CN113286828B - Colored curable resin composition - Google Patents

Colored curable resin composition Download PDF

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CN113286828B
CN113286828B CN201980088648.XA CN201980088648A CN113286828B CN 113286828 B CN113286828 B CN 113286828B CN 201980088648 A CN201980088648 A CN 201980088648A CN 113286828 B CN113286828 B CN 113286828B
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CN113286828A (en
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土谷崇夫
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L101/00—Compositions of unspecified macromolecular compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

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Abstract

The invention provides a colored curable resin composition capable of forming a color filter with excellent absorbance retention. The invention relates to a colored curable resin composition, which comprises a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises squaric acid represented by the formula (I)
Figure DDA0003155996880000012
And a dye colorant, wherein the resin contains a structural unit derived from N-substituted maleimide.

Description

Colored curable resin composition
Technical Field
The present invention relates to a colored curable resin composition.
Background
Color filters used in solid-state imaging devices such as liquid crystal display devices, electroluminescent display devices, plasma display devices, and the like, and CCD, CMOS sensors, and the like are manufactured from colored resin compositions. As a colorant used in such a colored resin composition, squaric acid is known
Figure BDA0003155996870000011
Dyes (patent documents 1 and 2, etc.).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2015-86379
Patent document 2: japanese patent application laid-open No. 2015-86380
Disclosure of Invention
However, conventionally known use of squaric acid
Figure BDA0003155996870000012
The color filter formed from the above colored curable resin composition containing a dye as a colorant may not sufficiently satisfy the absorbance retention. Accordingly, an object of the present invention is to provide a colored curable resin composition capable of forming a color filter having excellent absorbance retention.
The gist of the present invention is as follows.
[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,
the colorant is a colorant comprising a squaric acid represented by the formula (I)
Figure BDA0003155996870000013
The colorant of the dye is used as a coloring agent,
the resin contains a structural unit derived from N-substituted maleimide.
Figure BDA0003155996870000021
In the formula (I) of the formula (I),
R 1 ～R 4 each 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. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group.
R 5 ～R 8 Each independently represents a hydrogen atom or a hydroxyl group.
Ar 1 And Ar is a group 2 Each 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).
Figure BDA0003155996870000022
/>
In the formula (i) of the formula (I),
R 12 represents 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 m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group. When m is 2 or more, a plurality of R 12 May be the same or different, respectively. Represents a bonding site to a nitrogen atom.]
R 9 And R is 10 Each 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). An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group. ]
[2] A color filter formed from the colored curable resin composition according to [1 ].
[3] A display device comprising the color filter of [2 ].
The colored curable resin composition of the present invention can provide a color filter having excellent absorbance retention.
Detailed Description
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)), and a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)).
The colorant comprises a squaric acid represented by formula (I)
Figure BDA0003155996870000033
Dyes (hereinafter, sometimes referred to as compound (I)).
The resin contains structural units derived from N-substituted maleimides.
The colored curable resin composition of the present invention preferably further comprises a solvent (hereinafter, may be referred to as a solvent (E)).
The colored curable resin composition of the present invention may contain a leveling agent (hereinafter, may be referred to as leveling agent (F)).
In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.
< colorant (A) >)
The colorant (A) contains the compound (I). The present invention will be described in detail below using the formula (I), but the compound (I) further includes a compound having a resonance structure of the formula (I) and a structure obtained by rotating each group of the formula (I) about a bond axis of a single bond.
Figure BDA0003155996870000031
In the formula (I) of the formula (I),
R 1 ～R 4 each 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. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group.
R 5 ～R 8 Each independently represents a hydrogen atom or a hydroxyl group.
Ar 1 And Ar is a group 2 Each 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), preferably a group represented by the formula (i).
Figure BDA0003155996870000032
In the formula (i) of the formula (I),
R 12 represents 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 m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group. When m is 2 or more, a plurality of R 12 May be the same or different, respectively. Represents a bonding site to a nitrogen atom.]
R 9 And R is 10 Each 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 carbon atoms constituting the 1-valent saturated hydrocarbon group may beTo intercalate oxygen or sulfur atoms.]
In the formula (I), R is 1 ～R 4 Examples of the halogen atom in (a) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As R 1 ～R 4 、R 9 、R 10 、R 12 、Ar 1 And Ar is a group 2 Examples of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms include straight-chain alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl; branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl; alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and adamantyl.
Examples of the substituent of the saturated hydrocarbon group include halogen atoms such as fluorine atom, chlorine atom and iodine; a hydroxyl group; a carboxyl group; -NR a R b (R a And R is b Each independently is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; examples of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms as a substituent include those represented by the following formulas. In the following formula, the "x" represents a bonding site.
Figure BDA0003155996870000041
Examples of the group having an oxygen atom or a sulfur atom interposed between carbon atoms constituting the saturated hydrocarbon group include groups represented by the following formulas. In the following formula, the "x" represents a bonding site.
Figure BDA0003155996870000051
As R 12 A C2-20 unsaturated hydrocarbon group having 1 valence,examples thereof include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl.
Examples of the substituent of the unsaturated hydrocarbon group include halogen atoms such as fluorine atom, chlorine atom and iodine; a hydroxyl group; a carboxyl group; -NR c R d (R c And R is d Each independently is 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; etc.
As R 1 ～R 4 The hydrogen atom, the hydroxyl group and the alkyl group having 1 to 4 carbon atoms are preferable, the hydrogen atom, the hydroxyl group and the methyl group are more preferable, and the hydrogen atom is further preferable.
Preferably R 5 ～R 8 At least 1 of which is hydroxy. More preferably R 5 And R is 6 At least one of them is hydroxy, R 7 And R is 8 At least one of which is a hydroxyl group.
As R 9 And R is 10 The alkyl group having 3 to 14 carbon atoms which may have a substituent and the group represented by the formula (i) are preferable, and the linear alkyl group having 3 to 6 carbon atoms which may have a substituent, the linear or branched alkyl group having 7 to 14 carbon atoms which may have a substituent (for example, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, etc.), the group represented by the formula (i) are more preferable, and the linear alkyl group having 3 to 5 carbon atoms which has a hydroxyl group at the terminal, the linear alkyl group having 3 to 5 carbon atoms which has a carboxyl group at the terminal, and the 2-ethylhexyl group are more preferable.
As R 12 The saturated hydrocarbon group of (2) is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group.
As R 12 The unsaturated hydrocarbon group of (2) is preferably an alkenyl group having 2 to 4 carbon atoms, more preferably a vinyl group or an allyl group.
When m is 2 or more, at least 1R is preferable 12 Is a saturated hydrocarbon group. When m is 2 or more, more preferably all R 12 In the form of saturated hydrocarbon radicals, or as part of R 12 Is a saturated hydrocarbon group and a part of R 12 Is unsaturated hydrocarbon group.
m is preferably 1 to 5, more preferably 1 to 3.
Examples of the group represented by formula (i) include the following groups. Represents a bonding site to a nitrogen atom.
Figure BDA0003155996870000061
In the formula (I) of the present invention,
will be
Figure BDA0003155996870000062
The radicals indicated are designated X 1 And will->
Figure BDA0003155996870000063
The radicals indicated are designated X 2 When X is 1 And X 2 Examples of the group represented by the formula (A2-1) to (A2-9) include groups represented by the following formulas. Represents a bonding site to a carbon atom. />
Figure BDA0003155996870000064
Examples of the compound (I) include compounds (AII-1) to (AII-27) shown in Table 1.
TABLE 1
Compounds of formula (I) R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 X 1 X 2
(AII-1) H H H H H H H H A2-1 A2-1
(AII-2) H H H H H H H H A2-2 A2-2
(AII-3) H H H H H H H H A2-3 A2-3
(AII-4) H H H H H H H H A2-4 A2-4
(AII-5) H H H H H H H H A2-5 A2-5
(AII-6) H H H H H H H H A2-6 A2-6
(AII-7) H H H H H H H H A2-7 A2-7
(AII-8) H H H H H H H H A2-8 A2-8
(AII-9) H H H H H H H H A2-9 A2-9
(AII-10) H H H H H OH OH H A2-1 A2-1
(AII-11) H H H H H OH OH H A2-2 A2-2
(AII-12) H H H H H OH OH H A2-3 A2-3
(AII-13) H H H H H OH OH H A2-4 A2-4
(AII-14) H H H H H OH OH H A2-5 A2-5
(AII-15) H H H H H OH OH H A2-6 A2-6
(AII-16) H H H H H OH OH H A2-7 A2-7
(AII-17) H H H H H OH OH H A2-8 A2-8
(AII-18) H H H H H OH OH H A2-9 A2-9
(AII-19) H H H H OH OH OH OH A2-1 A2-1
(AII-20) H H H H OH OH OH OH A2-2 A2-2
(AII-21) H H H H OH OH OH OH A2-3 A2-3
(AII-22) H H H H OH OH OH OH A2-4 A2-4
(AII-23) H H H H OH OH OH OH A2-5 A2-5
(AII-24) H H H H OH OH OH OH A2-6 A2-6
(AII-25) H H H H OH OH OH OH A2-8 A2-8
(AII-26) H H H H OH OH OH OH A2-9 A2-9
(AII-27) H H H H OH OH OH OH A2-7 A2-7
More preferably, the compounds (AII-10) to (AII-18).
The compound represented by the formula (I) can be produced by reacting a compound represented by the formula (pt 3) with a compound represented by the formula (pt 1) and a compound represented by the formula (pt 2). In the present reaction, the amount of the compound represented by the formula (pt 3) to be used is preferably 0.05 to 0.8 mol, more preferably 0.1 to 0.6 mol, based on 1 mol of the total of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 2).
Figure BDA0003155996870000081
Wherein R is 1 ～R 10 、Ar 1 And Ar is a group 2 The same meanings as described above are indicated.
The reaction temperature is preferably 30℃to 180℃and more preferably 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, etc.; 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 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 the formula (pt 1) and the compound represented by the formula (pt 2).
The method for removing the compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of cooling after the completion of the reaction and filtering out precipitated crystals is mentioned. The filtered crystals are preferably washed with water or the like, followed by drying. Further purification may be carried out by a known method such as recrystallization, if necessary.
The compound represented by the formula (pt 1) can be produced by reacting the compound represented by the formula (IV-2) with the compound represented by the formula (IV-3) to produce the compound represented by the formula (IV-4), and then reacting the compound represented by the formula (IV-4) with the compound represented by the formula (IV-5).
Figure BDA0003155996870000091
In the formulae (IV-2) to (IV-5), R 1 、R 2 、R 5 、R 6 、R 9 And Ar is a group 1 The same meanings as described above are indicated.
As a method for producing the compound represented by the formula (IV-4) from the compound represented by the formula (IV-2) and the compound represented by the formula (IV-3), there are known various methods, for example, the method described in Eur.J.Org.chem.2012,3105-3111.
As a method for producing the compound represented by the formula (pt 1) from the compound represented by the formula (IV-4) and the compound represented by the formula (IV-5), there are known various methods, for example, the method described in J.Polymer Sciene Science Part A: polymer Chemistry 2012,50,3788-3796.
The compound represented by formula (pt 2) can be produced by the same method as described above.
The colorant (a) may contain a colorant other than the compound (I) in addition to the compound (I), and the colorant other than the compound (I) may be any one of a dye (hereinafter, sometimes referred to as a dye (A1)) and a pigment (hereinafter, sometimes referred to as a pigment (A2)), and the colorant other than the compound (I) may contain one or both of the dye (A1) and the pigment (A2).
The dye (A1) may be any known dye without particular limitation as long as it does not contain the compound (I), and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Examples of the dye include a compound classified into a substance having a color tone other than pigment (pigment) in color index (The Society of Dyers and Colourists publication) and a known dye described in a dyeing guide (color dyeing company). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitrodyes, and the like can be exemplified. Among them, organic solvent-soluble dyes are preferable.
Specifically, examples thereof include c.i. solvent yellow 4 (hereinafter, description of c.i. solvent yellow is omitted, and only numbers are 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. solvents 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. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. c.i. solvent dyes;
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, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 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. 335, 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, etc.;
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, 243, 244, 245, 246, 247, 248, 259, 250, 251, 252, 256, 257, 259, 260, 268, 274, 293.
C.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.;
c.i. disperse yellow 51, 54, 76;
c.i. disperse violet 26, 27;
c.i. disperse blue 1, 14, 56, 60, etc. c.i. disperse dyes;
c.i. basic red 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. active yellow 2, 76, 116;
c.i. active orange 16;
c.i. reactive dyes such as c.i. reactive red 36;
c.i. medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
c.i. media 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. medium 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. vehicle 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. medium 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. mediator dyes such as c.i. mediator green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;
C.I. vat dyes such as C.I. vat green 1, etc.
These dyes may be appropriately selected in accordance with the spectral spectrum of the desired color filter.
The pigment (A2) may be any known pigment, and examples thereof include pigments classified into pigments (pigment) in the color index (The Society of Dyers and Colourists publication).
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, etc.;
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, etc.;
C.i. pigment blue 15: 6. blue pigment such as 60;
violet pigments such as c.i. pigment violet 1, 19, 23, 29, 32, 36, 38;
green pigments such as c.i. pigment green 7, 36, 58;
brown pigments such as pigment brown 23, 25;
black pigments such as c.i. pigment black 1 and 7.
The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative having an acid group or a basic group introduced therein, a grafting treatment to the pigment surface with a polymer compound or the like, a micronization treatment by sulfuric acid micronization or the like, a washing treatment by an organic solvent, water or the like for removing impurities, a removal treatment by an ion exchange method or the like for ionic impurities, or the like, as required.
The pigment preferably has a uniform particle size. By performing the dispersion treatment by containing 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 cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of 2 or more. Examples of pigment dispersants include KP (manufactured by Xinyue chemical industry Co., ltd.), FLOWLEN (manufactured by Kyowa Co., ltd.), solsperse (manufactured by ZENECA Co., ltd.), EFKA (manufactured by CIBA Co.), AJISPER (manufactured by Weisu Fine chemical Co., ltd.), and Disperbyk (manufactured by BYK-Chemie Co., ltd.).
When the pigment dispersant is used, the amount thereof to be used is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, relative to the total amount of the pigment (A2). When the amount of the pigment dispersant is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is 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 even more preferably 1 to 50% by mass, based on the total amount of solid components. If the content of the colorant (a) is within the above range, the color density at the time of producing a color filter is sufficient, and the composition can contain the resin (B) and the polymerizable compound (C) in the desired amounts, so that a pattern with sufficient mechanical strength can be formed.
Here, the "total amount of solid components" in the present specification refers to 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 can be measured by a known analytical means such as liquid chromatography or gas chromatography.
The content of the compound (I) in the total amount of the colorant (a) is preferably 1 mass% or more, more preferably 3 mass% or more, and may be 100 mass% or less, 90 mass% or less, 60 mass% or less, or 40 mass% or less.
< resin (B) >)
The resin contains a resin comprising structural units derived from an N-substituted maleimide.
By containing the resin in the colored curable resin composition of the present invention, the absorbance retention of the color filter is improved.
The structural unit derived from an N-substituted maleimide is preferably a structural unit represented by the following formula (Bm).
Figure BDA0003155996870000141
[ in formula (Bm), R 13 Represents a saturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 3 to 20 carbon atoms which may have a substituent.]
Examples of the 1-valent saturated hydrocarbon group having 1 to 15 carbon atoms include straight-chain alkyl groups having 1 to 15 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl; branched alkyl groups having 3 to 15 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl; alicyclic saturated hydrocarbon groups having 3 to 15 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and adamantyl groups.
Examples of the substituent of the saturated hydrocarbon group include halogen atoms such as fluorine atom, chlorine atom and iodine; a hydroxyl group; a carboxyl group; -NR h R i (R h And R is i Each independently is 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; an aromatic hydrocarbon group having 6 to 15 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, etc.; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; a group represented by the following formula (m-1), and the like.
Figure BDA0003155996870000151
[ in the formula (m-1), the "represents a bonding site". ]
Examples of the 1-valent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, and terphenyl.
Examples of the substituent of the aromatic hydrocarbon group include a hydroxyl group; a carboxyl group; halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a sulfamoyl group; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; a group represented by the formula (m-1), and the like.
R 13 Is a 1-valent saturated hydrocarbon group having 1 to 6 carbon atoms and having a substituent, wherein the saturated hydrocarbon group is an alkyl group, and when the substituent is an aromatic hydrocarbon group having 6 to 15 carbon atoms, R 13 Represents a 1-valent aralkyl group having 7 to 21 carbon atoms.
Examples of the 1-valent aralkyl group having 7 to 21 carbon atoms include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl and the like.
Examples of the substituent of the aralkyl group include the same groups as those described as the substituent of the aromatic hydrocarbon group.
Examples of the 1-valent heterocyclic group having 3 to 20 carbon atoms include thienyl and benzo [ b ]]Thienyl, naphtho [2,3-b ]]Thienyl, thianthreneRadical, furyl radical, pyranyl radical, isobenzofuranyl radical, benzopyranyl radical (chromen radical), xanthenyl radical and phenone
Figure BDA0003155996870000152
A thianyl group (Phenoxathiinyl), a 2H-pyrrolyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group (indolizinyl group), an isoindolyl group, a 3H-indolyl group, an indolyl group, a 1H-indazolyl group, a Purinyl group (Purinyl group), a 4H-quinolizinyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a 4 aH-carbazolyl group, a beta-carbolinyl group, a phenanthridinyl group, an acridinyl group, an periclazinyl group (Perimidyl group), a phenanthrolinyl group (phenanthrinyl group), a phenazinyl group (phenarshenzinyl group), an isothiazolyl group, a phenothiazinyl group, a>
Figure BDA0003155996870000161
Oxazolyl, furazanyl, pheno +. >
Figure BDA0003155996870000162
Oxazinyl (Phenoxazinyl), isochromyl Man Ji (Isochromanyl), chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidinyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, thioxanthonyl, and the like.
Examples of the substituent of the heterocyclic group include the same groups as those described as the substituent of the aromatic hydrocarbon group.
As R 13 Preferably an alicyclic saturated hydrocarbon group having 3 to 8 carbon atoms, a 1-valent aromatic hydrocarbon group having 6 to 10 carbon atoms or a 1-valent aralkyl group having 7 to 11 carbon atoms.
Examples of the structural unit derived from N-substituted maleimide include structural units derived from N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaprooate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like, and among these, structural units derived from N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are preferable.
The resin (B) is preferably an alkali-soluble resin. The resins (B) exhibiting alkali solubility include the following resins [ K1] to [ K6 ].
Resin [ K1]: a copolymer comprising a structural unit derived from at least 1 monomer (a) (hereinafter sometimes referred to as "(a)") selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, 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, and a structural unit derived from an N-substituted maleimide (m) (hereinafter sometimes referred to as "(m)";
resin [ K2]: a copolymer composed of a structural unit derived from (a), a structural unit derived from (b), a structural unit derived from (m), and a structural unit derived from a monomer (c) copolymerizable with (a) (but different from (a), (b) and (m) (hereinafter sometimes referred to as "(c)");
resin [ K3]: a copolymer composed of structural units derived from (a) and structural units derived from (m);
resin [ K4]: a copolymer composed of a structural unit derived from (a), a structural unit derived from (m) and a structural unit derived from (c);
resin [ K5]: a copolymer comprising a structural unit derived from (b) and a structural unit derived from (m) added to the structural unit derived from (a);
Resin [ K6]: a copolymer comprising a structural unit obtained by adding a structural unit derived from (b) to (a) and further to (m) a carboxylic anhydride.
The structural unit derived from (a) preferably has a carboxyl group or carboxylic anhydride contained in (a) remaining unreacted. In the resins [ K1] and [ K2], the structural unit derived from (b) preferably has a cyclic ether structure having 2 to 4 carbon atoms and remaining in an unreacted state.
Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and o-, m-, 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-cyclohexene dicarboxylic 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-dicarboxyibicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Unsaturated dicarboxylic 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-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride;
unsaturated mono- [ (meth) acryloyloxyalkyl ] esters of polycarboxylic acids having 2 or more members such as mono- [ 2- (meth) acryloyloxyethyl ] succinate and mono- [ 2- (meth) acryloyloxyethyl ] phthalate;
unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.
Among them, 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) Refers to a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxetane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Monomers having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group are preferable.
In the present specification, "(meth) acrylic acid" means at least 1 kind selected from acrylic acid and methacrylic acid. The expressions "(meth) acryl" and "(meth) acrylate" and the like have the same meaning.
Examples of (b) include a monomer (b 1) having an oxetanyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b 1)"), a monomer (b 2) having an oxetanyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b 2)"), and a monomer (b 3) having a tetrahydrofuranyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b 3)").
Examples of the (b 1) include a monomer (b 1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-1)") and a monomer (b 1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-2)").
Examples of (b 1-1) include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, β -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -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, 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-tris (glycidoxymethyl) styrene, and the like.
Examples of the (b 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, celloxide 2000, (product of Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer A400, (product of Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100, (product of Daicel)), a compound represented by the formula (BI), and a compound represented by the formula (BII).
Figure BDA0003155996870000181
[ formula (BI) and formula (BII), R e And R is f Represents 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 e And X f Represents a single bond, O-R g －、＊－R g －O－、＊－R g -S-or O-R g －NH－。
R g Represents an alkanediyl group having 1 to 6 carbon atoms.
And represents a bonding site to O. ]
Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.
Examples of the alkyl group having a hydrogen atom substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.
As R e And R is f The hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group are preferable, and the hydrogen atom and methyl group are more preferable.
Examples of the alkanediyl group include methylene, ethylene, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl.
As X e And X f The single bond, methylene, ethylene, or-CH can be preferably mentioned 2 -O-and-CH 2 CH 2 O-more preferably represents a single bond or-CH 2 CH 2 -O- (. Times. Represents a bonding site to O).
The compound represented by the formula (BI) may be a compound represented by any one of the formulas (BI-1) to (BI-15), or the like. Among them, preferred are compounds represented by the formula (BI-1), the formula (BI-3), the formula (BII-5), the formula (BI-7), the formula (BI-9) or the formula (BI-11) to the formula (BI-15), and more preferred are compounds represented by the formula (BI-1), the formula (BI-7), the formula (BI-9) or the formula (BI-15).
Figure BDA0003155996870000201
Examples of the compound represented by the formula (BII) include compounds represented by any one of the formulas (BII-1) to (BII-15). Among them, the compounds represented by the formula (BII-1), the formula (BII-3), the formula (BII-5), the formula (BII-7), the formula (BII-9) or the formula (BII-11) to the formula (BII-15) are preferable, and the compounds represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15) are more preferable.
Figure BDA0003155996870000211
The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used singly or in combination of 2 or more. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, their content ratio [ compound represented by the formula (BI) ]: the compound represented by the formula (BII) is preferably 5: 95-95: 5, more preferably 20: 80-80: 20.
as (b 2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. Examples of (b 2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.
As (b 3), monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b 3) include tetrahydrofurfuryl acrylate (for example, viscoat V#150, manufactured by Osaka organic chemical industry Co., ltd.), tetrahydrofurfuryl methacrylate, and the like.
The (b) is preferably (b 1) from the viewpoint of enabling the obtained color filter to have higher reliability such as heat resistance and chemical resistance. Further, from the viewpoint of excellent storage stability of the colored curable resin composition, it is more preferable that (b 1-2).
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 ] acrylate 2,6 ]Decane-8-yl ester (which is known as dicyclohexyl (meth) acrylate ". Additionally, tricyclodecyl (meth) acrylate". The term "in this technical field" is also sometimes referred to as tricyclodecyl (meth) acrylate "), [5.2.1.0 ] tricyclo (meth) acrylate 2,6 ](meth) acrylates such as decen-8-yl ester (which is known as dicyclopentenyl (meth) acrylate "), -dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthalene (meth) acrylate, and benzyl (meth) acrylate;
Hydroxy 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-methylcyclo [2.2.1] hept-2-ene, 5-ethylcyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-diethoxy bicyclo [ 2.1] hept-2-ene, 5-diethoxy [ 2.1] bicyclohexa-2-ene, 5-hydroxy-2.1 ] hept-2-ene, 5-hydroxy-2.1-carbonyl, 5-di (hydroxymethyl) bicyclo [ 2.2.2.1 ] hept-2-ene, 5, 6-di (2.1 ] bicyclooxy-carbonyl-2.1 ] bicyclohept-2-ene, 5-bicyclooxy [ 2.1] hept-2-ene;
Styrene, alpha-methylstyrene, m-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.
In the resin [ K1], the proportion of the structural units derived from each unit is preferably 2 to 55 mol% of the structural units derived from (a), 2 to 85 mol% of the structural units derived from (b), 1 to 65 mol% of the structural units derived from (m), more preferably 5 to 50 mol% of the structural units derived from (a), 5 to 70 mol% of the structural units derived from (b), and 5 to 60 mol% of the structural units derived from (m), among all the structural units constituting the resin [ K1 ].
When the ratio of the structural units of the resin [ K1] is within the above range, the absorbance retention of the color filter obtained from the colored curable resin composition can be further improved.
The resin [ K1] can be produced by, for example, a method described in the literature "experimental method for polymer synthesis" (release by 1 st printing 1972, 3 months and 1 days of the same chemical company, 1 st edition, division of the Ministry of Kagaku Kogyo Co., ltd.) or a cited literature described in the literature.
Specifically, the following method is mentioned: the predetermined amounts of (a), (b) and (m), the polymerization initiator, the solvent and the like are added to the reaction vessel, and for example, a deoxidized atmosphere is formed by replacing oxygen with nitrogen, and heating and heat preservation are performed while stirring. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those commonly used in the art can be used. For example, the polymerization initiator may be an azo compound (e.g., 2 '-azobisisobutyronitrile or 2,2' -azobis (2, 4-dimethylvaleronitrile)), or an organic peroxide (e.g., benzoyl peroxide), and the solvent may be any solvent as long as the solvent dissolves the respective monomers, and examples thereof include the solvent (E) described below as the solvent (E) of the colored curable resin composition of the present invention.
The copolymer obtained may be used as it is, a concentrated or diluted solution, or a solid (powder) extracted by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be directly used for preparing the colored curable resin composition of the present invention, and thus the process for producing the colored curable resin composition of the present invention can be simplified.
In the resin [ K2], the proportion of the structural units derived from each unit is preferably 2 to 55 mol% of the structural units derived from (a), 2 to 85 mol% of the structural units derived from (b), 1 to 65 mol% of the structural units derived from (m), 1 to 50 mol% of the structural units derived from (c), more preferably 5 to 50 mol% of the structural units derived from (a), 5 to 70 mol% of the structural units derived from (b), 5 to 60 mol% of the structural units derived from (m), and 2 to 40 mol% of the structural units derived from (c), among all the structural units constituting the resin [ K2 ].
When the ratio of the structural units of the resin [ K2] is within the above range, the absorbance retention of the color filter obtained from the colored curable resin composition can be further improved.
The resin [ K2] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].
In the resin [ K3], the proportion of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a), 40 to 98 mol% of the structural units derived from (m), more preferably 10 to 55 mol% of the structural units derived from (a), and 45 to 90 mol% of the structural units derived from (m), out of all the structural units constituting the resin [ K3 ].
The resin [ K3] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].
In the resin [ K4], the proportion of the structural units derived from each unit is preferably 2 to 55 mol% of the structural units derived from (a), 1 to 65 mol% of the structural units derived from (m), 1 to 50 mol% of the structural units derived from (c), more preferably 5 to 50 mol% of the structural units derived from (a), 5 to 60 mol% of the structural units derived from (m), and 2 to 40 mol% of the structural units derived from (c), among all the structural units constituting the resin [ K1 ].
The resin [ K4] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].
As the first stage, the resin [ K5] was produced in the same manner as the above-mentioned method for producing the resin [ K1], to obtain a copolymer of (b) and (m). As in the above, the copolymer obtained may be used as it is, or may be concentrated or diluted, or may be taken out as a solid (powder) by a method such as reprecipitation.
The ratio of the structural units derived from (b) and (m) is preferably 5 to 95 mol% of the structural units derived from (b) and 5 to 95 mol% of the structural units derived from (m), more preferably 10 to 90 mol% of the structural units derived from (b) and 10 to 90 mol% of the structural units derived from (m), respectively, based on the total mole number of all the structural units constituting the copolymer.
Next, the inside of the flask is brought into an air atmosphere, and a catalyst for the reaction of (b) and (m) (e.g., tris (dimethylaminomethyl) phenol or the like), a catalyst for the reaction of carboxylic acid or carboxylic anhydride and a cyclic ether (e.g., hydroquinone or the like), and the like are placed in the flask, and reacted at 60 to 130 ℃ for 1 to 10 hours, for example, to react carboxylic acid or carboxylic anhydride of (a) with the cyclic ether from (b) of the copolymer of (b) and (m), thereby obtaining resin [ K5].
The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). The cyclic ether has high reactivity, and (b) used in the resin [ K5] is preferably (b 1) from the viewpoint of being less likely to remain unreacted (b).
The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m). The amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m).
The reaction conditions such as the charging method, the reaction temperature, and the time may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. The method of charging and the reaction temperature may 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 resin [ K6] is obtained by further reacting the resin [ K5] with a carboxylic anhydride. The carboxylic anhydride is reacted with the hydroxyl group produced by the reaction of the cyclic ether and the carboxylic acid or 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-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).
Specific examples of the resin (B) include 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid/N-phenylmaleimide copolymer, and 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymerImine copolymer, 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid/N-benzylmaleimide copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] acrylate 2,6 ]Decyl ester/(meth) acrylic acid/N-phenylmaleimide copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester/(meth) acrylic acid/N-benzyl maleimide copolymer and other resins [ K1 ]]；
Glycidyl (meth) acrylate/N-phenylmaleimide copolymer, glycidyl (meth) acrylate/N-cyclohexylmaleimide copolymer, glycidyl (meth) acrylate/benzyl/(meth) acrylic acid/N-benzylmaleimide copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid/N-phenylmaleimide copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid/N-benzylmaleimide copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] acrylate 2,6 ]Decyl ester/(meth) acrylic acid/N-phenylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Resin [ K2 ] such as decyl ester/(meth) acrylic acid/N-benzylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene/N-phenylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene/N-benzylmaleimide copolymer ]；
N-phenylmaleimide/(meth) acrylic acid copolymer, N-cyclohexylmaleimide/(meth) acrylic acid copolymer, N-benzylmaleimide/(meth) acrylic acid copolymer and other resins [ K3];
resins [ K4] such as benzyl (meth) acrylate/(meth) acrylic acid/N-phenylmaleimide copolymer, benzyl (meth) acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, benzyl (meth) acrylate/(meth) acrylic acid/N-benzylmaleimide copolymer, styrene/(meth) acrylic acid/N-phenylmaleimide copolymer, styrene/(meth) acrylic acid/N-benzylmaleimide copolymer, 2-hydroxyethyl (meth) acrylic acid/N-phenylmaleimide/(meth) acrylic acid, 2-hydroxyethyl (meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl (meth) acrylic acid;
resins [ K5] such as resins obtained by reacting a copolymer of (meth) acrylic acid and N-phenylmaleimide/(meth) acrylic acid glycidyl ester, resins obtained by reacting a copolymer of (meth) acrylic acid and N-cyclohexylmaleimide/(meth) acrylic acid glycidyl ester, and resins obtained by reacting a copolymer of (meth) acrylic acid and N-benzylmaleimide/(meth) acrylic acid glycidyl ester;
Resins obtained by reacting a copolymer of (meth) acrylic acid and N-phenylmaleimide/(meth) acrylic acid glycidyl ester with tetrahydrophthalic anhydride, resins obtained by reacting a copolymer of (meth) acrylic acid and N-cyclohexylmaleimide/(meth) acrylic acid glycidyl ester with tetrahydrophthalic anhydride, resins obtained by reacting a copolymer of (meth) acrylic acid and N-benzylmaleimide/(meth) acrylic acid glycidyl ester with tetrahydrophthalic anhydride, and the like [ K6 ].
Among them, the resin (B) is preferably a resin [ K1] to a resin [ K4], and more preferably a resin [ K1] and a resin [ K2].
The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and even more preferably 5000 to 30000. When the molecular weight is within the above range, the hardness of the color filter tends to be high, the residual film ratio tends to be high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be high.
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 70mg-KOH/g or more, more preferably 90mg-KOH/g or more, still more preferably 110mg-KOH/g or more, preferably 220mg-KOH/g or less, more preferably 210mg-KOH/g or less, still more preferably 200mg-KOH/g or less, in terms of solid matter conversion. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.
The content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, and even more preferably 17 to 65% by mass, based on the total amount of solid components. When the content of the resin (B) is within the above range, a colored pattern may be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.
The content of the resin (B) is preferably 10 to 95 parts by mass, more preferably 20 to 90 parts by mass, and even more preferably 30 to 85 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the resin (B) is within the above range, the absorbance retention of the obtained color filter is further improved.
The content of the resin (B) is preferably 55 to 95 parts by mass, and more preferably 60 to 90 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the resin (B) is within the above range, the absorbance retention of the obtained color filter is significantly improved.
When the content of the resin (B) is 10 to 60 parts by mass, preferably 20 to 55 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), the absorbance retention and the brightness of the obtained color filter are improved.
< polymerizable Compound (C) >)
The polymerizable compound (C) is a compound polymerizable by a living radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and is 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 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 even more preferably 10 to 55% by mass, based on the total amount of solid components. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.
Polymerization initiator (D) >)
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid, or the like under the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator generating active radicals include O-acyl oxime compounds, alkyl phenone compounds, triazine compounds, acyl phosphine oxide compounds, and bisimidazole compounds.
Examples of the O-acyloxime compound include O-acyloxime compounds having a diphenyl sulfide 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-cyclohexylpropan-1-one-2-imine; o-acyl oxime compounds having a carbazole skeleton such as 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-dioxacyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine; o-acyl oxime compounds having a fluorene skeleton such as 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone-O-acetoxime; etc. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (both of them are manufactured by BASF), N-1919 (manufactured by ADEKA), and DFI-091 (manufactured by Daito Chemix Co., ltd.) can be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-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-dioxacyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine and 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone-O-acetoxime. When these O-acyloxime compounds are used, there is a tendency to obtain a color filter with high brightness.
Examples of the alkylbenzene ketone compound include 2-methyl-2-morpholino-1- (4-methylsulfanyl phenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, and benzil dimethyl ketal. Commercial products such as Irgacure (registered trademark) 369, 907, 379 (all of them are manufactured by BASF corporation) may 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) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine.
Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and the like. Commercial products such as Irgacure 819 (registered trademark) manufactured by BASF corporation can be used.
Examples of the bisimidazole compound include 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenylbisimidazole and 2,2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbisimidazole (for example, with reference to JP-A6-75372, JP-A6-75373 and the like), 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetra (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent publication No. 48-38403, japanese patent application laid-open No. 62-174204, etc.), biimidazole compounds in which phenyl groups at the 4,4', 5' -positions are substituted with carboalkoxy groups (for example, refer to Japanese patent application laid-open No. 7-10913, etc.), and the like.
Examples of the polymerization initiator for acid production include 4-hydroxyphenyldimethyl sulfonium p-toluene sulfonate, 4-hydroxyphenyldimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluene sulfonate, 4-acetoxyphenyl methyl benzyl sulfonium hexafluoroantimonate, triphenylsulfonium p-toluene sulfonate, triphenylsulfonium hexafluoroantimonate, and diphenyliodo
Figure BDA0003155996870000301
P-toluenesulfonate, diphenyliodo->
Figure BDA0003155996870000302
Hexafluoroantimonate and the like->
Figure BDA0003155996870000303
Salts, nitrobenzyl tosylate, benzoin tosylate, 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' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, and the like; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, a titanocene compound, and the like.
As the polymerization initiator (D), a polymerization initiator containing at least 1 selected from the group consisting of an O-acyl oxime compound, an alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound is preferable, and a polymerization initiator containing an O-acyl oxime compound is more preferable.
The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, 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). When 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 shortened, so that the productivity of the color filter is improved.
Solvent (E) >, solvent (E)
The solvent (E) is not particularly limited, and solvents generally used in this field can be used. For example, the number of the cells to be processed, 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-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a solvent containing-COO-in the molecule, and a solvent containing-COO-in the molecule an ether solvent (a solvent containing-O-and not-COO-in the molecule) ether ester solvents (solvents containing-COO-and-O-in the molecule).
Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and gamma-butyrolactone.
Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-di
Figure BDA0003155996870000311
Alkyl, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, 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, 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, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
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, and mesitylene.
Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
Among the above solvents, an organic solvent having a boiling point of 120 to 180℃at 1atm is preferable in terms of coatability and drying property. 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, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.
The content of the solvent (E) 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 components of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, flatness at the time of coating becomes good, and the color density at the time of forming a color filter is not insufficient, so that display characteristics tend to become good.
< leveling agent (F) >)
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. They 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 DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by Dow Corning Toray co., ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by the singe chemical industry co., ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan co., ltd.) and the like are exemplified.
The fluorine-based surfactant includes surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD FC430, FLUORAD FC431 (manufactured by Sumitomo 3M (Inc.), MEGAFAC F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Inc.), F-top EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi (Inc.), surflon S381, surflon S382, surflon SC101, surflon SC105 (manufactured by Asahi Nitro) and E5844 (manufactured by Mitsubishi gold fine chemical corporation).
Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there are exemplified MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (DIC corporation), and the like.
The content of the leveling agent (F) is preferably 0.001 to 0.2 mass%, more preferably 0.002 to 0.2 mass%, and even more preferably 0.005 to 0.2 mass% based on the total amount of the colored curable resin composition. The content of the dispersant is not included in the content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.
< other Components >)
The colored curable resin composition of the present invention may contain, if necessary, additives known in the art such as a polymerization initiator, a filler, other polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent.
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-sulfanylpropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, and N-phenyl-3-aminopropyl triethoxysilane.
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), and if necessary, the solvent (E), the leveling agent (F), and other components.
Method for producing color filter
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include photolithography, inkjet method, and printing method. Among them, photolithography is preferable. Photolithography is a method of forming a colored composition layer by applying the colored curable resin composition to a substrate and drying the same, exposing the colored composition layer to light through a photomask, and developing the same. In the photolithography, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and may be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30. Mu.m, preferably 0.1 to 20. Mu.m, and more preferably 0.5 to 6. Mu.m.
As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like, silicon, a substrate having aluminum, silver/copper/palladium alloy thin films 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 by using a known or conventional apparatus and conditions. For example, the production can be performed as follows.
First, the colored curable resin composition is applied onto a substrate, and then dried by heating (prebaking) and/or drying under reduced pressure, thereby removing volatile components such as a solvent and drying the same to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit, and a spin coating method.
The temperature at which the heat drying is carried out is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
In the case of drying under reduced pressure, it is preferable to carry out the drying under a pressure of 50 to 150Pa at a temperature of 20 to 25 ℃.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.
Next, the coloring composition layer is exposed to light through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is 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 of less than 350nm may be cut off using a filter that cuts off this wavelength region, or light of around 436nm, around 408nm, or around 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 are cited.
In order to uniformly irradiate the entire exposure surface with parallel light and to precisely align the photomask with the substrate on which the coloring composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.
The exposed coloring composition layer is brought into contact with a developer and developed, whereby a coloring pattern is formed on the substrate. By development, the unexposed portion of the coloring composition layer is dissolved in a developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and 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. The developer may contain a surfactant.
The development method may be any of spin immersion (pad method), dipping, spraying, and the like. Further, the substrate can be inclined at an arbitrary angle during development.
After development, washing with water is preferable.
Further, the resulting colored pattern is preferably post-baked. The post-baking temperature is preferably 150 to 250 ℃, more preferably 160 to 235 ℃. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, the% and parts indicating the content or the amount used are mass-based unless otherwise specified.
In the following synthesis examples, compounds were identified by NMR (JNM-EX-270 (manufactured by Japanese electronics Co., ltd.).
(colorant Synthesis example 1)
10.0 parts of 2, 4-dimethylaniline (manufactured by Tokyo chemical industries, ltd.), 17.0 parts of 2-ethylhexanoate bromide (manufactured by Tokyo chemical industries, ltd.) and 44.0 parts of tetrabutylammonium bromide (manufactured by photochemical industries, ltd.) were mixed. The resulting mixture was stirred at 90℃for 8 hours. After completion of the reaction, 50 parts of a 10% aqueous sodium hydrogencarbonate solution was added, 100 parts of ethyl acetate was added, and the aqueous layer was discarded. The solvent was distilled off after repeating the washing with water and 10% hydrochloric acid 2 times. 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).
Figure BDA0003155996870000351
A compound represented by the formula (a-1) 1 H-NMR (270 MHz, delta value (ppm, TMS reference), DMSO-d 6 )
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 above-obtained formula (a-1), 2.2 parts of 3-bromophenol (manufactured by Tokyo chemical industry Co., ltd.), 0.015 parts of palladium acetate, 3.2 parts of sodium t-butoxide (manufactured by Tokyo chemical industry Co., ltd.), 0.055 parts of tri-t-butylphosphine (manufactured by Tokyo chemical industry 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 repeating the washing operation with water 2 times, the solvent was distilled off. The residue was purified by silica gel column 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).
Figure BDA0003155996870000361
A compound represented by the formula (a-2) 1 H-NMR (270 MHz, delta value (ppm, TMS reference), DMSO-d 6 )
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 industry 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 completion of the reaction, the solvent was distilled off, 15 parts of acetic acid was added thereto, and then, 100 parts of 18% saline solution was added dropwise thereto, and the precipitated solid was filtered off. The filtered solid was washed with hexane. The obtained solid was dried under reduced pressure at 60℃for 24 hours to obtain 4.9 parts of a compound represented by the formula (AII-10).
Figure BDA0003155996870000362
A compound represented by the formula (AII-10) 1 H-NMR (270 MHz, delta value (ppm, TMS reference), DMSO-d 6 )
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)
The structure of the compound was confirmed by MASS spectrometry (LC; model 1200 by Agilent; model LC/MSD by Agilent).
(colorant Synthesis example 2)
50 parts of m-bromophenol (manufactured by Tokyo chemical industries, ltd.) and 30 parts of imidazole (manufactured by Tokyo chemical industries, ltd.) were dissolved in 500 parts of methylene chloride (manufactured by Kanto chemical industries, ltd.) and cooled to 0 ℃, followed by dropwise addition of 48 parts of t-butyldimethylchlorosilane (manufactured by Tokyo chemical industries, ltd.). After the completion of the dropwise addition, the temperature was raised to 23℃and the mixture was stirred for 16 hours. After the completion of the reaction, the organic layer was extracted with water, and after concentrating the solvent, the mixture was separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by the formula (a-3).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 287.0
Accurate molecular weight: +286.0
Figure BDA0003155996870000371
15 parts of 2, 4-dimethylaniline (manufactured by Tokyo chemical Co., ltd.), 35 parts of a compound represented by the formula (a-3), 14 parts of potassium hydroxide (manufactured by Wako pure chemical industries, ltd.), 2 parts of tetrabutylammonium bromide (manufactured by Tokyo chemical Co., ltd.), and 0.6 part of bis (tri-t-butylphosphine) palladium (0) (manufactured by Aldrich Co., ltd.) were dissolved in 250 parts of toluene (manufactured by Kanto chemical Co., ltd.) and 15 parts of water, and the mixture was heated to 90℃and stirred for 30 minutes. After the completion of the reaction, the organic layer was extracted and concentrated, and then separated and purified by silica gel column chromatography to obtain 14 parts of the compound represented by the formula (a-4).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 328.3
Accurate molecular weight: +327.2
Figure BDA0003155996870000381
14 parts of the compound represented by the formula (a-4) and 10 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo chemical Co., ltd.) were dissolved in 255 parts of toluene (manufactured by Kao chemical Co., ltd.), and the mixture was heated to 90℃and stirred for 1 hour. After the completion of the reaction, the organic layer was extracted with water, and after concentrating the solvent, the mixture was separated and purified by silica gel column chromatography to obtain 15 parts of the compound represented by the formula (a-5).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 442.3
Accurate molecular weight: +441.2
Figure BDA0003155996870000382
15 parts of a compound represented by the formula (a-5) was dissolved in 150 parts of tetrahydrofuran (manufactured by Kabushiki Kaisha), cooled to 0℃and 15 parts of a tetra-n-butylammonium fluoride 1M tetrahydrofuran solution (manufactured by Tokyo chemical Co., ltd.) were added dropwise. After the completion of the dropwise addition, the temperature was raised to 23℃and stirred for 2 hours. After the completion of the reaction, the solvent was concentrated, and the mixture was separated and purified by silica gel column chromatography to obtain 12 parts of the compound represented by the formula (a-6).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 328.2
Accurate molecular weight: +327.2
Figure BDA0003155996870000383
12 parts of a compound represented by the formula (a-6) was dissolved in 240 parts of tetrahydrofuran (manufactured by Kabushiki Kaisha), cooled to 0℃and 180 parts of a borane 1M tetrahydrofuran solution (manufactured by Kaisha). After the completion of the dropwise addition, the mixture was stirred for 30 minutes, water was added thereto, tetrahydrofuran was concentrated, and the organic layer was extracted with ethyl acetate. After concentrating the solvent, separation and purification were performed by silica gel column chromatography to obtain 6 parts of a compound represented by the formula (a-7).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 314.2
Accurate molecular weight: +313.2
Figure BDA0003155996870000391
6 parts of a compound represented by the formula (a-7) and 0.2 part of lithium hydroxide monohydrate (and Wako pure chemical industries, ltd.) were dissolved in 20 parts of methanol (manufactured by Kanto chemical Co., ltd.), 20 parts of tetrahydrofuran (manufactured by Kanto chemical Co., ltd.) and 10 parts of water, and stirred at 23℃for 1 hour. After the completion of the reaction, the organic solvent was concentrated, and the organic layer was extracted with ethyl acetate, and then separated and purified by silica gel column chromatography to obtain 4 parts of the compound represented by the formula (a-8).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 300.2
Accurate molecular weight: +299.2
Figure BDA0003155996870000392
4 parts of a compound represented by the formula (a-8) and 0.8 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (manufactured by Wako pure chemical industries, ltd.) were dissolved in 40 parts of toluene (manufactured by Kanto Chemie Co., ltd.) and 10 parts of n-butanol (manufactured by Kanto Chemie Co., ltd.) and the temperature was raised to 140℃and stirred for 2 hours. After concentrating the solvent, separation and purification were performed by silica gel column chromatography to obtain 1.6 parts of the compound represented by the formula (AII-17).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 677.3
Accurate molecular weight: +676.3
Figure BDA0003155996870000401
(colorant Synthesis example 3)
50 parts of 3-bromoanisole (manufactured by Tokyo chemical industries, ltd.) was dissolved in 36.1 parts of 2,4, 6-trimethylaniline (manufactured by Tokyo chemical industries, ltd.) and 434 parts of toluene (manufactured by Kato chemical industries, ltd.) to prepare a solution, and 30 parts of potassium hydroxide (manufactured by Kato chemical industries, ltd.), 25 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo chemical industries, ltd.) and 1.4 parts of bis (tri-t-butylphosphine) palladium (0) (manufactured by Tokyo chemical industries, ltd.) were mixed with the solution. After heating to 90℃and stirring for 5 hours, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 52.1 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 50.2 parts of a compound represented by the formula (a-9).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 242.3
Accurate molecular weight: +241.2
Figure BDA0003155996870000402
33 parts of a compound represented by the formula (a-9), 26.8 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo chemical Co., ltd.) and 286 parts of toluene (manufactured by Kagaku chemical Co., ltd.) were mixed and heated at 100℃for 16 hours with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 30.7 parts of the compound represented by the formula (a-10).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 356.2
Accurate molecular weight: +355.2
Figure BDA0003155996870000411
10 parts of a compound represented by the formula (a-10) was dissolved in 95 parts of methylene chloride (manufactured by Kabushiki Kaisha chemical Co., ltd.) and cooled to 0℃with stirring. 28.2 parts of boron tribromide (Fuji film and Wako pure chemical industries, ltd.) was added dropwise while stirring. After the completion of the dropwise addition, the temperature was slowly raised and stirred at 10℃for 4 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed to distill off the solvent, whereby 9.1 parts of a crude product was obtained. Wherein 48% of the compound represented by the formula (a-11) and 36% of the compound represented by the formula (a-12) are contained.
Figure BDA0003155996870000412
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ] ] + 342.2
Accurate molecular weight: +341.2
Figure BDA0003155996870000413
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 328.1
Accurate molecular weight: +327.2
A solution of 13.2 parts of thionyl chloride (manufactured by Tokyo chemical Co., ltd.) in 72 parts of methanol (manufactured by Kabushiki Kaisha chemical Co., ltd.) was cooled to 0℃and 9.1 parts of the obtained crude product comprising the compound represented by the formula (a-11) and the compound represented by the formula (a-12) was added with stirring. The reaction was allowed to react for 16 hours at room temperature. The solvent was distilled off under reduced pressure to obtain 8.3 parts of a crude product containing the compound represented by the formula (a-11). The obtained crude product was purified by silica gel column chromatography to obtain 7.4 parts of a compound represented by the formula (a-11).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 342.2
Accurate molecular weight: +341.2
2 parts of a compound represented by the formula (a-11), 26.3 parts of a borane 1M tetrahydrofuran solution (manufactured by Kabushiki Kaisha, kaisha) and 18 parts of tetrahydrofuran (manufactured by Kabushiki Kaisha) were mixed at 0℃and heated to 10℃and stirred for 5 hours. After the reaction, water was added to quench the reaction, and the mixture was extracted with an organic solvent. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 1.64 parts of the compound represented by the formula (a-13).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 300.2
Accurate molecular weight: +299.2
Figure BDA0003155996870000421
2.5 parts of the compound represented by the formula (a-13) and 0.55 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Fuji photo-active pharmaceutical ingredients, manufactured by Fuji photo-co., ltd.) were dissolved in 50 parts of toluene (manufactured by Kao chemical Co., ltd.) and 50 parts of n-butanol (manufactured by Kao chemical Co., ltd.) and heated at 110℃for 6 hours with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 2.7 parts of a compound represented by the formula (AII-18).
And (3) identification: (mass spectrometry) ionization mode = esi+: m/z= [ m+h ]] + 677.4
Accurate molecular weight: +676.4
Figure BDA0003155996870000422
Synthesis example 1 of resin
A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere, and 223 parts of 3-methoxybutanol and 110 parts of 3-methoxybutyl acetate were added thereto, followed by heating to 70℃with stirring. Next, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decan-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0 2,6 ]180 parts of a mixture of decane-9-yl acrylic acid esters (mixing ratio 1:1), 54 parts of acrylic acid, 67 parts of N-cyclohexylmaleimide and 180 parts of 3-methoxybutanol.
On the other hand, a mixed solution in which 6 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 150 parts of 3-methoxybutyl acetate was added dropwise to the flask over 5 hours using another dropping pump. After the completion of the addition of the polymerization initiator, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a solution of the copolymer (resin (B-1)) having a B-type viscosity (23 ℃) of 130mPas and a solid content of 30.9%. The weight average molecular weight (Mw) of the resulting copolymer was 8800, the acid value in terms of solid content was 137mg-KOH/g, and the dispersity was 1.76. The resin (B-1) has the following structural units.
Figure BDA0003155996870000431
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.
The device comprises: HLC-8120GPC (manufactured by Tosoh Co., ltd.)
Column: TSK-GELG2000HXL
Column temperature: 40 DEG C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
Concentration of solid component in the detection liquid: 0.001 to 0.01 mass%
Sample injection amount: 50 mu L
A detector: RI (RI)
Calibration standard substance: TSK STANDARD PolySTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corp.)
The dispersion was defined as the ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above.
Synthesis example 2 of resin
A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere, and 185 parts of 3-methoxybutanol and 216 parts of propylene glycol monomethyl ether acetate were added thereto, followed by heating to 70℃with stirring. Next, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decan-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0 2,6 ]149 parts of a mixture of decane-9-yl acrylic acid esters (mixing ratio 1:1), 45 parts of acrylic acid, N-cyclohexylmaleimide 56158 parts of 3-methoxybutanol.
On the other hand, a mixed solution obtained by dissolving 8 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator in 183 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask using another dropping pump for 5 hours. After the completion of the addition of the polymerization initiator, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-2)) solution having a type B viscosity (23 ℃) of 22mPas and a solid content of 26.1%. The weight average molecular weight (Mw) of the resulting copolymer was 8900, the acid value in terms of solid content was 143mg-KOH/g, and the dispersity was 1.92. The resin (B-2) has the same structural unit as the resin (B-1).
(Synthesis example 3 of resin)
A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere, and 248 parts of propylene glycol monomethyl ether acetate was added thereto, followed by stirring and heating to 80 ℃. Next, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decan-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0 2 ,6 ]52 parts of a mixture of decane-9-yl acrylic acid esters (mixing ratio 1:1), 42 parts of acrylic acid, 141 parts of N-cyclohexylmaleimide and 352 parts of propylene glycol monomethyl ether acetate.
On the other hand, a mixed solution in which 20 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 145 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump. After the completion of the addition of the polymerization initiator, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B-3)) having a B-type viscosity (23 ℃) of 18mPas and a solid content of 25.7%. The weight average molecular weight (Mw) of the resulting copolymer was 8000, the acid value in terms of solid content was 119mg-KOH/g, and the dispersity was 2.09. The resin (B-3) has the same structural unit as the resin (B-1).
(Synthesis example 4 of resin)
A proper amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with nitrogen191 parts of propylene glycol monomethyl ether acetate and 79 parts of propylene glycol monomethyl ether were added to the atmosphere, and the mixture was heated to 80℃while stirring. Next, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decan-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0 2,6 ]112 parts of a mixture of decane-9-yl acrylic acid esters (mixing ratio 1:1), 80 parts of acrylic acid, 128 parts of N-cyclohexylmaleimide and 258 parts of propylene glycol monomethyl ether.
On the other hand, a mixed solution in which 7 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 145 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump. After the completion of the addition of the polymerization initiator, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a solution of the copolymer (resin (B-4)) having a B-type viscosity (23 ℃) of 75mPas and a solid content of 34.7%. The weight average molecular weight (Mw) of the resulting copolymer was 8800, the acid value in terms of solid content was 181mg-KOH/g, and the dispersity was 2.20. The resin (B-4) has the same structural unit as the resin (B-1).
(Synthesis example 5 of resin)
A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere, and 149 parts of diethylene glycol ethyl methyl ether and 110 parts of propylene glycol monomethyl ether were added thereto, followed by stirring and heating to 70 ℃. Next, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decan-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0 2,6 ]45 parts of a mixture of decane-9-yl acrylic acid esters (mixing ratio: 1:1), 75 parts of acrylic acid, 180 parts of N-cyclohexylmaleimide and 309 parts of diethylene glycol methyl ether.
On the other hand, a mixed solution in which 5 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator was dissolved in 127 parts of propylene glycol monomethyl ether was added dropwise to the flask using another dropping pump for 5 hours. After the completion of the addition of the polymerization initiator, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature, whereby a copolymer (resin (B-5)) having a type B viscosity (23 ℃) of 66mPas and a solid content of 34.5% was obtained. The weight average molecular weight (Mw) of the resulting copolymer was 9000, the acid value in terms of solid content was 183mg-KOH/g, and the dispersity was 2.06.
The resin (B-5) has the same structural unit as the resin (B-1).
(Synthesis example 6 of resin)
A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, followed by stirring and heating to 85 ℃. Next, 19 parts of methacrylic acid and 3, 4-epoxytricyclo [5.2.1.0 were added dropwise to the flask over about 5 hours using a dropping pump 2,6 ]Decan-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0 2,6 ]171 parts of decane-9-yl acrylate (mixing ratio: 1:1) was dissolved in 40 parts of propylene glycol monomethyl ether acetate.
On the other hand, a solution in which 26 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 120 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 5 hours using another dropping pump. After the completion of the addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature, to obtain a solution of the copolymer (resin (B-6)) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-2) was 8000, the dispersity was 1.98, and the acid value in terms of solid content was 53mg-KOH/g. The resin (B-6) has the following structural units.
Figure BDA0003155996870000461
Examples 1 to 9 and comparative example 1
[ preparation of colored curable resin composition ]
The components were mixed so as to have the compositions shown in table 2, to obtain a colored curable resin composition.
Figure BDA0003155996870000471
In table 2, each component represents the following compound.
Colorant (A-1): a compound represented by the formula (AII-10)
Colorant (A-2): a compound represented by the formula (AII-17)
Colorant (A-3): a compound represented by the formula (AII-18)
Resin (B-1): resin (B-1) (solid content conversion)
Resin (B-2): resin (B-2) (solid content conversion)
Resin (B-3): resin (B-3) (solid content conversion)
Resin (B-4): resin (B-4) (solid content conversion)
Resin (B-5): resin (B-5) (solid content conversion)
Resin (B-6): resin (B-6) (solid content conversion)
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Japanese chemical Co., ltd.)
Polymerization initiator (D-1): n-1919 (ADEKA Co., ltd.; O-acyl oxime Compound)
Polymerization initiator (D-2): DFI-091 (O-acyl oxime Compound, manufactured by Daito Chemix Co., ltd.)
Polymerization initiator (D-3): n-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF corporation; O-acyl oxime Compound)
Solvent (E-1): 4-hydroxy-4-methyl-2-pentanone
Solvent (E-2): propylene glycol monomethyl ether acetate
Solvent (E-3): 3-Methoxybutyl acetate
Solvent (E-4): 3-methoxy-1-butanol
Solvent (E-5): diethylene glycol methyl ethyl ether
Solvent (E-6): propylene glycol monomethyl ether
Leveling agent (F-1): polyether modified silicone oil (Dow Corning Toray Co., ltd. "Toray Silicone SH 8400")
[ production of colored coating film ]
The colored curable resin composition was applied to a 5cm square glass substrate (EAGLE 2000; manufactured by Corning) by spin coating so that the film thickness after post-baking was 2.0. Mu.m, and then baked at 100℃for 3 minutes to form a colored composition layer. After cooling, the film was subjected to an exposure machine (TME-150 RSK; TOPCON, manufactured by TOPCON Co., ltd.) at a rate of 100mJ/cm under an atmospheric atmosphere 2 The coloring composition layer was irradiated with light at an exposure dose (365 nm basis). Thereafter, the resulting film was post-baked in an oven at 230℃for 30 minutes to obtain a colored coating film.
[ evaluation of Process Property ]
1. Absorbance retention
The maximum absorbance was obtained from the spectroscopic spectra measured after the pre-baking and after the post-baking, and the retention rate of the maximum absorbance was calculated from the following formula. The results are shown in Table 3.
Absorbance retention (Δabs.max) =maximum absorbance after post-bake/maximum absorbance after pre-bake
The higher the absorbance retention means higher adaptability in the film forming process.
Figure BDA0003155996870000501
2. Chromaticity of
The chromaticity of the colored coating film formed from the colored curable resin compositions of examples 1 and 3 and comparative example 1 was determined from the spectral spectrum measured by a colorimeter (OSP-SP-200; manufactured by Olympus Co., ltd.) and the characteristic function of the C light source, and xy chromaticity coordinates (x, Y) and Y in the XYZ color system of CIE were obtained. The results are shown in Table 4. The larger the value of Y, the higher the luminance.
TABLE 4
Example 1 Example 3 Comparative example 1
Y 93.6 94.4 90.7
Industrial applicability
According to the colored resin composition of the present invention, a color filter having excellent absorbance retention can be formed.

Claims (3)

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,
the colorant is a colorant comprising a squaric acid represented by formula (I)
Figure FDA0004100748010000013
The colorant of the dye is used as a coloring agent,
the resin is a resin containing a structural unit derived from N-substituted maleimide, and is any one of the following resins [ K1] and [ K2],
the resin [ K1] is a copolymer composed of a structural unit derived from at least 1 monomer (a) selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond, and a structural unit derived from N-substituted maleimide (m);
The resin [ K2] is a copolymer composed of a structural unit derived from the (a), a structural unit derived from the (b), a structural unit derived from the (m), and a structural unit derived from a monomer (c) copolymerizable with the (a) and different from the (a), (b) and (m);
the content of the resin is 55 to 95 parts by mass relative to 100 parts by mass of the total amount of the resin and the polymerizable compound,
Figure FDA0004100748010000011
in the formula (I) of the present invention,
R 1 ～R 4 each 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, an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group,
R 5 ～R 8 each independently represents a hydrogen atom or a hydroxyl group,
Ar 1 and Ar is a group 2 Each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i),
Figure FDA0004100748010000012
in the formula (i), the amino acid sequence of the formula (i),
R 12 represents 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, m represents an integer of 0 to 5, an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group, and when m is 2 or more, a plurality of R' s 12 And each may be the same or different, represents a bonding site to a nitrogen atom,
R 9 And R is 10 Each 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), and an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group.
2. A color filter formed from the colored curable resin composition according to claim 1.
3. A display device comprising the color filter of claim 2.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013037348A (en) * 2011-07-08 2013-02-21 Sumitomo Chemical Co Ltd Colored photosensitive resin composition
CN104513510A (en) * 2013-09-26 2015-04-15 住友化学株式会社 Coloring and solidifying resin composition
JP2016104860A (en) * 2014-11-25 2016-06-09 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2016117858A (en) * 2014-12-22 2016-06-30 住友化学株式会社 Colored curable resin composition
JP2016170282A (en) * 2015-03-12 2016-09-23 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Colored curable resin composition
JP2017008287A (en) * 2014-11-25 2017-01-12 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2018081210A (en) * 2016-11-16 2018-05-24 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Coloration curable resin composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9350676B2 (en) 2012-12-11 2016-05-24 Qualcomm Incorporated Method and apparatus for classifying flows for compression
JP5869536B2 (en) 2013-08-08 2016-02-24 Ｋｙｂ株式会社 Manufacturing data management method for casting products

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013037348A (en) * 2011-07-08 2013-02-21 Sumitomo Chemical Co Ltd Colored photosensitive resin composition
CN104513510A (en) * 2013-09-26 2015-04-15 住友化学株式会社 Coloring and solidifying resin composition
JP2016104860A (en) * 2014-11-25 2016-06-09 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2017008287A (en) * 2014-11-25 2017-01-12 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2016117858A (en) * 2014-12-22 2016-06-30 住友化学株式会社 Colored curable resin composition
JP2016170282A (en) * 2015-03-12 2016-09-23 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Colored curable resin composition
JP2018081210A (en) * 2016-11-16 2018-05-24 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Coloration curable resin composition

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