represented by the formula (2) is preferred.

In the formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms.

p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R ²³ may be the same or different, and when q is 2 or more, a plurality of R ²⁴ may be the same or different.

^Examples of the alkyl group having a carbon number of 1 to 4 representing R ²¹ , R ²² , R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a secondary butyl group. Base, tertiary butyl, etc.

R ²¹ and R ²² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ²³ and R ²⁴ are preferably a methyl group.

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

As the compound (1), a compound represented by the formula (3) is preferred.

In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms.

R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms].

^Examples of the alkyl group having 1 to 4 carbon atoms of R ³¹ to R ³⁶ include the same as those described above.

R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ³³ to R ³⁶ are each independently a hydrogen atom or a methyl group.

As the compound (1), for example, a compound represented by any one of the formulae (1-1) to (1-15) can be mentioned. Among them, from the viewpoint of excellent solubility in an organic solvent, it is preferred to use a compound represented by formula (1-1), formula (1-2) or formula (1-5) to formula (1-12). .

The method for producing the compound (1) includes a compound represented by the formula (1a), a compound represented by the formula (1b), and a compound represented by the formula (1c) in the presence of an organic solvent or without a solvent. The method of carrying out the reaction. From a yield point of view, It is preferred to carry out the reaction in the absence of a solvent. The reaction temperature is preferably from 30 ° C to 180 ° C, more preferably from 80 ° C to 130 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 3 hours to 8 hours.

[In the formulae (1b) and (1c), R ¹ to R ⁴ each have the same meaning as described above].

Examples of the organic solvent include a hydrocarbon solvent such as toluene or xylene; a halogenated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or chloroform; an alcohol solvent such as methanol, ethanol or butanol; and a nitro hydrocarbon solvent such as nitrobenzene; a ketone solvent such as isobutyl ketone; a guanamine solvent such as 1-methyl-2-pyrrolidone;

The compound of the formula (1b) and the compound of the formula (1c) are used in an amount of 1 mol to 8 mol per mol, preferably 1 mol, per mol of the compound represented by the formula (1a). Below 5 ears below the ear. It can be reacted separately in stages or simultaneously.

From the viewpoint of easy production of the compound (1), it is preferred that the compound represented by the formula (1b) and the compound represented by the formula (1c) have the same structure.

The method of obtaining the compound (1) of the objective compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture may be mixed with an acid (for example, acetic acid or the like), and the precipitated crystals may be filtered. It is preferred that the acid is added to the aqueous solution after the acid solution is prepared in advance. The temperature at which the reaction mixture is added is preferably 10 ° C or more and 50 ° C or less. Further, after that, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are washed with water or the like, and preferably dried. Further, if necessary, it can be re-refined by a known method such as recrystallization.

The content of the compound (1) in the colored curable resin composition of the present invention is preferably 0.025% by mass or more and 48% by mass or less based on the total amount of the solid content, and is preferably 0.08% by mass or more and 42% by mass or less. Preferably, it is more preferably 0.1% by mass or more and 30% by mass or less. Here, the "total amount of solid content" in the present specification means the amount by which the solvent content is removed from the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component relative thereto can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

Further, the colorant (A) contains both the pigment (A1) and/or the dye (A2) and the compound (1), and the content of the compound (1) is 0.5 with respect to the total amount of the colorant (A). The mass% or more is preferably 80% by mass or less, more preferably 1% by mass or more and 70% by mass or less, and still more preferably 1% by mass or more and 50% by mass or less.

<Pigment (A1)>

As the pigment (A1), a known pigment can be used without particular limitation, and examples thereof include a compound classified into a pigment by a Colour Index (published by The Society of Dyers and Colourists).

As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109 can be cited. Yellow pigments such as 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, Orange pigments such as 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue (CIPigment Blue) 15, 15:3, 15:4, 15:6, 60, 80 and other blue pigments; CI Pigment Violet (CIPigment Violet) 1, 19, 23 , 29, 32, 36, 38 and other purple pigments; CI pigment green (CIPigment Green) 7, 36, 58 and other green pigments; CI pigment brown (CIPigment Brown) 23, 25 and other brown pigments; CI pigment black (CIPigment Black) 1, 7 and other black pigments.

As a pigment, it is a blue pigment such as CIPigment Blue 15, 15:3, 15:4, 15:6, 60, and a purple pigment such as CIPigment Violet 1, 19, 23, 29, 32, 36, 38, etc. Preferably, CIPigment Blue 15:3, 15:6 and CIPigment Violet 23 are preferred, and CIPigment Blue 15:6 is preferred. In the case where the coloring-curable resin composition of the present invention is prepared as a blue colored curable resin composition, the penetration spectrum is easily optimized, and the light resistance and resistance of the color filter are improved. The quality of the product became good.

The pigment may be subjected to rosin treatment as needed, surface treatment using a pigment derivative introduced with an acidic group or a basic group, graft treatment of a pigment surface by a polymer compound or the like, and microparticles by a sulfuric acid micronization method or the like. The treatment or the removal treatment by an organic solvent or water to remove impurities, the removal treatment by an ion exchange method such as ionic impurities, or the like.

The pigment is preferably one having a uniform particle size. A pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained by containing a pigment dispersant and performing a dispersion treatment.

Examples of the pigment dispersant include a cationic dispersant such as a cationic type, an anionic type, a nonionic type, an amphoteric type, a polyester type, a polyamine type, and an acrylic type. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersing agent, KP (Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyowa Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by CIBA Co., Ltd.) can be cited. ), Ajisper (Ajinomoto Fine techno), Disperbyk (BYK Chemical Co., Ltd.), etc.

When the pigment dispersant is used, the amount thereof is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 50% by mass, based on the pigment (A1). When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a relatively uniformly dispersed state can be obtained.

When the colorant (A) contains the pigment (A1), the content of the pigment (A1) is preferably 20% by mass or more and 99.5% by mass or less based on the total amount of the coloring agent (A), and is preferably 30% by mass or more and 99% by mass. % below is better.

<dye (A2)>

The dye (A2) is not particularly limited as long as it is different from the compound (1), and known dyes can be used, and examples thereof include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mord dyes, and acid dyes. A dye such as a sulfonamide derivative of an amine salt or an acid dye, for example, a compound classified into a dye (other than a pigment and having a hue) by a color index (published by The Society of Dyers and Colourists), or a dyeing note A known dye described in (Color Dyeing Company). Further, depending on the chemical structure, examples thereof include an azo dye, a cyanine dye, a triphenylmethane dye, a xanthene dye, an indigo dye, a naphthoquinone dye, a quinone imine dye, and a methine group. Dye, azomethine dye, squarylium Dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, an organic solvent-soluble dye is preferred.

Specifically, CISolvent Yellow 4 (CI Solvent Yellow 4; hereinafter, the description of CI Solvent Yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI Solvent Red 45, 49, 125, 130, 218; CI Solvent Orange 2, 7, 11, 15, 26, 56; CI Solvent Blue (CI solvent) Blue) 4, 5, 37, 67, 70, 90; CI Solvent Gree (CI Solvent Green) 1, 4, 5, 7, 34, 35 and other CI solvent dyes, CIAcid Yellow (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; CIAcid Red (CI Acid Red) 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 5 7, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CIAcid Orange 6, CI, 6, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CIAcid violet (CI Acid Violet) 6B, 7, 9, 17, 19, 30, 102; CIAcid Blue (CI Acid Blue) 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335; CIAcid Green 1, CI, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CIDirect 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; CIDirect Red (CI Direct Dye Red) 79, 82, 83, 84, 91, 92, 96 , 97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234 , 241, 243, 246, 250; CIDirect Orange (CI Direct Dye Orange) 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CIDirect Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CIDirect Blue (CI Direct Dye Blue) 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CIDirect Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. CI Direct dyes, CI Disperse Yellow 54, 76 and other CI disperse dyes, CIBasic Red 1, 10; CIBasic Blue 1, 3, 5, 7, 9, 19, 24, 25,26,28,29,40,41,54,58,59,64,65,66,67,68; CIBasic Green 1; etc. CI basic dye, CIReactive Yellow 2, 76, 116; CIReactive Orange 16; CIReactive Red36; and other CI reactive dyes, CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CIMordant Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 , 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CIMordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CIMordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32 , 37, 40, 41, 44, 45, 47, 48, 53, 58; CI Mordant Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; CIMordant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34 CI dyes such as 35, 41, 43, and 53, and CI dyes such as CIVat Green1.

For these dyes, it is only necessary to select a spectroscopic spectrum suitable for the desired color filter. Among them, blue dyes, purple dyes, and red dyes are preferred.

When the coloring agent (A) contains the dye (A2), the content of the dye (A2) is preferably 0.5% by mass or more and 35% by mass or less based on the total amount of the coloring agent (A), and is preferably 1% by mass or more and 30% by mass. % below is better.

As the coloring agent (A), a coloring agent made of the compound (1) and the pigment (A1) and a coloring agent made of the compound (1), the pigment (A1) and the dye (A2) are preferred.

When the coloring agent (A) is a coloring agent made of the compound (1) and the pigment (A1), the content of these is preferably the same as the total amount of the coloring agent (A).

Compound (1): 0.5% by mass or more and 80% by mass or less

Pigment (A1): 20% by mass or more and 99.5% by mass or less, more preferably

Compound (1): 1% by mass or more and 50% by mass or less

Pigment (A1): 50% by mass or more and 99% by mass or less.

When the coloring agent (A) is a coloring agent made of the compound (1), the pigment (A1), and the dye (A2), the content of these is preferably the same as the total amount of the coloring agent (A).

Compound (1): 0.5% by mass or more and 7.95% by mass or less

Pigment (A1): 20% by mass or more and 99% by mass or less

Dye (A2): 0.5% by mass or more and 35% by mass or less, more preferably

Compound (1): 1% by mass or more and 50% by mass or less

Pigment (A1): 49% by mass or more and 98% by mass or less

Dye (A2): 1% by mass or more and 30% by mass or less.

The content of the colorant (A) is desirably 5 to 60% by mass, more desirably 8 to 55% by mass, and more desirably 10 to 50% by mass based on the total amount of the solid content. When the content of the coloring agent (A) is within the above range, since the color density when the color filter is sufficient, and the required amount of the resin (B) and the polymerizable compound (C) can be contained in the composition, the machine can be formed. A pattern of sufficient strength.

<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].

The resin [K1] is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter referred to as "(a)"), and a ring having a carbon number of 2 to 4. a copolymer of a monomer having an ether structure and an ethylenically unsaturated bond (b) (hereinafter referred to as "(b)"); a resin [K2] (a) and (b), and a sum (a) Copolymerized monomer (c) (only, with (a) and (b) different) (hereinafter referred to as "(c)"); copolymer [K3] (a) and (c); resin [K4] at ( a) a resin which reacts with (b) in the copolymer of (c); a resin which reacts (a) in the copolymer of (b) and (c); a resin [K6] at ( b) a resin which reacts with (a) in the copolymer of (c) and then reacts the carboxylic anhydride.

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

Among these, from the viewpoint of copolymerization reactivity, or from the viewpoint of solubility of the obtained resin to an aqueous alkaline solution, acrylic acid, methacrylic acid, maleic anhydride or the like is preferred.

(b), for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, a propylene oxide ring, and a tetrahydrofuran ring) and ethylene are not A polymerizable compound of a saturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

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

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), and having an oxypropylene group and ethylene Monomer (b2) of the unsaturated bond (hereinafter referred to as "(b2)"), monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3)") Situation) and so on.

(b1), for example, a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon having a linear or branched shape is epoxidized (hereinafter referred to as "(b1-1)") In the case of the monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and a ring. Oxypropyl vinyl ether, o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxy Propyl ether, p-vinylbenzyl epoxypropyl ether, α-methyl-o-vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-甲Base-p-vinylbenzylepoxypropyl ether, 2,3-bis(glycidoxyoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2 , 5-bis(epoxypropyloxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-paran (epoxypropyloxymethyl) Styrene, 2,3,5-glycol (epoxypropyloxymethyl)styrene, 2,3,6-glycol (epoxypropyloxymethyl)styrene, 3,4,5 - ginseng (epoxypropyloxymethyl)styrene, 2,4,6-glycol (epoxypropyloxymethyl)styrene, and the like.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), (A) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A 400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; A compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ⁵¹ and R ⁵² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ⁵¹ and X ⁵² represents: a single ^{bond, -R 53 -, * - R} 53 -O -, * - R 53 -S-, or * -R ⁵³ -NH-.

R ⁵³ represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates the bond key with O].

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

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

The R ⁵¹ and R ⁵² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

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

As X ⁵¹ and X ⁵² , a single bond, a methylene group, an ethylidene group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O- are preferable, and more preferably, a single bond or a * -CH ₂ CH ₂ -O- (* indicates a bond with O).

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

The compound represented by the formula (II) may, for example, be a compound represented by any one of the formulae (II-1) to (II-15). Preferably, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II) -15) the compound shown. More preferably, it is a compound represented by Formula (II-1), Formula (II-7), Formula (II-9) or Formula (II-15).

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

As the (b2), a monomer having an oxypropylene group and a (meth)acryloxy group is preferred. As (b2), 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, 3-ethyl- 3-methylpropenyloxymethyl propylene oxide, 3-ethyl-3-propenyloxymethyl propylene oxide, 3-methyl-3-methylpropenyloxyethyl propylene oxide, 3-methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-propenyloxyethyl ring Oxypropane and the like.

As the (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, BISCOAT V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), from the heat resistance of the obtained color filter, In terms of higher reliability such as resistance to defects, (b1) is preferred. Further, from the viewpoint of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

As (c), for example, (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl (meth) acrylate, (methyl) ) butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (methyl) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate ( In this technical field, the conventional name is "dicyclopentanyl (meth) acrylate". Further, there is a case called "tricyclodecyl (meth) acrylate), tricyclo(meth) acrylate [5.2. 1.0 ^2,6 ]decene-8-yl ester (in the technical field, the customary name is "dicyclopentenyl (meth)acrylate)", dicyclopentyloxyethyl (meth)acrylate, ( Isobornyl methyl methacrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate , (meth) acrylate, etc. (meth) acrylates; a hydroxyl group-containing (meth) acryloyl ester such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, itaconic acid Dicarboxylic acid diester such as ethyl ester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2 - alkene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1 Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy- 5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2. 1]hept-2-ene, 5-tris-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-benzene Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2.1]heptane-2- a bicyclic unsaturated compound such as 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide , N-benzyl maleimide, 3-maleimide benzyl acid N-succinimide, 4-maleimide butyric acid N-succinimide, 6-male Derivatization of dicarbonyl succinimide such as N-succinimide, 3-maleimide propionate N-succinimide, N-(9-acridinyl)maleimide Species; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, ethylene chloride, chlorination Methylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoamylene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmalazone An amine, a bicyclo[2.2.1]hept-2-ene or the like is preferred.

In the resin [K1], the ratio derived from the individual structural units is in the entire structural unit constituting the resin [K1].

Structural unit derived from (a): 2 to 60 mol%

The structural unit derived from (b): 40 to 98% by mole is preferred,

Structural unit derived from (a): 10 to 50 mol%

The structural unit derived from (b): 50 to 90 mol% is more preferable.

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

Resin [K1], for example, can be referred to the document "Experimental Method for Polymer Synthesis" (Dazu Takashi, Institute of Chemicals, 1st Edition, 1st, 1st, 1972, March 1, 1972) and the literature The cited documents are produced and manufactured.

Specifically, for example, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction container, and for example, a nitrogen gas is substituted for nitrogen to form a deoxidizing atmosphere, and the mixture is stirred. A method of heating and keeping warm. In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and can be used as a general user in the field. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or The organic peroxide (such as benzamidine peroxide) may be a solvent (E) which is a solvent of the coloring curable resin composition, and the like.

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

In the resin [K2], the ratio derived from individual structural units In the full structural unit of the resin [K2],

Structural unit derived from (a): 2 to 45 mol%

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

Structural unit derived from (c): 1 to 65 mol% is preferred,

Structural unit derived from (a): 5 to 40 mol%

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

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

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance and mechanical strength of the obtained pattern are Good tendencies.

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

In the resin [K3], the ratio derived from the individual structural units is in the entire structural unit constituting the resin [K3].

Structural unit derived from (a): 2 to 60 mol%

The structural unit derived from (c): 40 to 98 mol% is preferred,

Structural unit derived from (a): 10 to 50 mol%

The structural unit derived from (c): 50 to 90 mol% is more preferred.

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

The resin [K4], after obtaining the copolymer of (a) and (c), (b) having a cyclic ether having 2 to 4 carbon atoms and (a) having a carboxylic acid and/or It is produced by addition of a carboxylic anhydride.

First, the copolymer of (a) and (c) is produced in the same manner as the method described in the production method of the resin [K1]. In this case, the ratio derived from the individual structural units is preferably the same ratio as those listed in the resin [K3].

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

Continuing the manufacture of the co-polymers of (a) and (c), replacing the environment inside the flask from nitrogen to air, and reacting the catalyst (b), carboxylic acid or carboxylic anhydride with a cyclic ether (eg, dimethyl The resin [K4] can be produced by putting a polymerization inhibitor (for example, hydroquinone or the like) and the like into a flask, for example, at 60 to 130 ° C for 1 to 10 hours.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. In this range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be improved. . Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily left, (b) is preferably used as the resin (K4), and (b1-1) is more preferable. .

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

The method of loading, the reaction temperature and time, etc. The manufacturing equipment and the heat generated by the polymerization are appropriately adjusted. Further, similarly to the polymerization conditions, the production method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.

The resin [K5] was obtained in the same manner as in the above-described method for producing the resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be directly used as a solution after the reaction, or a solution which has been concentrated or diluted, or may be taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of the entire structural unit constituting the aforementioned copolymer. Take

Structural unit derived from (b): 5 to 95% by mole

The structural unit derived from (c): preferably 5 to 95 mol%,

Structural unit derived from (b): 10 to 90 mol%

The structural unit derived from (c): 10 to 90 mol% is more preferable.

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

The amount of (a) used for the reaction in the aforementioned copolymer is preferably from 5 to 80 moles relative to (b) 100 moles. Since the reactivity of the cyclic ether is high and the unreacted (b) does not easily remain, the (b1) is preferably used as the (b) used in the resin [K5], and the (b1-1) is more preferable.

Resin [K6] is a tree in which resin carboxylic anhydride is further reacted in resin [K5] fat.

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

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydrogen. Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene An anhydrous (Himic anhydride) or the like. The amount of the carboxylic anhydride to be used is preferably from 0.5 to 1 mol per mol of the amount of (a) used.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, and 3,4-epoxytricycloacrylate [ 5.2.1.0 ^2.6 ]Resin such as mercaptoester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth) acrylate, glycidyl methacrylate / styrene / (meth) acrylic acid copolymer, an acrylic epoxy-3,4-tricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- a resin such as cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloxymethyl propylene oxide/(meth)acrylic acid/styrene copolymer [K2]; Resin such as benzyl (meth) acrylate / (meth) acrylate copolymer, styrene / (meth) acrylate copolymer [K3]; benzyl (meth) acrylate / (meth) acrylate copolymer Addition of a resin of glycidyl (meth) acrylate to a glycidyl (meth) acrylate in a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (A a resin such as a resin obtained by adding a glycidyl (meth)acrylate to a copolymer of acrylic acid [K4]; a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate a resin obtained by reacting a (meth)acrylic acid with a resin such as a resin which reacts with (meth)acrylic acid in a copolymer of tricyclodecyl (meth) acrylate/styrene/glycidyl methacrylate [K5]; further reacting tetrahydrophthalic anhydride with a (meth)acrylic acid-reactive resin in a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate Resin such as resin [K6].

Among them, as the resin (B), the resin [K1], the resin [K2], and the resin [K4] are preferred.

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

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

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

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

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by active radicals and/or an acid generated from heat or a polymerization initiator (D), for example, it can be listed. The compound having a polymerizable ethylenically unsaturated bond or the like is preferably a (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentenol octa (meth) acrylate, trine pentaerythritol hepta (meth) acrylate Ester, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol 九 (meth) acrylate, gin (2-(methyl) propylene methoxyethyl) trimeric isocyanate, ethylene glycol Modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modification Dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like.

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

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

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

<Polymerization initiator (D)>

The polymerization initiator (D) is produced by the action of light or heat A compound which starts the polymerization by a living radical, an acid or the like is not particularly limited, and a known polymerization initiator can be used.

As the polymerization initiator (D), as long as it contains an alkylphenone compound, three A polymerization initiator of at least one of the group consisting of a compound, a decylphosphine oxide compound, an O-antimony compound, and a biimidazole compound, preferably having a polymerization initiation of an O-tellurium compound The agent is better.

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

Hereinafter, * indicates a keying key.

As the O-indole compound, for example, N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy group can be mentioned. 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylindenyl)-9H-indazol-3-yl]ethane- 1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolyl) Benzyloxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylhydrazine -9H-carbazol-3-yl]-3-cyclopentylpropan-1-amine, N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl) )-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE 01, OXE 02 (above, BASF Corporation, N-1919 (made by Adeka)) can be used.

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

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

As the compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[ 4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane - 1-ketone oligomer, α,α-diethoxyethyl benzene, benzyl dimethyl ketal, and the like.

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

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

Examples of the compound of the mercaptophosphine oxide include 2,4,6-trimethylbenzylidenediphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can be used.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, reference: JPH06-75372-A, JPH 06-75373-A, etc.), 2, 2'-double ( 2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis Oxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-double (2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to: JPS48-38403-B, JPS62-174204-A, etc.), 4, An imidazole compound in which a phenyl group at the 4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, refer to JPH07-10913-A, etc.) and the like.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Affinity compound; benzophenone, methyl orthobenzylbenzylate, 4-phenylbenzophenone, 4-benzylindolyl-4'-methyldiphenyl sulfide, 3,3',4 a benzophenone compound such as 4'-tetrakis(tertiary butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Anthraquinone compounds such as hydrazine, camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (especially an amine) to be described later.

As the acid generator, for example, 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, (4-acetoxyphenyl) Dimethyl sulfonium p-toluene sulfonate, benzyl (4-acetoxyphenyl) methyl hydrazine hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate a salt, a diphenylsulfonium p-toluenesulfonate, a diphenylphosphonium hexafluoroantimonate or the like, or a toluenesulfonic acid nitrobenzyl ester or a benzoin tosylate.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the productivity is improved because of the high sensitivity and the tendency to shorten the exposure time.

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound used to promote polymerization of a polymerizable compound which starts polymerization by a polymerization initiator, or a sensitizer. The polymerization starting aid (D1) is usually used together with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxy fluorene compound, a thioxanthone compound, and a carboxylic acid compound.

As the amine compound, there may be mentioned: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzylate, ethyl 4-dimethylaminobenzylate, 4-dimethyl Isoamyl benzyl benzylate, 2-dimethylaminoethyl benzylate, 2-ethylhexyl 4-dimethylaminobenzylate, N,N-dimethyl-p-toluidine, 4 , 4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone; Millerone), 4,4'-bis(diethylamino)benzophenone, 4,4'- The bis(ethylmethylamino)benzophenone or the like is preferably 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

As the alkoxy oxime compound, there may be mentioned: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthioacetic acid. Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

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

<Organic Metal Compound (M)>

The organometallic compound (M) is an organic compound having a maximum molar absorption coefficient ε (hereinafter referred to as "ε _M ") in the visible light region (wavelength 380 nm to 780 nm) smaller than the ε _{M of the} compound (1). Metal compound. The organometallic compound is an organometallic complex or a metal salt of an organic acid which is a ligand having a negative, neutral or positive ligand centered on a metal atom or a metal ion. Among them, those which are dissolved in an organic solvent are preferred.

The ε _{M of the} organometallic compound (M) can be adjusted by diluting 0.1 g of the organometallic compound (M) with ethyl lactate to 0.250 L, and the absorption spectrum of the visible light region is measured by an ultraviolet-visible spectrophotometer. Calculated using the law of Lambert-Beer.

When two or more compounds (1) are contained in the colored curable resin composition of the present invention, the compound (1) having the smallest ε _M is used as a standard.

The organic metal compound (M) is ε _M ratio of the compound (1) ε _M is small, 1000 or less is desirable, is 500 or less is desirable, more desirably 100 or less, it is more desirable is 80 or less, particularly preferably 60 or less. When ε _{M is} in the above range, the brightness of the color filter tends to be high, which is preferable. Further, the present invention is colored curable resin composition containing at least one compound (1), the organometallic compound (M) is ε _M ratio of the compound (1) of the minimum ε _M ε _M small. Further, according to the present invention, the colored curable resin composition contains two or more organometallic compound (M), an organometallic compound of the maximum ε _M (M) of ε _M ratio of the compound (1) ε _M is small.

As the metal atom constituting the organometallic compound (M) or the metal of the metal ion, a typical metal and a transition metal can be cited.

As a typical metal, for example, a group 1 element (alkali metal) of a periodic table, a group 2 element (alkaline earth metal), a group 12 element (zinc group), a group 13 element (boron group), An atom of a metal element contained in a Group 14 element (carbon group) or a Group 15 element (nitrogen group).

Specifically, bismuth (Be), magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), strontium (Rb), strontium (Sr), cadmium (Cd), Indium (In), tin (Sn), strontium (Cs), barium (Ba), mercury (Hg), strontium (Tl), lead (Pb), bismuth (Bi), strontium (Fr), radium (Ra), etc. atom.

Among them, magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), antimony (Rb), antimony (Sr), indium (In), antimony (Cs) and antimony ( Ba) is preferable, and atoms of aluminum (Al), zinc (Zn), indium (In), and barium (Ba) are preferred, and aluminum (Al), zinc (Zn), and indium (In) are preferred. The child is better.

Examples of the transition metal include, for example, a Group 3 element (钪 group) of a periodic table, a Group 4 element (Titanium group), a Group 5 element (Vanadium group), a Group 6 element (Chromium group), and The atom of the metal element contained in the group 7 element (manganese group), the group 4 to group 10 element (iron group) of the fourth cycle, and the group 8 to 10 element (platinum group) of the fifth to sixth cycles.

Specifically, cerium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) , yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), niobium (Tc), yttrium (Ru), rhenium (Rh), palladium (Pd), silver (Ag), lanthanum (La) , Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb , Er (Er), Tm (Tm), Yb, Lu, Hf, Ta, T (W), T (Re), O (Os), O (Ir) , platinum (Pt), gold (Au) and the like.

Among them, bismuth (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), etc. A series (ie, the fourth cycle) is preferred, and cobalt (Co) and nickel (Ni) are more preferred.

The ligand in the case where the organometallic compound (M) is an organometallic complex is not particularly limited, and may be a monodentate ligand or a polydentate ligand. The molecular weight of one of the above ligands is preferably 20 or more and 500 or less.

As the ligand, for example, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, benzonitrile, oxalato, acetato, ethanolato, 1-butanethiol may be mentioned. 1-butanethiolato, thiophenolate, 2,2'-thiobis(4-trioctyl) phenate, 2,4-pentanedionato, 2 , 2,6,6-tetramethyl-3,5-heptanedione, trifluoro-2,4-pentanedione, hexafluoro-2,4-pentanedione, ethyl Indoleacetate, dimethylamine, diethylamine, tetraethylammonium, piperidine, N-methylaniline, pyridine, 2-phenylpyridine, Ethylenediamine, N,N,N',N'-tetramethylethylenediamine, 1,2-diaminocyclohexane, 2,2'-bipyridine, 1,10-morpholine, Ethylene Aminotetraacetate, 1,4,8,11-tetraazacyclotetradecane, gin(2-aminoethyl)amine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, dimethyl Phenylphosphine, triphenylphosphine, diphenylphosphine, tricyclohexylphosphine, cyclopentadiene, pentamethylcyclopentadiene, cyclooctene, 1,5-cyclooctadiene, bicyclo [2.2.1 G-8,5-diene, benzene, naphthalene, allyl and the like.

As the above-mentioned ligand, it is preferred that the ligand does not contain an aromatic ring, and an acetate group, an acetoacetone group, a hexafluoroacetone group, a diethyldithioamine group. Carbamate and di-n-butyldithiocarbamate are preferred.

The organometallic complex may have at least one ligand derived from an organic compound, and may have a ligand other than the above. As such a ligand, for example, a fluorine group, a chlorine group, a bromine group, an iodine group, a hydroxo group, a hydrate, a pendant oxy group, a peroxy group (peroxo), a carbonyl group, and a carbonic acid group are exemplified. A carbonato, a cyano group, an amine, a sulfato group, a nitro group, a nitrito group, a phosphato group, a thiocyanato group, an isothiocyanate group or the like.

When the organometallic compound (M) is a metal salt of an organic acid, the molecular weight of one of the organic acids is preferably 20 or more and 500 or less.

As the organic acid, for example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, N,N-bis(2-hydroxyethyl) can be cited. Dithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, N,N-dibenzyldithiocarbamic acid, diethyldithiophosphoric acid, diisopropyl Dithiophosphoric acid, 2-hydroxypropionic acid, stearic acid, tartaric acid, oxalic acid, and the like.

As the organometallic compound (M), for example, ginseng (2- Hydroxypropionic acid aluminum, bis(2-ethylhexanoate)hydroxy aluminum, bis(2-thiopyridine-N-oxide) zinc, bis(2-hydroxypropionic acid) zinc, bis(2-hydroxypropane) Acid, bismuth (stearic acid) hydrazine, bismuth tartrate, bismuth oxalate, a compound described in JP2011-118365-A and JP2004-295116-A.

Preferably, the organometallic compound containing at least one group selected from the group consisting of -C(=O)- and -C(=S)- is preferably selected from the group consisting of the compound represented by the formula (F1). A compound of the formula (F2) and at least one compound of the group of the hydrates are preferred. When the organometallic compound (M) is a compound such as this, it tends to be improved in solubility in an organic solvent.

[In the formula (F1), W ¹ , W ² , M ¹ and x each have the same meaning as described above].

[In the formula (F2), W ³ , W ⁴ , M ² and y each have the same meaning as described above].

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in W ¹ and W ² include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, and a tertiary butyl group. Base, pentyl, hexyl and the like. Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which a hydrogen atom is substituted with a hydroxyl group include, for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, and a 2-hydroxy group. Propyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4 - Hydroxybutyl and the like. Among them, an ethyl group, a butyl group and a 2-hydroxyethyl group are preferred.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in W ¹ and W ² include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a propylphenyl group or a butylphenyl group; and a benzyl group; An arylalkyl group or the like. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in which a hydrogen atom is substituted with a hydroxyl group include a hydroxyphenyl group and a hydroxymethylphenyl group. Among them, a phenyl group and a benzyl group are desirable.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in W ³ and W ⁴ include the same groups as those related to W ¹ and W ² .

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which a hydrogen atom is substituted by a halogen atom may, for example, be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a chloromethyl group or a chlorine group. Ethyl, dichloroethyl, chloropropyl, chlorobutyl, bromobutyl, iodobutyl, and the like. Among them, a methyl group, a tertiary butyl group or a trifluoromethyl group is preferred.

As the compound represented by the formula (F1), for example, bis[N,N-bis(2-hydroxyethyl)dithiocarbamic acid]zinc, bis(N,N-dimethyldithio) may be mentioned. Zinc amide, zinc bis(N,N-diethyldithiocarbamic acid), zinc bis(N,N-dibutyldithiocarbamic acid), bis(N-ethyl-N -Phenyldithiocarbamic acid)zinc, bis(N,N-dibenzyldithiocarbamic acid)zinc or the like.

Examples of the compound represented by the formula (F2) include ginseng (2,4-pentanedione) aluminum (III) and ginseng (trifluoro-2,4-pentanedione) aluminum (III). Reference (2,4-pentanedione) indium (III), ginseng (2,2,6,6-tetramethyl-3,5-heptanedione) indium (III), ginseng (trifluoro-2 , 4-pentanedione) indium (III), bis(2,4-pentanedione) anthracene, bis(hexafluoro-2,4-pentanedione) anthracene, double (2,2,6,6-tetramethyl-3,5-heptanedione) ruthenium, bis(2,4-pentanedione) nickel(II), bis(N,N-dibutyl Thiocarbamic acid) nickel (II), bis(2,4-pentanedione)cobalt (II), bis(hexafluoro-2,4-pentanedione)cobalt (II), and the like.

As the organometallic compound (M), it is bis(2,4-pentanedione)nickel(II), bis(2,4-pentanedione)cobalt (II), and ginseng (2,4-pentyl) Alkanedione) Indium (III), ginseng (2,4-pentanedione) aluminum (III), bis(hexafluoro-2,4-pentanedione)cobalt (II), bis(N,N- Zinc dibutyldithiocarbamate, zinc bis[N,N-bis(2-hydroxyethyl)dithiocarbamic acid], and such hydrates are preferred. When such a compound is present, a high-contrast color filter can be obtained, and the solubility of the compound in an organic solvent tends to be improved, which is preferable because a foreign color is less likely to generate a color filter.

The content of the organometallic compound (M) is preferably 0.1 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C), and is 0.5 parts by mass or more and 15 parts by mass or less. The following is preferable, and it is more preferably 1 part by mass or more and 10 parts by mass or less. When the content of the organometallic compound (M) is within the above range, a color filter having a high brightness and a high contrast can be obtained.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and -O- in the molecule), an ether solvent (a solvent containing -O- in the molecule, and containing no -COO-), an ether ester solvent ( a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule, and a solvent containing no -COO-), an alcohol solvent (containing OH in the molecule, and containing no -O-, -CO- and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and Ethylene 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-butyl Alcohol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzo Ether, phenethyl ether (Phenetole), methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropyl. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropane Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2 Ethyl ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl 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.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 can be mentioned. -pentanone, cyclopentanone, Cyclohexanone, isophorone, and the like.

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

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

Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above-mentioned solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 180 ° C or less is preferred. As the solvent (E), it is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred as propylene glycol monomethyl ether acetate Propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are preferred.

The content of the solvent (E) is desirably 70 to 95% by mass, and more desirably 75 to 92% by mass based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is desirably 5 to 30% by mass, more desirably 8 to 25% by mass.

When the content of the solvent (E) is within the above range, the flatness at the time of application is further improved, and when the color filter is formed, the display characteristics tend to be improved because there is no doubt that the color density is insufficient.

<Interacting Agent (F)>

Examples of the surfactant (F) include a ruthenium-based surfactant, a fluorine-based surfactant, and a ruthenium-based surfactant having a fluorine atom. Such can It has a polymerizable group in the side chain.

Examples of the oxime-based surfactant include a surfactant having a decane bond in the molecule. Specifically, Toray silicone DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (trade name; Toray‧Dow Corning (share) system), KP321, KP322, KP323, KP324 KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF 4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, FLUORAD (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), MEGAFAC (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and R30, same as RS-718-K (DIC), EF-TOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronic Co., Ltd.), Surflon (registered trademark) S381 And S382, the same SC101, the same SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Research Institute Co., Ltd.).

Examples of the oxime-based surfactant having a fluorine atom include a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, BL30, F475, F477, and F443 (DIC).

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

The content of the surfactant (F) relative to the composition of the colored curable resin The total amount of the particles is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably 0.01% by mass or more and 0.05% by mass or less. Further, the content does not include the content of the aforementioned pigment dispersant. When the content of the surfactant (F) is within the above range, the flatness of the coating film can be further improved.

<Other ingredients>

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

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be prepared, for example, by mixing the compound (1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the organometallic compound (M), and It is prepared by using the pigment (A1), the dye (A2), the polymerization initiation aid (D1), the surfactant (F), the solvent (E), and other components to be used.

In the case of containing the pigment (A1), it is preferred to mix the pigment (A1) with a part or all of the solvent (E) in advance, and to disperse it by using a bead mill or the like until the average particle diameter of the pigment becomes 0.2 μm or less. Around. At this time, a part or all of the resin (B) and the aforementioned pigment dispersant may be blended as needed. In the obtained pigment dispersion liquid, the coloring resin composition for the purpose can be prepared by mixing the remaining components and the like so as to have a predetermined concentration.

The dye (A2) in the case where the compound (1) and the dye (A2) are contained may be previously dissolved in a part or all of the solvent (E) to prepare a solution in advance. Preferably, the solution is filtered using a filter having a pore diameter of about 0.01 to 1 μm.

Preferably, the mixed color-curable resin composition is filtered using a filter having a pore diameter of about 0.01 to 10 μm.

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

The method of producing the colored pattern of the color filter of the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. In the lithography process, the colored curable resin composition of the present invention is applied onto a substrate, and volatile components such as a solvent are removed and dried to form a composition layer. Next, a method of exposing and developing the composition layer through a photomask. After development, a colored pattern can be formed by heating as needed. In the method of forming the colored pattern, the colored coating film of the cured product of the composition layer can be formed by using no mask and/or no image formation during exposure. The obtained coloring pattern and coloring coating film can be regarded as a color filter.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more desirably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda-lime glass coated with cerium oxide, or polycarbonate, polymethyl methacrylate or polyparaphenyl may be used. A resin plate such as diethyl formate or ruthenium is formed with an aluminum, silver, silver/copper/palladium alloy film or the like on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

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

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

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

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

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

The temperature at the time of heat drying is preferably 30 to 120 ° C, 50 to 110 ° C is more preferred. Further, as the heating time, it is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

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

Next, the composition layer is irradiated with ultraviolet rays through a photomask (not shown), and the unnecessary portion (unexposed portion) is selectively removed by the developing liquid to obtain a film which reaches the polycrystalline ruthenium film 22c. The pixel-formed composition layer of the contact hole 201 in the drain region is washed with water.

By the development, the unexposed portion of the composition layer is dissolved in the developing liquid to be removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of these basic compounds is desirably 0.01 to 10% by mass, more desirably 0.03 to 5% by mass. Further, the developing solution may contain a surfactant.

As the developing method, any one of a puddle method, a dipping method, and a spray method can be used. Furthermore, the substrate can be tilted at an arbitrary angle during development.

Thereafter, in order to reflow and/or harden the composition layer on which the contact hole 201 is formed, for example, in the range of 150 to 250 ° C, it is desirable to heat the temperature in the range of 160 to 235 ° C. It is preferably from 1 to 120 minutes and heated for 10 to 60 minutes. The colored curable resin composition layer 23A is formed. This colored curable resin composition layer 23A corresponds to the color filter of the present invention.

By repeating this operation, a coloring-curable resin composition layer 23A is formed from the red colored curable resin composition, the green colored curable resin composition, and the blue colored curable resin composition, respectively, and is formed for each pixel column. Color filter including red color filter 23a, green color filter 23b, and blue color filter 23c Layer 23 (see Fig. 2). The region between the respective filters of the color filter layer 23 serves as a mixed region of adjacent colors, and since this region is a light-blocking region opposed to the signal line 27, it is particularly unobstructed in quality. Moreover, the area between the filters may not be colored.

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

Next, on the photosensitive resin film 29, a transparent conductive material such as ITO (Indium-Tin Oxide: oxide mixed film of indium and tin) is formed by, for example, sputtering, and the ITO film is etched by photolithography. The pattern is patterned by technique and etching to form a transparent pixel electrode 24 (see Fig. 3). Further, the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) in accordance with the device to be fabricated. Thereafter, after the alignment film is formed by a known method, the liquid crystal display device can be manufactured by adhering the driving substrate to the counter substrate.

According to the colored curable resin composition of the present invention, a color filter excellent in brightness and contrast can be produced. The color filter can be used as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state imaging device.

Example

Next, the present invention will be further specifically described by way of examples. In the example, the content and the % and the amount of use are indicated, and the quality is not based on the limitation.

In the following synthesis examples, the compounds were identified by mass analysis (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

[Synthesis Example 1]

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

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

[Synthesis Example 2]

The compound of the formula (1-6) was obtained in the same manner as in the synthesis of the compound except that N-isopropyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound of formula (1-6) (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4 Exact Mass: 658.3

[Synthesis Example 3]

In a flask equipped with a condenser and a stirring device, a mixture of a compound represented by the formula (A2-1a) and a compound of the formula (A2-1b) (trade name: Chugai Aminol Fast Pink R; manufactured by Sino-foreign Chemical Co., Ltd.) was charged, and chloroform was added. 150 parts and 8.9 parts of N,N-dimethylformamide were added to the mixture at a temperature of 20 ° C or lower while stirring, and 10.9 parts of sulfite chloride was added dropwise thereto. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was carried out for 5 hours while maintaining the same temperature, followed by cooling to 20 ° C. The reaction solution after cooling was kept at 20 ° C or lower while stirring, and a mixed liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Next, after the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals are filtered, washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dye (A2-1) (a compound of the formula (A2-1-1) to the formula (A2-1-8)). The mixture) 11.3 parts.

[Synthesis Example 4]

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was flowed into a nitrogen atmosphere at 0.02 L/min, and 305 parts of ethyl lactate was placed, and the mixture was heated to 70 ° C while stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1), The mixture was dissolved and prepared by dissolving 240 parts of the molar ratio of 50:50 and 140 parts of ethyl lactate. The solution was taken for 4 hours using a dropping funnel and dropped into a flask kept at 70 °C.

On the other hand, a solution of 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 225 parts of ethyl lactate was used for 4 hours using another dropping funnel. Into the flask. After completion of the dropwise addition of the solution of the polymerization initiator, the temperature was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3 × 10 ⁴ , a molecular weight distribution of 2.5, a solid content of 35.4%, and a solid content conversion. The acid value was a resin B1 solution of 103 mg KOH/g. The resin B1 has the structural unit shown below.

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

Device; K2479 (Shimadzu Corporation (stock) system)

Pipe column; Shimadzu Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 mL/min

Detector; RI

Standard material for calibration; TSK Standard Polystyrene F-40, F-4, F-288, A-2500, A-500 (made by Tosoh)

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

Examples 1 to 6 and Comparative Example 1

Each component was mixed so as to have the composition shown in Table 1, and the colored curable resin composition was obtained.

¹⁾ "A1-1" is a premixed propylene glycol monomethyl ether acetate in an amount of the mixed acrylic pigment dispersant and "E-1" in column ³⁾ .

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

In Table 1, each component represents the following.

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

(A) Colorant: 1-6: a compound represented by the formula (1-6)

(A) Colorant: A1-1: C.I. Pigment Blue 15:6 (pigment)

(A) Colorant: A2-1: Dye (A2-1)

(B) Resin: B-1: Resin B1 solution

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

(D) Polymerization initiator: N-benzyloxyl-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation )

(M) organometallic compound: M-1: bis(dibutyldithiocarbamic acid) zinc

(M) organometallic compound: M-2: bis[bis(2-hydroxyethyl)dithiocarbamic acid]zinc

(M) organometallic compound: M-3: ginseng (2,4-pentanedione) indium

(M) organometallic compound: M-4: ginseng (2,4-pentanedione) aluminum

(M) organometallic compound: M-5: bis(2,4-pentanedione)nickel(II)

(M) organometallic compound: M-6: bis(2,4-pentanedione)cobalt (II)

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

(E) Solvent: E-2: Propylene glycol monomethyl ether

(E) Solvent: E-3: ethyl lactate

(F) Surfactant: Fluorine-based surfactant (MEGAFAC (registered trademark) F554; DIC (share) system)

[Calculation of Mohr Absorption Coefficient]

In the measuring flask, the sample was weighed in an amount of 0.1 g, and then diluted with ethyl lactate to become 0.250 L. For this solution, an absorption spectrum was measured by an ultraviolet-visible spectrophotometer (V-650 DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), and the visible light region was calculated using the Law of Lambert-Beer ( The maximum value [ε _M ] of the molar absorption coefficient ε in 380 nm to 780 nm. The results are shown in Table 2.

[Formation of coloring pattern]

The colored curable composition was applied by a spin coating method on a glass substrate (EAGLE XG; manufactured by Corning Incorporated) of 2 square meters, and then prebaked at 100 ° C for 3 minutes to obtain a colored composition layer. After cooling, the glass substrate on which the colored composition layer was formed was placed at a distance of 100 μm from the quartz glass mask, and exposed to an exposure apparatus (TME-150RSK; TOPCON) to 150 mJ/cm ² in an atmosphere. Exposure (365 nm reference) light irradiation. As the reticle, a pattern in which a line and space of 100 μm is formed is used. After the light irradiation, the coating film was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 28 ° C for development, and after being washed with water, in an oven. After baking at 220 ° C for 20 minutes, a colored pattern was obtained.

[Measurement of film thickness]

The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 3.

[Color Evaluation]

The coloring pattern on the obtained glass substrate was measured by using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the chromaticity of the C light source was used to measure the xy chromaticity in the XYZ color system of CIE. Coordinate (x, y) and tristimulus value Y. A large value of Y indicates a high brightness. The results are shown in Table 3.

[Comparative evaluation]

A coloring coating film was formed on the glass substrate in the same manner as the formation of the coloring pattern except for exposure under the use of a mask. For the obtained coating film, a comparative color measuring machine (CT-1: Maker, BM-5A, light source; F-10) was used, and the blank value was measured as 30,000. The glass substrate on which the colored coating film was formed was used as a measurement sample by a polarizing film (POLAX-38S; manufactured by LUCEO Co., Ltd.). The results are shown in Table 3.

As a result of the examples, it was confirmed that the coloring pattern obtained by the colored curable resin composition of the present invention is blue having high brightness, and the contrast is also high. Thus, the pattern obtained by the colored curable resin composition of the present invention is useful as a high-density color filter. Further, it is understood that the display device including the color filter has excellent display characteristics.

According to the colored curable resin composition of the present invention, a high-density color filter can be formed.

21‧‧‧ glass substrate

22‧‧‧TFT (switching element)

22a‧‧‧Gate electrode

22b‧‧‧gate insulating film

22c‧‧‧Multi-crystalline enamel film

22d‧‧‧Protective film

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

27‧‧‧ signal line

201‧‧‧connection hole

Claims (5)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an organometallic compound, wherein the colorant contains a compound represented by the formula (1), and a molybdenum in the visible region of the organometallic compound The maximum absorption coefficient is smaller than the maximum value of the Mohr absorption coefficient in the visible light region of the compound represented by the formula (1). In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent, and R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and hydrogen contained in the saturated hydrocarbon group The atom may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. , -CH ₂ - contained in the above saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ -, and R ¹ and R ³ may form a ring containing a nitrogen atom together with a nitrogen atom, R ² and R ⁴ A ring containing a nitrogen atom may be formed together with a nitrogen atom, and R ⁵ represents -OH, -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ , R ⁶ and R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 4, and m is 2 or more, The plurality of R ⁵ may be the same or different, and R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and Z ⁺ represents ⁺ N(R ¹¹ ). _4, Na ⁺ or K ^+, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a carbon number of 1 20 monovalent saturated hydrocarbon group, R ⁹ and R ¹⁰ may be bonded to each other to form 3 to 10 of nitrogen-containing heterocyclic ring together with the nitrogen atom, R ¹¹ each independently represent a monovalent hydrogen atom, a C 1-20 saturated The hydrocarbon group is also an aralkyl group having a carbon number of 7 to 10. The colored curable resin composition according to claim 1, wherein the organometallic compound is selected from the group consisting of a compound represented by the formula (F1), a compound represented by the formula (F2), and a hydrate of the compounds. At least one of the groups, In the formula (F1), W ¹ and W ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group The hydrogen atom may be substituted by a hydroxyl group, M ¹ represents a metal atom, x represents an integer of 1 to 3, and when x is 2 or more, a plurality of W ¹ and W ² may be the same or different from each other. In the formula (F2), W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted by a halogen atom, M ² represents a metal atom, and y represents An integer of 1 to 3, when y is 2 or more, a plurality of W ³ and W ⁴ may be identical to each other or may be different. The colored curable resin composition according to claim 1 or 2, wherein the colorant further contains a pigment. A color filter formed by the colored curable resin composition according to any one of claims 1 to 3. A display device comprising the color filter of claim 4 of the patent application.