CN113376959A

CN113376959A - Colored curable resin composition

Info

Publication number: CN113376959A
Application number: CN202110244088.1A
Authority: CN
Inventors: 土谷崇夫
Original assignee: Sumitomo Chemical Co Ltd; Dongwoo Fine Chem Co Ltd; Sumika Technology Co Ltd
Current assignee: Sumitomo Chemical Co Ltd; Dongwoo Fine Chem Co Ltd; Sumika Technology Co Ltd
Priority date: 2020-03-10
Filing date: 2021-03-05
Publication date: 2021-09-10
Also published as: TW202140683A; JP2021143326A; KR20210114872A

Abstract

The present invention addresses the problem of providing a colored curable resin composition that can suppress a decrease in maximum absorption in the visible light region even in a film formation step such as an exposure step and a post-baking step. The colored curable resin composition contains a colorant, a resin, a polymerizable compound, a polymerization initiator and an antioxidant, wherein the colorant contains a squaric acid having a maximum absorption in the visible light region

Description

Colored curable resin composition

Technical Field

The present invention relates to a colored curable resin composition.

Background

In liquid crystal display device, electroluminescent display device, plasma display, etcColor filters used in display devices and solid-state imaging devices such as CCD and CMOS sensors are made of colored curable resin compositions. As a colorant used in such a colored curable resin composition, a squaric acid is known

Dyes (patent documents 1,2, etc.).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-86379

Patent document 2: japanese patent laid-open publication No. 2015-86380

Disclosure of Invention

However, for the presence of squaric acid

In the above-mentioned colored curable resin composition of a dye, if post-baking is performed after exposure, the maximum absorption in the visible light region may be reduced. Accordingly, an object of the present invention is to provide a colored curable resin composition which can suppress a decrease in the maximum absorption in the visible light region even in a film forming step such as an exposure step and a post-baking step.

The gist of the present invention is as follows.

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and an antioxidant,

the colorant contains squaric acid having maximum absorption in visible light region

The dye is a mixture of a dye and a water,

the antioxidant contains a phenolic antioxidant.

[2] The colored curable resin composition according to [1], wherein the phenolic antioxidant is a compound having no vinyl group or no ethylene-1, 1-diyl group.

[3] The colored curable resin composition according to [1] or [2], wherein the phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one carbon atom in 2 ortho positions to the phenolic hydroxyl group, and a hydrogen atom or an alkyl group is bonded to the other carbon atom.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one carbon atom in 2 ortho positions to the phenolic hydroxyl group, and a hydrogen atom, a methyl group or a primary alkyl group is bonded to the other carbon atom.

[5]According to [1]～[4]The colored curable resin composition according to any one of the preceding claims, wherein the antioxidant and the squaric acid are present in the composition

Mass ratio of dye (antioxidant/squaric acid)

Dye) is 0.8 or more.

[6]According to [1]～[5]The colored curable resin composition according to any one of the preceding claims, wherein the squaraine

The dye is a compound represented by formula (AI).

[ in the formula (AI) ],

R¹～R⁴each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The methylene group constituting the 1-valent saturated hydrocarbon group may be substituted with-O-or-S-.

R⁵～R⁸Each independently represents a hydrogen atom or a hydroxyl group.

Ar¹And Ar²Each independently represents a group represented by formula (i).

[ in the formula (i),

R¹²represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxyl group or a carboxyl group, and m represents an integer of 0 to 5. The methylene group constituting the 1-valent saturated hydrocarbon group may be substituted with-O-or-S-. When m is 2 or more, plural R¹²Each may be the same or different. Denotes the bonding site to the nitrogen atom.]

R⁹And R¹⁰Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by the formula (i). The methylene group constituting the 1-valent saturated hydrocarbon group may be substituted with-O-or-S-.]

[7]According to [1]～[6]The colored curable resin composition according to any one of the preceding claims, wherein the squaraine

The dye is a compound represented by formula (AII).

[ in the formula (AII),

R⁵～R⁸Each independently represents a hydrogen atom or a hydroxyl group.

Ar¹And Ar²Each independently represents a group represented by formula (i).

[ in the formula (i),

R¹²to representA 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxyl group or a carboxyl group, and m represents an integer of 0 to 5. The methylene group constituting the 1-valent saturated hydrocarbon group may be substituted with-O-or-S-. When m is 2 or more, plural R¹²Each may be the same or different. Denotes the bonding site to the nitrogen atom.]

R¹³And R¹⁴Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxyl group, and a methylene group constituting the 1-valent saturated hydrocarbon group may be substituted by-O-or-S-.]

[8] A color filter comprising the colored curable resin composition according to any one of [1] to [7 ].

[9] A display device comprising the color filter of [8 ].

According to the present invention, a colored curable resin composition that can suppress a decrease in the maximum absorption in the visible light region even in a film forming step can be provided.

Detailed Description

< colored curable resin composition >

The colored curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as a colorant (a)), a resin (hereinafter, sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)), a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)), and an antioxidant (hereinafter, sometimes referred to as an antioxidant (E)), and the colorant (a) contains a squaric acid having a maximum absorption in the visible light region

The dye, wherein the antioxidant (E) contains a phenol antioxidant. In the present specification, the compounds exemplified as the respective components may be used alone or in combination of a plurality of compounds unless otherwise specified.

< colorant (A) >)

The colorant (A) contains a squaric acid having a maximum absorption in the visible light region

A dye. The visible light region referred to herein is a wavelength region of 380nm to 780 nm. The above squaric acid

The dye is preferably a compound having an absorption maximum at 390nm or more (preferably 400nm or more) and less than 700nm (preferably 650nm or less).

As the above-mentioned squaric acid

The dye is not particularly limited as long as it is a compound having a maximum absorption in the visible light region, and a known squarylium acid can be used

The dye is preferably a compound represented by the formula (AI).

[ in the formula (AI) ],

R⁵～R⁸Each independently represents a hydrogen atom or a hydroxyl group.

Ar¹And Ar²Each independently represents a group represented by formula (i).

[ in the formula (i),

R¹²represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxyl group or a carboxyl group,m represents an integer of 0 to 5. The methylene group constituting the 1-valent saturated hydrocarbon group may be substituted with-O-or-S-. When m is 2 or more, plural R¹²Each may be the same or different. Denotes the bonding site to the nitrogen atom.]

As R¹～R⁴Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R¹～R⁴、R⁹、R¹⁰And R¹²Examples of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl groups; a branched alkyl group having 3 to 20 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and adamantyl.

Examples of the substituent for the saturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom; a hydroxyl group; a carboxyl group; -NR^aR^b(R^aAnd R^bEach independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; examples of the substituted 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms include a group represented by the following formula. In the following formulae, a represents a bonding site.

Examples of the group in which the methylene group constituting the saturated hydrocarbon group is substituted by-O-or-S-, include groups represented by the following formulae. In the following formulae, a represents a bonding site.

As R¹²Examples of the 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms in the (a) include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

Examples of the substituent for the unsaturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom; a hydroxyl group; a carboxyl group; -NR^cR^d(R^cAnd R^dEach independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

As R¹～R⁴The alkyl group is preferably a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a hydroxyl group or a methyl group, and still more preferably a hydrogen atom.

As R⁵～R⁸Preferably at least one is hydroxy, more preferably R⁵And R⁶At least one of them is hydroxyl, R⁷And R⁸At least one of them is a hydroxyl group, more preferably R⁵And R⁶Wherein either one of them is a hydroxyl group or R⁷And R⁸One of them is a hydroxyl group.

As R⁹And R¹⁰The alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms which may have a substituent or a branched alkyl group having 3 to 20 carbon atoms which may have a substituent, more preferably a linear alkyl group having 1 to 10 carbon atoms which may have a substituent or a branched alkyl group having 3 to 10 carbon atoms which may have a substituent, and still more preferably a linear alkyl group having 1 to 5 carbon atoms which has a hydroxyl group at the terminal, a linear alkyl group having 1 to 5 carbon atoms which has a carboxyl group at the terminal, or a branched alkyl group having 3 to 10 carbon atoms.

As R¹²The alkyl group is preferably a substituted or unsubstituted 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms.

m is preferably 1 to 5, more preferably 1 to 3.

As Ar¹And Ar²Preferably, the group represented by the formula (ii).

[ in the formula (ii),

R¹⁵represents a hydroxyl group, a carboxyl group, or a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxyl group, and p represents an integer of 0 to 5. The methylene group constituting the 1-valent saturated hydrocarbon group may be substituted with-O-or-S-. When p is 2 or more, plural R¹⁵Each may be the same or different.

R¹⁶Represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and q represents an integer of 0 to 5. Wherein p + q represents an integer of 0 to 5. The methylene group constituting the 1-valent saturated hydrocarbon group may be substituted with-O-or-S-. When q is 2 or more, plural R¹⁶Each may be the same or different.

Denotes the bonding site to the nitrogen atom. ]

As R¹⁵Examples of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms include the groups exemplified above for the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms. Among these, a linear alkyl group having 1 to 20 carbon atoms is preferable, a linear alkyl group having 1 to 10 carbon atoms is more preferable, and a linear alkyl group having 1 to 5 carbon atoms is even more preferable.

The hydroxyl group or carboxyl group of a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably bonded to the molecular chain end of the saturated hydrocarbon group.

Examples of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxyl group include groups represented by the following formulae. In the following formulae, a represents a bonding site.

As R¹⁵Preferably, the hydrocarbon group is a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms and a hydroxyl group. In addition, form R¹⁵At least one of methylene groups of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably substituted by-O-. As a constituent R¹⁵Examples of the group in which at least one of methylene groups of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms is substituted with-O-include groups represented by the following formulae. In the following formulae, a represents a bonding site.

As R¹⁶The 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and the 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent are exemplified by the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and the 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent described above. Among these, a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferable, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable, a linear alkyl group having 1 to 3 carbon atoms is further preferable, and a methyl group is particularly preferable.

p is preferably an integer of 0 to 3, more preferably an integer of 0 to 1, and particularly preferably 1.

q is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.

Among the compounds represented by the formula (AI), the compounds represented by the formula (AII) are more preferable. By reacting the above squaric acid

The dye is a compound represented by the formula (AII), and can further inhibit decrease of maximum absorption in a film forming process and color change in the film forming processAnd (4) transforming.

[ in the formula (AII),

R¹～R⁸、Ar¹and Ar²As described above.

As R¹³And R¹⁴Examples of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms include the groups exemplified above for the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms. Among these, a linear alkyl group having 1 to 20 carbon atoms is preferable, a linear alkyl group having 1 to 10 carbon atoms is more preferable, and a linear alkyl group having 1 to 5 carbon atoms is even more preferable.

R in the formula (AII)¹～R⁸、Ar¹And Ar²The preferred embodiment of (c) is the same as described above.

Examples of the compound represented by the formula (AI) include compounds represented by the formulae (AI-1) to (AI-60) shown in tables 1 to 2, and among them, compounds represented by the formulae (AI-1) to (AI-20) are preferable from the viewpoint of availability of raw materials.

The compound represented by the formula (AI) is more preferably a compound represented by the formula (AI-1) to the formula (AI-5), the formula (AI-11) to the formula (AI-20),

more preferably represented by the formulae (AI-11) to (AI-20),

more preferably represented by the formulae (AI-11) to (AI-15).

[ Table 1]

R¹～R⁴

R⁵

R⁶

R⁷

R⁸

R⁹

R¹⁰

Ar¹

Ar²

(AI-1)

H

OH

H

x-1

y-1

(AI-2)

H

OH

H

x-1

y-2

(AI-3)

H

OH

H

x-1

y-3

(AI-4)

H

OH

H

x-1

y-4

(AI-5)

H

OH

H

x-1

y-5

(AI-6)

H

OH

H

x-2

y-1

(AI-7)

H

OH

H

x-2

y-2

(AI-8)

H

OH

H

x-2

y-3

(AI-9)

H

OH

H

x-2

y-4

(AI-10)

H

OH

H

x-2

y-5

(AI-11)

H

OH

H

x-3

y-1

(AI-12)

H

OH

H

x-3

y-2

(AI-13)

H

OH

H

x-3

y-3

(AI-14)

H

OH

H

x-3

y-4

(AI-15)

H

OH

H

x-3

y-5

(AI-16)

H

OH

H

x-4

y-1

(AI-17)

H

OH

H

x-4

y-2

(AI-18)

H

OH

H

x-4

y-3

(AI-19)

H

OH

H

x-4

y-4

(AI-20)

H

OH

H

x-4

y-5

(AI-21)

H

x-1

y-1

(AI-22)

H

x-1

y-2

(AI-23)

H

x-1

y-3

(AI-24)

H

x-1

y-4

(AI-25)

H

x-1

y-5

(AI-26)

H

x-2

y-1

(AI-27)

H

x-2

y-2

(AI-28)

H

x-2

y-3

(AI-29)

H

x-2

y-4

(AI-30)

H

x-2

y-5

[ Table 2]

R¹～R⁴

R⁵

R⁶

R⁷

R⁸

R⁹

R¹⁰

Ar¹

Ar²

(AI-31)

H

x-3

y-1

(AI-32)

H

x-3

y-2

(AI-33)

H

x-3

y-3

(AI-34)

H

x-3

y-4

(AI-35)

H

x-3

y-5

(AI-36)

H

x-4

y-1

(AI-37)

H

x-4

y-2

(AI-38)

H

x-4

y-3

(AI-39)

H

x-4

y-4

(AI-40)

H

x-4

y-5

(AI-41)

H

OH

x-1

y-1

(AI-42)

H

OH

x-1

y-2

(AI-43)

H

OH

x-1

y-3

(AI-44)

H

OH

x-1

y-4

(AI-45)

H

OH

x-1

y-5

(AI-46)

H

OH

x-2

y-1

(AI-47)

H

OH

x-2

y-2

(AI-48)

H

OH

x-2

y-3

(AI-49)

H

OH

x-2

y-4

(AI-50)

H

OH

x-2

y-5

(AI-51)

H

OH

x-3

y-1

(AI-52)

H

OH

x-3

y-2

(AI-53)

H

OH

x-3

y-3

(AI-54)

H

OH

x-3

y-4

(AI-55)

H

OH

x-3

y-5

(AI-56)

H

OH

x-4

y-1

(AI-57)

H

OH

x-4

y-2

(AI-58)

H

OH

x-4

y-3

(AI-59)

H

OH

x-4

y-4

(AI-60)

H

OH

x-4

y-5

In tables 1 to 2, x-1 to x-4 represent groups represented by the following formulae ([ lambda ] denotes a bonding site).

In tables 1 to 2, y-1 to y-5 represent groups represented by the following formulae ([ beta ] denotes a bonding site).

The compound represented by the formula (AI) can be produced, for example, by reacting a compound represented by the formula (pt1), a compound represented by the formula (pt2) and a compound represented by the formula (pt 3). In this reaction, the total amount of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is preferably 1.5 to 2.5mol based on 1mol of the compound represented by the formula (pt 3).

In the formula, R¹～R¹⁰、Ar¹And Ar²Each means the same as described above.

The reaction temperature is preferably from 30 ℃ to 180 ℃, more preferably from 80 ℃ to 140 ℃. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform and the like; alcohol solvents such as methanol, ethanol, isopropanol, butanol, etc.; nitrohydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone, and the like, and these solvents may be used in combination. Among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent to be used is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass, based on 1 part by mass of the total of the compound represented by formula (pt1) and the compound represented by formula (pt 2).

The method for removing the compound represented by the formula (AI) as the target compound from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of distilling off a solvent from a reaction solution to obtain a target product; cooling after the reaction is completed, and filtering to collect precipitated crystals. The filtered crystals are preferably washed with water or the like and then dried. Further, if necessary, the extract may be further purified by a known method such as column chromatography or recrystallization.

The above squaric acid in the colorant (A)

The content of the dye is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 95% by mass or more, and may be 100% by mass.

The colorant (A) contains the above-mentioned squaric acid

The dye may further contain a squaric acid other than the above-mentioned dyes

Colorants other than dyes, other than the above-mentioned squaric acids

The colorant different from the dye may be any of a dye (hereinafter, sometimes referred to as a dye (a1)) and a pigment (hereinafter, sometimes referred to as a pigment (a 2)). With the above squaric acid

Dyes different colorants may contain one or both of these dyes (a1) and pigments (a 2).

The dye (A1) is not limited to the above squaric acid

The dye is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. As The Dye, for example, The color index (The Society of Dye) can be mentionedrs and Colourists) as a substance having a color tone in addition to a pigment, known dyes described in the dyeing guidelines (color dyeing companies). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be cited. Among these, organic solvent-soluble dyes are preferred.

Specifically, there may be mentioned c.i. solvent yellow 4 (hereinafter, the description of c.i. solvent yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189,

c.i. solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

c.i. solvent orange 2, 7, 11, 15, 26, 56, 77, 86,

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

c.i. solvent blue 4,5, 14, 18, 35, 36, 37, 45, 58, 59: 1. 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

c.i. solvent dyes such as c.i. solvent green 1,3, 4,5, 7, 28, 29, 32, 33, 34, 35;

c.i. 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,

c.i. acid red 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 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,

c.i. acid oranges 6, 7, 8,10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173,

c.i. acid violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102,

c.i. acid blue 1,3,5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90: 1. 91, 92, 93: 1. 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1. at least one of the first and second electrodes 335 and 340,

c.i. acid green 1,3,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50: 1. 58, 63, 65, 80, 104, 105, 106, 109, and the like c.i. acid dyes;

c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141,

c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250,

c.i. direct oranges 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107,

c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104,

c.i. direct blue 1,2,3,6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 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, 256, 244, 246, 247, 245, 250, 251, 252, 257, 275, 268, 248,

c.i. direct dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

c.i. disperse yellows 51, 54, 76,

C.I. disperse Violet 26, 27,

c.i. disperse dyes such as c.i. disperse blue 1, 14, 56, 60, etc.;

c.i. basic reds 1, 10,

c.i. basic blue 1,3,5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89,

C.I. basic violet 2,

c.i. basic red 9,

c.i. basic dyes such as c.i. basic green 1;

c.i. reactive yellow 2, 76, 116,

C.I. reactive orange 16,

c.i. reactive dyes such as c.i. reactive red 36;

c.i. mordant yellow 5, 8,10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65,

c.i. mordant red 1,2,3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95,

c.i. mordant oranges 3,4,5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48,

c.i. mordant violet 1, 1: 1.2, 3,4,5,6, 7, 8,10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58,

c.i. mordant blue 1,2,3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84,

c.i. mordant dyes such as c.i. mordant green 1,3, 4,5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and the like;

c.i. vat dyes such as c.i. vat green 1, and the like.

These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

The pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in The color index (published by The Society of Dyers and Colourists).

Examples of the pigment include yellow pigments such as c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;

c.i. pigment blue 15:6, 60, etc.;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58;

c.i. brown pigments such as pigment brown 23, 25;

and black pigments such as c.i. pigment black 1 and 7.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment of the pigment surface with a polymer compound or the like, micronization treatment by sulfuric acid micronization or the like, cleaning treatment with an organic solvent, water or the like for removing impurities, treatment for removing ionic impurities by an ion exchange method or the like, as required.

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

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by Lubrizol Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), AJISPER (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

When a pigment dispersant is used, the amount thereof is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on the total amount of the pigment (a 2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the colorant (a) in the colored curable resin composition is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass, based on the total amount of solid components. When the content of the colorant (a) is within the above range, the color density in the production of a color filter is sufficient, and the resin (B) and the polymerizable compound (C) can be contained in the composition in necessary amounts, so that a pattern having sufficient mechanical strength can be formed.

The "total amount of solid components" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured by a known analytical means such as liquid chromatography or gas chromatography.

< resin (B) >

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

Resin [ K1 ]: a copolymer having a structural unit derived from at least 1 (a) (hereinafter sometimes referred to as "(a)") selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

resin [ K2 ]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) (hereinafter, may be referred to as "(c)";

resin [ K3 ]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

resin [ K4 ]; a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);

resin [ K5 ]; a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c);

resin [ K6 ]; a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride, and a structural unit derived from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexenedicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as 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 and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of dibasic or higher polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl ] succinate and mono [2- (meth) acryloyloxyethyl ] phthalate;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

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

(b) The polymerizable compound has, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Preferably, the monomer has a cyclic ether having 2-4 carbon atoms and a (meth) acryloyloxy group.

Examples of (b) include a monomer (b1) (hereinafter sometimes referred to as "(b 1)") having an oxirane group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as "(b 2)") having an oxetanyl group and an ethylenically unsaturated bond, and a monomer (b3) (hereinafter sometimes referred to as "(b 3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

Examples of (b1) include a monomer (b1-1) (hereinafter sometimes referred to as "(b 1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b1-2) (hereinafter sometimes referred to as "(b 1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

Examples of (b1-1) include glycidyl (meth) acrylate, (. beta. -methylglycidyl (meth) acrylate, (. beta. -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, (. alpha. -methyl-o-vinylbenzyl glycidyl ether, (. alpha. -methyl-m-vinylbenzyl glycidyl ether, (. alpha. -methyl-p-vinylbenzyl glycidyl ether), 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, p-vinylbenzyl glycidyl ether, p-vinylbenzyl ether, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, p-vinylbenzyl, p-vinyl acetate, p-vinyl acetate, and a-vinyl acetate, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of (b1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Co., Ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (I) and a compound represented by the formula (II).

[ formula (I) and formula (II),

R^aand R^bRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^aAnd X^bRepresents a single bond, — R^c-、*-R^c-O-、*-R^c-S-or-R^c-NH-。

R^cRepresents an alkanediyl group having 1 to 6 carbon atoms.

Denotes the bonding site to O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-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, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

As R^aAnd R^bPreferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

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

As X^aAnd X^bPreferred examples thereof include a single bond, methylene, ethylene and-CH₂-O-and-CH₂CH₂-O-, and more preferably a single bond, — CH₂CH₂-O- (. indicates a bonding site to O).

Examples of the compound represented by the formula (I) include compounds represented by any of the formulae (I-1) to (I-15). Among them, preferred are compounds represented by the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formulae (I-11) to (I-15), and more preferred are compounds represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any of the formulae (II-1) to (II-15). Among them, preferred are compounds represented by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formulae (II-11) to (II-15), and more preferred are compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of 2 or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio [ the compound represented by the formula (I): the compound represented by the formula (II) ] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, and 3-ethyl-3-acryloxyethyloxetane.

As (b3), monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V #150, manufactured by Osaka organic chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

The component (b) is preferably (b1) from the viewpoint of enabling the obtained color filter to have higher reliability such as heat resistance and chemical resistance. From the viewpoint of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ] meth) acrylate^2,6]Decan-8-yl ester (which is known as "dicyclopentyl (meth) acrylate" and may be referred to as "tricyclodecanyl (meth) acrylate" as a common name in the art), and tricyclo (meth) acrylate [5.2.1.0 ]^2,6]Decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid esters such as dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, bicyclic unsaturated compounds such as 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

styrene, alpha-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

Among these, 2-hydroxyethyl (meth) acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [ K1], the ratio of the structural units derived from the respective monomers among all the structural units constituting the resin [ K1], is preferably:

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

Structural units derived from (b): 40 to 98 mol percent,

more preferably:

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

Structural units derived from (b): 50 to 90 mol%.

When the ratio of the structural units of the resin [ K1] is in the above range, the colored curable resin composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance of the resulting color filter.

The resin [ K1] can be produced, for example, by referring to the method described in "Experimental method for Polymer Synthesis" (published by Otsuka corporation, 1 st edition, 1 st Ed.3/1 1972) and the cited literature described in this document.

Specifically, the predetermined amounts of (a) and (b), a polymerization initiator, a solvent and the like are added to a reaction vessel, and, for example, oxygen is replaced with nitrogen to form a deoxygenated atmosphere, and the mixture is heated and kept warm while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and the like), organic peroxides (benzoyl peroxide, and the like), solvents in which the monomers are soluble, and the like described below as the solvent (F) of the colored curable resin composition of the present invention.

The copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, in the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention, and therefore, the production process of the colored curable resin composition of the present invention can be simplified.

In the resin [ K2], the ratio of the structural units derived from the respective monomers among all the structural units constituting the resin [ K2], is preferably:

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

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

Structural units derived from (c): 1 to 65 mol% of a surfactant,

more preferably:

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

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

Structural units derived from (c): 5 to 60 mol%.

When the ratio of the structural units of the resin [ K2] is in the above range, the colored curable resin composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance, heat resistance, and mechanical strength of the resulting color filter.

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

In the resin [ K3], the ratio of the structural units derived from the respective monomers among all the structural units constituting the resin [ K3], is preferably:

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

Structural units derived from (c): 40 to 98 mol percent,

more preferably:

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

Structural units derived from (c): 50 to 90 mol%.

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

The resin [ K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and/or a carboxylic acid anhydride of (a).

First, a copolymer of (a) and (c) was produced in the same manner as in the method described for producing resin [ K1 ]. In this case, the ratio of the structural units derived from the respective monomers is preferably the same as the ratio recited in the resin [ K3 ].

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

After the production of the copolymer of (a) and (c), the atmosphere in the flask is then changed from nitrogen to air, and (b), a reaction catalyst for a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (for example, hydroquinone) are placed in the flask and reacted at 60 to 130 ℃ for 1 to 10 hours to produce a resin [ K4 ].

(b) The amount of (b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). When the content is within this range, the storage stability of the colored curable resin composition, the developability in forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be well balanced. From the viewpoint of high reactivity of the cyclic ether and difficulty in leaving unreacted (b), the (b) used for the resin [ K4] is preferably (b1), and more preferably (b 1-1).

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

The reaction conditions such as the charging method, the reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. Similarly to the polymerization conditions, the method of charging and the reaction temperature may be appropriately adjusted in consideration of the production facilities, the amount of heat generated by polymerization, and the like.

The resin [ K5] was subjected to the same production method as that for the resin [ K1] as the first step, to obtain a copolymer of (b) and (c). The copolymer obtained in the same manner as described above may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) to the total molar number of all the structural units constituting the above-mentioned copolymer is preferably:

structural units derived from (b): 5 to 95 mol%

Structural units derived from (c): 5 to 95 mol% of a surfactant,

more preferably:

structural units derived from (b): 10 to 90 mol%

Structural units derived from (c): 10 to 90 mol%.

The resin [ K5] can be obtained by further reacting the cyclic ether derived from (b) and contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic acid anhydride contained in (a) under the same conditions as in the process for producing the resin [ K4 ].

The amount of (a) to be used in the reaction with the copolymer is preferably 5 to 80 mol based on 100 mol of (b). From the viewpoint of high reactivity of the cyclic ether and difficulty in leaving unreacted (b), the (b) used for the resin [ K5] is preferably (b1), and more preferably (b 1-1).

The resin [ K6] was obtained by further reacting the resin [ K5] with a carboxylic acid anhydride. The hydroxyl group resulting from the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride is reacted with the carboxylic anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1mol based on 1mol of the amount of (a).

Specific examples of the resin (B) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and an acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ]^2,6]Resins [ K1] such as decyl ester/(meth) acrylic acid copolymers](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0 ]^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3- (meth) acryloyloxymethyl oxetane/(meth) acrylic acid/styreneResin such as olefin copolymer [ K2](ii) a Resins [ K3] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer and styrene/(meth) acrylic acid copolymer](ii) a Resins obtained by adding benzyl (meth) acrylate/(meth) acrylic acid copolymer and glycidyl (meth) acrylate, resins obtained by adding tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer and glycidyl (meth) acrylate, and resins obtained by adding tricyclodecyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer and glycidyl (meth) acrylate [ K4 [ ] -resin](ii) a Resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) with (meth) acrylic acid, and resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) with (meth) acrylic acid [ K5](ii) a Resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) with (meth) acrylic acid and further reacting the resulting resin with tetrahydrophthalic anhydride [ K6]]And the like.

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

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. When the molecular weight is within the above range, the color filter tends to have high hardness, a high residual film ratio, good solubility of unexposed portions in a developer, and high resolution of a colored pattern.

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

The acid value of the resin (B) is preferably 30 to 170mg-KOH/g, more preferably 40 to 150mg-KOH/g, and still more preferably 50 to 135mg-KOH/g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1g of the resin (B), and can be determined by titration using an aqueous potassium hydroxide solution, for example.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of solid components. If the content of the resin (B) is within the above range, the colored pattern can be 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 polymerizable by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and preferably a (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and the like, Caprolactone modified dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, and still more preferably 10 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 forming a colored pattern and the chemical resistance of the color filter tend to be improved.

< polymerization initiator (D) >)

The polymerization initiator (D) is not particularly limited as long as it is a compound which can generate an active radical, an acid, or the like by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. As the polymerization initiator generating active radicals, for example, an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound can be cited.

As the above-mentioned O-acyloxime compound, for example, examples thereof include O-acyloxime compounds having a diphenylsulfide skeleton such as N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine; n-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, and mixtures thereof, O-acyloxime compounds having a carbazole skeleton, such as N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine; and O-acyloxime compounds having a fluorene skeleton such as 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone O-acetyloxime. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.), DFI-091 (manufactured by Daito Chemix Co., Ltd.), PBG-327 (manufactured by Kyowa Kagaku Kaisha Co., Ltd.) and the like can be used. Wherein the O-acyloxime compound is preferably selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine and 1- [7- (2-methylbenzoyl) -9, at least 1 of 9-dipropyl-9H-fluoren-2-yl ] ethanone O-acetyl oxime. These O-acyloxime compounds tend to give color filters having high brightness.

Examples of the above-mentioned alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, and the like, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzil dimethyl ketal, and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (manufactured by BASF) can be used.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethyl ] triazine Alkenyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.

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

Examples of the biimidazole compound include 2,2 ' -bis (2-chlorophenyl) -4, 4', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4, 4', 5,5 ' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 ' -bis (2-chlorophenyl) -4, 4', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2-chlorophenyl) -4, 4', 5,5 ' -tetrakis (alkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4, 4', 5,5 ' -tetrakis (dialkoxyphenyl) biimidazole, 2,2 ' -bis (2-chlorophenyl) -4, 4', 5,5 ' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, Japanese patent publication No. 48-38403 and Japanese patent application laid-open No. 62-174204), and biimidazole compounds in which the phenyl group at the 4,4', 5,5 ' -position is substituted with a carboalkoxy group (カルボアルコキシ group) (see, for example, Japanese patent application laid-open No. 7-10913).

Examples of the polymerization initiator generating an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl-methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium

P-toluenesulfonate and diphenyliodine

Hexafluoroantimonate and the like

Salts, nitrobenzyl tosylates, benzoin tosylates, and the like.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ',4, 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like.

The polymerization initiator (D) is preferably a polymerization initiator containing at least 1 selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a bisimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be short, so that the productivity of the color filter tends to be improved.

< antioxidant (E) >

The antioxidant (E) contains a phenolic antioxidant. The colored curable resin composition of the present invention contains a phenolic antioxidant, and thus can suppress a decrease in the maximum absorption in the film forming step.

As the phenol antioxidant, known phenol antioxidants can be used, and examples thereof include Irganox (registered trademark) 1010: pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (manufactured by BASF corporation), Irganox (registered trademark) 1076: octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF corporation), Irganox (registered trademark) 1330: 3,3 ', 3 ", 5,5 ', 5 ″ -hexa-tert-butyl-a, a ', a ″ - (mesitylene-2, 4, 6-triyl) tri-p-cresol (manufactured by BASF corporation), Irganox (registered trademark) 3114: 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione (manufactured by BASF corporation), Irganox (registered trademark) 3790: 1,3, 5-tris ((4-tert-butyl-3-hydroxy-2, 6-xylyl) methyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione (manufactured by BASF corporation), Irganox (registered trademark) 1035: thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (manufactured by BASF corporation), Irganox (registered trademark) 1135: phenylalanic acid 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester (manufactured by BASF corporation), Irganox (registered trademark) 1520L: 4, 6-bis (octylthiomethyl) o-cresol (manufactured by BASF), Irganox (registered trademark) 3125 (manufactured by BASF), Irganox (registered trademark) 565: 2, 4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5' -di-tert-butylanilino) -1,3, 5-triazine (manufactured by BASF corporation), Irganox (registered trademark) 1726: 1,3, 5-tris [2- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] ethyl ] hexahydro-1, 3, 5-triazine-2, 4, 6-trione (manufactured by BASF corporation), ADK STAB (registered trademark) AO-80: 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5.5] undecane (manufactured by ADEKA Co., Ltd.), ADK STAB (registered trademark) AO-20: 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione (manufactured by ADEKA), ADK STAB (registered trademark) AO-30: 4,4',4 "- (1-methylpropanyl-3-ylidene) tris (6-tert-butyl-m-cresol) (4,4', 4" - (1-methylpropanyl-3-ylidine) tris (6-tert-butyl-m-cresol)) (manufactured by ADEKA corporation), ADK STAB (registered trademark) AO-40: 6,6 '-di-tert-butyl-4, 4' -butylidenebispresol (manufactured by ADEKA corporation), ADK STAB (registered trademark) AO-50: octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by ADEKA corporation), ADK STAB (registered trademark) AO-60: pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (manufactured by ADEKA corporation), ADK STAB (registered trademark) AO-330: 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4, 6-trimethylbenzene (manufactured by ADEKA corporation), Sumilizer (registered trademark) BHT: 2, 6-di-t-butyl-p-cresol (manufactured by sumitomo chemical corporation), Sumilizer (registered trademark) GA-80: 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5.5] undecane (manufactured by sumitomo chemical corporation), Sumilizer (registered trademark) GP: 2-tert-butyl-6-methyl-4- {3- [ (2,4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1,3,2] dioxaphosphorin-6-yl) oxy ] propyl } phenol (manufactured by sumitomo chemical co., ltd.), Sumilizer (registered trademark) GS: 2- [1- (2-hydroxy-3, 5-di-tert-pentylphenyl) ethyl ] -4, 6-di-tert-pentylphenyl ═ acrylate (manufactured by sumitomo chemical co., ltd.), Sumilizer (registered trademark) GM: 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl ═ acrylate (manufactured by sumitomo chemical corporation), Cyanox 1790: 1,3, 5-tris ((4-tert-butyl-3-hydroxy-2, 6-xylyl) methyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione (manufactured by Sitech Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.), and the like.

The phenol-based antioxidant is preferably a compound having no vinyl group or ethylene-1, 1-diyl group. By using the phenol antioxidant, a decrease in the maximum absorption in the film forming step can be suppressed, but the color change (Δ Eab) may be increased. However, by using a compound having no vinyl group or ethylene-1, 1-diyl group as the phenol antioxidant, not only a decrease in the maximum absorption in the film forming step but also a color change can be suppressed.

The number of phenolic hydroxyl groups of the 1-molecule phenolic antioxidant is preferably 1 to 5, more preferably 1 to 4, and still more preferably 2 to 4.

Among the phenol antioxidants, hindered phenol antioxidants are preferred. The hindered phenol antioxidant is preferably a compound in which a tertiary alkyl group is bonded to at least one carbon atom in the 2 ortho positions to the phenolic hydroxyl group;

more preferably a compound in which a tertiary alkyl group is bonded to one carbon atom in the 2 ortho positions to the phenolic hydroxyl group, and a hydrogen atom or an alkyl group is bonded to the other carbon atom;

further preferred are compounds in which a tertiary alkyl group is bonded to one carbon atom in the 2 ortho positions to the phenolic hydroxyl group, and a hydrogen atom, a methyl group or a primary alkyl group is bonded to the other carbon atom;

particularly preferred are compounds in which a tertiary alkyl group is bonded to one carbon atom in the 2 ortho positions of the phenolic hydroxyl group, and a hydrogen atom or a methyl group is bonded to the other carbon atom.

Further, as the hindered phenol-based antioxidant, a compound having 2 or more phenolic hydroxyl groups in the molecule, and having a tertiary alkyl group bonded to one carbon atom in 2 ortho positions to the phenolic hydroxyl group and a hydrogen atom, a methyl group or a primary alkyl group bonded to the other carbon atom is preferable.

Examples of the alkyl group include a methyl group, a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group.

Examples of the primary alkyl group include an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, and a 2-ethylhexyl group, and an ethyl group and a n-propyl group are preferable.

Examples of the secondary alkyl group include isopropyl group and isobutyl group.

Examples of the tertiary alkyl group include a tertiary butyl group, a tertiary amyl group, a tertiary hexyl group, and a1, 1, 2-trimethylpropyl group, and the like, and a tertiary butyl group and a tertiary amyl group are preferable, and a tertiary butyl group is more preferable.

Specifically, as the hindered phenol antioxidant, preferred are compounds having at least one carbon atom in the ortho-position, such as Irganox (registered trademark) 1010, Irganox (registered trademark) 1076, Irganox (registered trademark) 1330, Irganox (registered trademark) 3114, Irganox (registered trademark) 3790, Irganox (registered trademark) 1035, Irganox (registered trademark) 1135, Irganox (registered trademark) 3125, Irganox (registered trademark) 565, ADK STAB (registered trademark) AO-80, ADK STAB (registered trademark) AO-20, ADK STAB (registered trademark) AO-30, ADK STAB (registered trademark) AO-40, ADK STAB (registered trademark) trademark-50, ADK STAB (registered trademark) AO-60, ADK STAB (registered trademark) AO-330, Sumilizer (registered trademark) BHT, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) Cys-ox GM 1790, and the like, and compounds having at least one carbon atom in the ortho-position, such as a tertiary butyl group GM 172,

more preferably, Irganox (registered trademark) 1010, Irganox (registered trademark) 1076, Irganox (registered trademark) 1330, Irganox (registered trademark) 3114, Irganox (registered trademark) 3790, Irganox (registered trademark) 1035, Irganox (registered trademark) 1135, Irganox (registered trademark) 3125, Irganox (registered trademark) 565, ADK STAB (registered trademark) AO-80, ADK STAB (registered trademark) AO-20, ADK STAB (registered trademark) AO-30, ADK STAB (registered trademark) AO-40, ADK STAB (registered trademark) AO-50, ADK STAB (registered trademark) AO-60, ADK STAB (registered trademark) AO-330, Suizor (registered trademark) bonding BHT, Suizor (registered trademark) GA-80, Suizor (registered trademark) milometer 90, Cyanox1790, etc., a hydroxyl group bonded to one of the adjacent carbon atom in GP 2, and a tertiary butyl group of the other carbon atom in GP, A compound of a methyl group or a tert-butyl group,

further preferred are compounds having a tert-butyl group bonded to one carbon atom in the 2 ortho positions to the phenolic hydroxyl group and a hydrogen atom or a methyl group bonded to the other carbon atom, such as Irganox (registered trademark) 3790, ADK STAB (registered trademark) AO-80, ADK STAB (registered trademark) AO-30, ADK STAB (registered trademark) AO-40, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) GP, and Cyanox1790,

particularly preferred are compounds having 2 or more phenolic hydroxyl groups, a t-butyl group bonded to one carbon atom in the 2 ortho-positions of the phenolic hydroxyl group, and a hydrogen atom or a methyl group bonded to the other carbon atom, such as Irganox (registered trademark) 3790, ADK STAB (registered trademark) AO-80, ADK STAB (registered trademark) AO-30, ADK STAB (registered trademark) AO-40, Sumilizer (registered trademark) GA-80, and Cyanox 1790.

As the antioxidant (E), other antioxidants may be used in combination with the phenolic antioxidants. As other antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine antioxidants, and the like can be used.

The content of the phenolic antioxidant in the antioxidant (E) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 95% by mass or more, or may be 100% by mass.

Antioxidant (E) and the above-mentioned squaric acid

Mass ratio of dye (antioxidant (E)/squaric acid)

Dye) is preferably 0.8 or more, more preferably 1.0 or more, further preferably 1.5 or more, particularly preferably 2.0 or more, preferably 13 or less, more preferably 10 or less, further preferably 8 or less.

The content of the antioxidant (E) is preferably 0.5 to 20% by mass, more preferably 1 to 17% by mass, and still more preferably 1.5 to 15% by mass, based on the total amount of the solid content.

< solvent (F) >

The colored curable resin composition of the present invention preferably further contains a solvent (F). The solvent (F) is not particularly limited, and a solvent generally used in this field can be used. Examples thereof include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and not containing-O-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dibutylene glycol

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone (hereinafter sometimes referred to as diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

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

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

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

Among the above solvents, from the viewpoint of coatability and drying properties, an organic solvent having a boiling point of 120 to 180 ℃ at 1atm is preferable. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone alcohol, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diacetone alcohol, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (F) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total content of the solid content in the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (F) is within the above range, the flatness at the time of coating becomes good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to be good.

< leveling agent (G) >

The colored curable resin composition of the present invention may further contain a leveling agent (G). Examples of the leveling agent (G) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF 46, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan contract Co., Ltd.) may be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, the examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi electro chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Asahi Flon SC105 (manufactured by Nitro Kabushiki Kaisha) and E5844 (manufactured by Dajinjin chemical research).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (available from DIC Co., Ltd.).

The content of the leveling agent (G) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.2% by mass, and still more preferably 0.005 to 0.2% by mass, based on the total amount of the colored curable resin composition. The content of the dispersant is not included in the content. If the content of the leveling agent (G) is within the above range, the flatness of the color filter can be improved.

< other ingredients >

The colored curable resin composition of the present invention may contain additives known in the art, such as a polymerization initiation aid, a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, as required.

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared, for example, by mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the antioxidant (E), and, if necessary, the solvent (F), the leveling agent (G), and other components.

< method for manufacturing color filter >

Examples of the method for producing a colored pattern using the colored curable resin composition of the present invention include a photolithography method, an ink jet method, a printing method, and the like. Among them, photolithography is preferable. The photolithography method is a method in which the colored curable resin composition is applied onto a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed without using a photomask and/or without performing development during exposure. The colored pattern or the colored coating film thus formed is the color filter of the present invention.

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

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass having a surface coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy, or the like formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be performed under known or conventional apparatus and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored composition layer.

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

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

When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the colored composition layer is exposed to light to form a colored coating film. In addition, when forming the colored pattern, the colored composition layer is exposed through a photomask. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use may be used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given.

In order to uniformly irradiate the entire exposure surface with parallel light beams or to precisely align the photomask with the substrate on which the colored composition layer is formed, an exposure apparatus such as a mask aligner or a stepper is preferably used.

The color composition layer after exposure is brought into contact with a developer to develop the color composition layer, thereby forming a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in a developer and removed by development. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of spin immersion, spraying, and the like. In addition, the substrate may be inclined at an arbitrary angle at the time of development.

It is preferable to carry out water washing after development.

Further, the obtained colored coating film or colored pattern is preferably subjected to postbaking. The post-baking temperature is preferably 150-250 ℃, and more preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

According to the present invention, a colored curable resin composition having high adaptability in a film forming step can be provided. The color filter produced from the colored curable resin composition is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL display devices, electronic paper, and the like) and solid-state imaging devices.

Examples

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples described below, and it goes without saying that modifications can be appropriately added within a range that can accommodate the gist described above and below, and all of them are included in the technical scope of the present invention. In the examples, unless otherwise specified,% and part of the contents or amounts used are by mass.

[ colorant Synthesis example 1]

10.0 parts of 2, 4-dimethylaniline (manufactured by Tokyo chemical industry Co., Ltd.), 17.0 parts of 2-ethylhexane bromide (manufactured by Tokyo chemical industry Co., Ltd.), and 44.0 parts of tetrabutylammonium bromide (manufactured by photochemical industry Co., Ltd.) were mixed. The resulting mixture was stirred at 90 ℃ for 8 hours. After the reaction, 50 parts of a 10% aqueous sodium bicarbonate solution was added, 100 parts of ethyl acetate was added, and the aqueous layer was discarded. The washing with water and 10% hydrochloric acid was repeated 2 times, and the solvent was distilled off. The obtained oil was dried under reduced pressure at 60 ℃ for 24 hours to obtain 9.3 parts of a compound represented by the following formula (a-1).

Watch of formula (a-1)Of the compounds shown¹H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d₆)

δ0.85(m，6H)、1.23-1.42(br，8H)、1.59(br，1H)、2.04(s，3H)、2.12(s，3H)、2.91(d，2H)、4.37(br，1H)、6.38(d，1H)、6.75(s，1H)、6.77(d，1H)

3.0 parts of the compound represented by the formula (a-1) obtained above, 2.2 parts of 3-bromophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.015 part of palladium acetate, 3.2 parts of sodium tert-butoxide (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.055 part of tri-tert-butylphosphine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 25.6 parts of toluene were mixed and stirred at 100 ℃ for 15 hours. To the resulting mixture were added 30 parts of ethyl acetate and 100 parts of water, and the aqueous layer was discarded. After washing with water was repeated 2 times, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane ═ 1/1), and the obtained oil was dried under reduced pressure at 60 ℃ for 24 hours to obtain 1.9 parts of a compound represented by the following formula (a-2).

Process for producing compound represented by the formula (a-2)¹H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d₆)

δ0.85(m，6H)、1.23-1.42(br，8H)、1.55(br，1H)、1.94(s，3H)、2.27(s，3H)、2.90(d，2H)、6.37(d，1H)、6.75(s，1H)、6.76(d，1H)、6.92-7.14(m，4H)、8.93(s，1H)

4.4 parts of the compound represented by the formula (a-2) obtained above, 0.8 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (manufactured by Tokyo chemical Co., Ltd.), 90.0 parts of 1-butanol and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125 ℃ for 3 hours while removing the generated water using a Dean-Stark tube. After the reaction was completed, the solvent was distilled off, 15 parts of acetic acid was added thereto, and the mixture was added dropwise to 100 parts of 18% saline solution, and the precipitated solid was collected by filtration. The filtered solid was washed with hexane. The resulting solid was dried under reduced pressure at 60 ℃ for 24 hours to obtain 4.9 parts of a compound represented by the formula (AI-1).

Process for producing compound represented by the formula (AI-1)¹H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d₆)

δ0.87(m，12H)、1.21-1.57(m，16H)、1.72(br，2H)、2.05(s，6H)、2.36(s，6H)、3.37(br，2H)、3.78(br，2H)、6.00(br，4H)、6.97-7.12(m，6H)、7.77-7.95(m，2H)、11.35(s，1H)、12.06(s，1H)

[ Synthesis example 2 of coloring agent ]

50 parts of m-bromophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 500 parts of methylene chloride (manufactured by Kanto Kasei Kogyo Co., Ltd.), cooled to 0 ℃ and 48 parts of t-butyldimethylchlorosilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise. After the addition, the temperature was raised to 23 ℃ and the mixture was stirred for 16 hours. After the reaction, the organic layer was extracted with water, and the solvent was concentrated and then separated and purified by silica gel column chromatography to obtain 74 parts of a compound represented by the formula (1-10). The structure of the compound was confirmed by MASS analysis (LC; model 1200 by Agilent, MASS; LC/MSD by Agilent).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺287.0

Precise molecular weight: +286.0

45 parts of 4-amino-3, 5-xylenol (manufactured by Tokyo chemical Co., Ltd.) was dissolved in 400 parts of tetrahydrofuran (manufactured by Kanto chemical Co., Ltd.). To the solution, 127 parts of di-tert-butyl dicarbonate (manufactured by Tokyo chemical Co., Ltd.) was added and dissolved. The reaction was stirred at 23 ℃ for 16 hours. After completion of the reaction, the solvent was distilled off to obtain 51 parts of a crude product. The obtained crude product was purified by stirring at 23 ℃ for 2 hours in a mixed solvent of 90 parts of ethyl acetate (manufactured by Kanto chemical Co., Ltd.) and 272 parts of n-hexane (manufactured by Kanto chemical Co., Ltd.) to obtain 47 parts of a compound represented by the formula (1-33).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺238.3

Precise molecular weight: +237.1

20 parts of 2-bromoethanol (manufactured by Tokyo chemical Co., Ltd.) was dissolved in 333 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.). To the solution were added 32.4 parts of triethylamine (manufactured by Kanto chemical Co., Ltd.) and 0.156 part of 4-dimethylaminopyridine (manufactured by Kanto chemical Co., Ltd.), and 28.95 parts of tert-butyldimethylsilyl chloride (manufactured by Tokyo chemical Co., Ltd.) was added and dissolved with stirring. The reaction was stirred at 23 ℃ for 16 hours. The solvent was distilled off to obtain 20 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by the formula (1-34).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺239.1

Precise molecular weight: +238.0

47 parts of the compound represented by the formula (1-33) and 141.5 parts of a bromine compound represented by the formula (1-34) were dissolved in 447 parts of dimethylformamide (manufactured by Kanto chemical Co., Ltd.). 138.2 parts of potassium carbonate (manufactured by Kanto chemical Co., Ltd.) was added to the solution, and the mixture was stirred at 70 ℃ for 16 hours to effect a reaction. After the reaction, the solvent was distilled off, and an extraction operation was performed using an organic solvent to obtain 49 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 41 parts of a compound represented by the formula (1-35).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H-t-Bu⁺]⁺339.2

Precise molecular weight: +395.3

41 parts of the compound represented by the formula (1-35) was dissolved in 1, 4-bis

424 parts of an alkane (manufactured by Kanto chemical Co., Ltd.) were charged with hydrogen chloride (about 4mol/L, 1, 4-bis)

An alkane solution) (manufactured by Tokyo chemical industry Co., Ltd.) in 263 parts was stirred at 23 ℃ for 1 hour to carry out deprotection. After the reaction, the solvent was distilled off to obtain 36 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 22 parts of a compound represented by the formula (1-36).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺182.2

Precise molecular weight: +181.1

22 parts of the compound represented by the formula (1-36) was dissolved in 293 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.). To the solution were added 10.8 parts of imidazole (manufactured by Kanto chemical Co., Ltd.) and 22 parts of t-butyldimethylsilyl chloride (manufactured by Tokyo chemical Co., Ltd.) to dissolve them. The reaction was stirred at 23 ℃ for 16 hours. The solvent was distilled off to obtain 23 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by the formula (1-37).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺296.3

Precise molecular weight: +295.2

15 parts of the compound represented by the formula (1-10) and 14.5 parts of the compound represented by the formula (1-37) were dissolved in 130 parts of toluene (manufactured by Kanto chemical Co., Ltd.), and 5.7 parts of potassium hydroxide (manufactured by Kanto chemical Co., Ltd.), 15 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo chemical Co., Ltd.), and 0.26 part of bis (tri-t-butylphosphine) palladium (0) (manufactured by Tokyo chemical Co., Ltd.) were mixed in the solution. After heating to 90 ℃ and stirring for 20 minutes, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 15 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 12 parts of a compound represented by the formula (1-38).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺502.4

Precise molecular weight: +501.3

12 parts of the compound represented by the formula (1-38), 11.9 parts of methyl 4-chloro-4-oxobutanoate (manufactured by Tokyo chemical Co., Ltd.), and 41.6 parts of toluene (manufactured by Kanto chemical Co., Ltd.) were mixed, stirred at 90 ℃ for 1 hour, and heated. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 5.9 parts of a compound represented by the formula (1-39).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺616.3

Precise molecular weight: +615.3

After 5.9 parts of the compound represented by the formula (1-39) was dissolved in 52.4 parts of tetrahydrofuran (manufactured by Kanto chemical Co., Ltd.) and cooled to 0 ℃, 11 parts of a 1M tetrahydrofuran solution of tetrabutylammonium fluoride (manufactured by Tokyo chemical Co., Ltd.) was added dropwise thereto, and the mixture was stirred at 23 ℃ for 2 hours after the completion of the addition. After the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was subjected to an extraction operation with an organic solvent and concentrated to obtain 4.3 parts of a compound represented by the formula (1-40).

And (3) identification:(mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺388.2

Precise molecular weight: +387.2

4.3 parts of the compound represented by the formula (1-40), 56.4 parts of a borane in 1M tetrahydrofuran (manufactured by Kanto chemical Co., Ltd.), and 38.2 parts of tetrahydrofuran (manufactured by Kanto chemical Co., Ltd.) were mixed at 0 ℃ and the mixture was stirred for 16 hours while raising the temperature to 23 ℃. After the reaction is finished, adding water for quenching, and extracting by using an organic solvent. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 2.3 parts of a compound represented by the formula (1-41).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺346.3

Precise molecular weight: +345.2

2.3 parts of the compound represented by the formula (1-41) and 0.38 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (FUJIFILM Wako Pure Chemical Co., Ltd.) were dissolved in 80 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 19 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) and stirred at 120 ℃ for 4 hours and heated. After the reaction was completed, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of a compound represented by formula (AI-15).

And (3) identification: (mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺769.8

Precise molecular weight: +768.4

[ example of Synthesis of resin ]

An appropriate amount of the solution was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrerAfter replacing nitrogen with nitrogen, 280 parts of propylene glycol monomethyl ether acetate was added and the mixture was heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]A mixture of decane-9-yl ester (mixing ratio 1:1)289 parts, propylene glycol monomethyl ether acetate 125 parts. On the other hand, a mixed solution of 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the flask was held at 80 ℃ for 4 hours and then cooled at room temperature to obtain a copolymer (resin (B-1)) solution having a B-type viscosity (23 ℃) of 125 mPas and a solid content of 35.1%. The resulting copolymer had a weight average molecular weight Mw of 9200, a dispersity of 2.08 and a solid acid value of 77 mg-KOH/g. The resin (B-1) has the following structural unit.

Examples 1 to 15 and comparative examples 1 to 3

[ preparation of colored curable resin composition ]

The respective components were mixed so as to have the compositions shown in table 3, thereby obtaining colored curable resin compositions. In table 3, the unit of the content of each composition is "part".

[ Table 3]

In table 3, each component represents the following compound.

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

Colorant (a-2): a compound represented by the formula (AI-15)

Resin (B-1): resin (B-1) (conversion of solid content)

Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kabushiki Kaisha)

Polymerization initiator (D-1): n-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime Compound; manufactured by Henzhou powerful New electronic Material Co., Ltd.)

Antioxidant (E-1): 4,4' - (1-methylpropanyl-3-ylidene) tris (6-tert-butylmetacresol) (ADK STAB (registered trademark) AO-30; manufactured by ADEKA K.K.)

Antioxidant (E-2): 6,6 '-di-tert-butyl-4, 4' -butylidenebispresol (ADK STAB (registered trademark) AO-40; manufactured by ADEKA K.K.)

Antioxidant (E-3): 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5.5] undecane (Sumilizer (registered trademark) GA-80; manufactured by Sumitomo chemical Co., Ltd.)

Antioxidant (E-4): pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (ADK STAB (registered trademark) AO-60; manufactured by ADEKA K.K.)

Antioxidant (E-5): 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione (ADK STAB (registered trademark) AO-20; manufactured by ADEKA K.K.)

Antioxidant (E-6): 2-tert-butyl-6-methyl-4- {3- [ (2,4,8, 10-tetra-tert-butyldibenzo [ d, f ]][1,3,2]II

Phosphaheptin-6-yl) oxy]Propyl } phenol (Sumilizer (registered trademark) GP; manufactured by Sumitomo chemical Co., Ltd.)

Antioxidant (E-7): 2- [1- (2-hydroxy-3, 5-di-t-pentylphenyl) ethyl ] -4, 6-di-t-pentylphenyl ═ acrylate (Sumilizer (registered trademark) GS; manufactured by Sumitomo chemical Co., Ltd.)

Antioxidant (E-8): methacrylic acid 1,2,2,6, 6-pentamethyl-4-piperidyl ester (ADK STAB (registered trademark) LA 82; manufactured by ADEKA K.K.)

Antioxidant (E-9): 2,2,6, 6-tetramethyl-4-piperidyl methacrylate (ADK STAB (registered trademark) LA 87; manufactured by ADEKA K.K.)

Solvent (F-1): diacetone alcohol

Solvent (F-2): propylene glycol monomethyl ether acetate

Leveling agent (G-1): polyether-modified Silicone oil (Toray Silicone SH8400, manufactured by Dow Corning Toray corporation)

[ preparation of colored coating film ]

The colored curable resin composition was applied onto a 5cm square glass substrate (EAGLE 2000; manufactured by CORNING) by a spin coating method so that the post-baking film thickness became 2.0. mu.m, and then pre-baked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to 100mJ/cm of light using an exposure machine (TME-150 RSK; manufactured by Topcon K.K.) under an atmospheric atmosphere²The exposure amount (365nm basis) of (b) is irradiated with light to the colored composition layer. Thereafter, the resultant film was postbaked in an oven at 230 ℃ for 30 minutes to obtain a colored coating film.

[ evaluation ]

1. Absorbance retention ratio

The maximum absorbance in the visible light region was determined from the spectra measured using a color measuring instrument (OSP-SP-200; manufactured by Olympus corporation) after the prebaking and after the postbaking, and the retention of the maximum absorbance was calculated from the following equation. The results are shown in Table 4.

Max (absorbance retention ratio) max after baking/max after prebaking

The higher the absorbance retention ratio, the higher the suitability in the film forming step.

2. Color change (Delta Eab)

The spectrum was measured using a color measuring instrument (OSP-SP-200; manufactured by Olympus corporation) after the prebaking and after the postbaking, and the xy chromaticity coordinates (x, Y) and stimulus value Y in the XYZ color system of CIE were measured using the characteristic function of the C light source. From the measurement values, the following were measured in accordance with JIS Z8730: 2009(7. method for calculating color difference) the color difference Δ Eab was calculated, and the results are shown in table 4. A smaller Δ Eab means a smaller color change.

[ Table 4]

Industrial applicability

The present invention can provide a colored curable resin composition having high adaptability in a film forming step, and is therefore useful as a colored curable resin composition used for color filters of display devices and solid-state imaging devices.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and an antioxidant,

the colorant contains a squaric acid having a maximum absorption in the visible region

The dye is a mixture of a dye and a water,

the antioxidant contains a phenolic antioxidant.

2. The colored curable resin composition according to claim 1, wherein the phenolic antioxidant is a compound having no vinyl group and no ethylene-1, 1-diyl group.

3. The colored curable resin composition according to claim 1 or 2, wherein the phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one carbon atom in 2 ortho positions to the phenolic hydroxyl group, and a hydrogen atom or an alkyl group is bonded to the other carbon atom.

4. The colored curable resin composition according to any one of claims 1 to 3, wherein the phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one carbon atom in 2 ortho positions to the phenolic hydroxyl group, and a hydrogen atom, a methyl group or a primary alkyl group is bonded to the other carbon atom.

5. The colored curable resin composition according to any one of claims 1 to 4, wherein the antioxidant and the squaric acid are

Mass ratio of dye i.e. antioxidant/squaric acid

The dye is more than 0.8.

6. The colored curable resin composition according to any one of claims 1 to 5, wherein the squaric acid

The dye is a compound represented by a formula (AI),

in the formula (AI), the reaction mixture is,

R¹～R⁴each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a substituted or unsubstituted 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, and a methylene group constituting the 1-valent saturated hydrocarbon group may be substituted by-O-or-S-,

R⁵～R⁸each independently represents a hydrogen atom or a hydroxyl group,

Ar¹and Ar²Each independently represents a group represented by the formula (i),

R⁹and R¹⁰Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by the formula (i), wherein a methylene group constituting the 1-valent saturated hydrocarbon group may be substituted by-O-or-S-,

in the formula (i), the reaction mixture is,

R¹²represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxyl group or a carboxyl group, and m represents an integer of 0 to 5The methylene group of the 1-valent saturated hydrocarbon group may be substituted by-O-or-S-, and when m is 2 or more, plural R' S¹²Each may be the same or different, and represents a bonding site to a nitrogen atom.

7. The colored curable resin composition according to any one of claims 1 to 6, wherein the squaric acid

The dye is a compound represented by a formula (AII),

in the formula (AII), the compound is shown in the specification,

R⁵～R⁸each independently represents a hydrogen atom or a hydroxyl group,

R¹³and R¹⁴Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxyl group, and a methylene group constituting the 1-valent saturated hydrocarbon group may be substituted by-O-or-S-,

in the formula (i), the reaction mixture is,

R¹²represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxyl group or a carboxyl group, m represents an integer of 0 to 5, methylene groups constituting the 1-valent saturated hydrocarbon group may be substituted by-O-or-S-, and when m is 2 or more, a plurality of R' S¹²Each may be the same or different, and represents a bonding site to a nitrogen atom.

8. A color filter comprising the colored curable resin composition according to any one of claims 1 to 7.

9. A display device comprising the color filter of claim 8.