CN113383021B - Colored curable resin composition - Google Patents

Colored curable resin composition Download PDF

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CN113383021B
CN113383021B CN201980091164.0A CN201980091164A CN113383021B CN 113383021 B CN113383021 B CN 113383021B CN 201980091164 A CN201980091164 A CN 201980091164A CN 113383021 B CN113383021 B CN 113383021B
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CN113383021A (en
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土谷崇夫
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/06—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules
    • C08F291/10—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules on to macromolecules containing epoxy radicals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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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  • Materials For Photolithography (AREA)
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Abstract

The invention provides a colored curable resin composition capable of forming a color filter with excellent absorbance retention. The present invention relates to a colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant is a colorant comprising a squarylium dye represented by the formula (I), and the acid value of the resin in terms of solid content is 100 to 200mg-KOH/g.

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 and CMOS sensors are manufactured from colored resin compositions. As a colorant used in such a colored resin composition, squarylium dyes are known (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
The invention provides a colored curable resin composition capable of forming a color filter with 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 an onium squarate dye represented by the formula (I),
the acid value of the resin is 100 to 200mg-KOH/g in terms of solid content.
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).
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 contains an onium squarate dye represented by the formula (I) (hereinafter, sometimes referred to as a compound (I)).
The acid value of the resin is 100-200 mg-KOH/g in terms of solid content.
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.
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. To form the 1-valent saturated hydrocarbon groupAn oxygen atom or a sulfur atom may be inserted between carbon atoms of (a).
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).
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.]
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 ring having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and adamantylAnd a hydrocarbon group.
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; examples of the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which has a substituent include alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl groups and ethoxycarbonyl groups, and examples thereof include groups represented by the following formulas. In the following formula, the bonding site is represented.
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 bonding site is represented.
As R 12 Examples of the 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms include vinyl, 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.
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 end, the linear alkyl group having 3 to 5 carbon atoms which has a carboxyl group at the end, 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 a 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.
In the formula (I) of the present invention,
will beThe radicals indicated are designated X 1 And is combined with
Will beThe 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.
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 1), a compound represented by the formula (pt 2), and a compound represented by the formula (pt 3). 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).
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).
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 dyes include compounds classified into substances having a color tone other than pigments in the color index (The Society of Dyers and Colourists publication) and known dyes described in dyeing guidelines (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, 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. 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, 90:1, 91, 92, 93, 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, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 280, 290, 278, 296, 315, 340, 1:340;
c.i. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 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. 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 of c.i. mediator green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc.,
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 as 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, 60 etc. blue pigment;
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 Lubrizol 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 (B) is an alkali-soluble resin having a predetermined acid value. The colored curable resin composition of the present invention contains a compound represented by the formula (I) and a resin (B) having a predetermined acid value, whereby the absorbance retention of the color filter is improved.
The resin (B) includes the following resins [ K1] to [ K6 ].
A resin [ K1]: a copolymer having a structural unit derived from at least 1 monomer (a) (hereinafter sometimes referred to as "(a)") selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond;
a resin [ K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) (which is different from (a) and (b) (hereinafter sometimes referred to as "(c)") copolymerizable with (a);
a resin [ K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
a resin [ K4] is a copolymer having a structural unit derived from (a), a structural unit obtained by adding a structural unit derived from (a) to a structural unit derived from (b), and a structural unit derived from (c);
a resin [ K5] is a copolymer having a structural unit derived from (a), a structural unit derived from (b) added with a structural unit derived from (a), and a structural unit derived from (c);
The resin [ K6] is a copolymer comprising a structural unit derived from (a), a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride, and a structural unit derived from (c).
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-, and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-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 acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride; unsaturated mono- [ (meth) acryloyloxyalkyl ] esters of polycarboxylic acids having 2 or more members such as succinic acid mono [ 2- (meth) acryloyloxyethyl ester ], phthalic acid mono [ 2- (meth) acryloyloxyethyl ester ], and the like; 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 same meaning applies to the "(meth) acryl" and "(meth) acrylate" and the like.
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 (registered trademark) 2000, (product of Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer (registered trademark) A400, (product of Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer (registered trademark) M100, (product of Daicel)), a compound represented by the formula (BI), and a compound represented by the formula (BII).
[ 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, -R g －、*－R g －O－、*－R g -S-or-R g －NH－。
R g Represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents the 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 A single bond, methylene, ethylene, or-CH may be preferably mentioned 2 -O-and-CH 2 CH 2 O-, more preferably a single bond, -CH 2 CH 2 -O- (x) 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, compounds represented by the formula (BI-1), the formula (BI-3), the formula (BI-5), the formula (BI-7), the formula (BI-9) or the formula (BI-11) to the formula (BI-15) are preferable, and compounds represented by the formula (BI-1), the formula (BI-7), the formula (BI-9) or the formula (BI-15) are more preferable.
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.
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, the content ratio of the compound represented by the formula (BI) to the compound represented by the formula (BII) is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.
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.
As (b), in view of enabling higher reliability such as heat resistance and chemical resistance of the obtained color filter, it is preferable to use (b 1). Further, from the viewpoint of excellent storage stability of the color 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 dicyclopentyl (meth) acrylate ". Additionally, it is sometimes referred to as tricyclodecyl (meth) acrylate"), [5.2.1.0 ] tricyclo (meth) acrylate, as a conventional name in this technical field) 2,6 ](meth) acrylic esters 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, naphthyl (meth) acrylate, benzyl (meth) acrylate, and the like, as a conventional name;
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;
N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaprooate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide;
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.
As (c), styrene, vinyl toluene, N-substituted maleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoints of copolymerization reactivity and heat resistance.
In the resin [ K1], the ratio 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 (b), more preferably 10 to 50 mol% of the structural units derived from (a), and 50 to 90 mol% of the structural units derived from (b), 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, a method is exemplified in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and a deoxidized atmosphere is produced by substituting oxygen with nitrogen, for example, 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 ratio of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a), 2 to 95 mol% of the structural units derived from (b), 1 to 65 mol% of the structural units derived from (c), more preferably 5 to 50 mol% of the structural units derived from (a), 5 to 80 mol% of the structural units derived from (b), and 5 to 60 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 ratio 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 (c), more preferably 10 to 50 mol% of the structural units derived from (a), and 50 to 90 mol% of the structural units derived from (c), among all the structural units constituting the resin [ K3 ].
When the ratio of the structural units of the resin [ K3] 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 [ K3] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].
The resin [ K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms to the carboxylic acid and/or carboxylic anhydride of (a). Further, by making the molar amount of (b) smaller than (a), a part of the structural unit derived from (a) can be left without reacting with (b).
First, copolymers of (a) and (c) are produced in the same manner as described in the method for producing the resin [ K1 ]. In this case, the ratio of the structural units derived from each unit is preferably the same ratio as the ratio of the structural units derived from each unit as exemplified in the resin [ K3 ].
Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms of (b).
After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air by nitrogen, and a reaction catalyst (e.g., tris (dimethylaminomethyl) phenol) or a reaction catalyst (e.g., hydroquinone) or the like) for the carboxylic acid or carboxylic anhydride and a cyclic ether, and a polymerization inhibitor (e.g., hydroquinone or the like) or the like are placed in the flask and reacted at, for example, 60 to 130℃for 1 to 10 hours, whereby the resin [ K4] can be produced.
(b) The amount of (a) to be used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). In this range, there is a tendency that the balance of the storage stability of the colored curable resin composition, the developability at the time of forming a pattern, the solvent resistance, the heat resistance, the mechanical strength and the sensitivity of the obtained pattern becomes good. The cyclic ether has high reactivity, and (b) used in the resin [ K4] 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 (c). 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 (c).
The reaction conditions such as the charging method, the reaction temperature, and the time may be appropriately adjusted in consideration of production facilities, 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 production equipment, the amount of heat generated by polymerization, and the like, similarly to the polymerization conditions.
As the first stage, the copolymer of (a) and (b) and (c) was obtained in the same manner as the above-mentioned method for producing the resin [ K1 ]. 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 (a), (b) and (c) is preferably 2 to 60 mol% of the structural unit derived from (a), 2 to 95 mol% of the structural unit derived from (b), 1 to 65 mol% of the structural unit derived from (c), more preferably 5 to 50 mol% of the structural unit derived from (a), 5 to 80 mol% of the structural unit derived from (b) and 5 to 60 mol% of the structural unit derived from (c), respectively, relative to the total molar number of all the structural units constituting the copolymer.
Further, the resin [ K5] can be obtained by reacting a carboxylic acid or carboxylic anhydride of (a) with a cyclic ether of (b) of a copolymer of (a) and (b) and (c) under the same conditions as those of the process for producing the resin [ K4 ].
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 resin [ K6] is obtained by further reacting the resin [ K5] with a carboxylic anhydride.
The resin [ K6] can be produced by reacting the hydroxyl group of the resin [ K5] produced by the reaction of a cyclic ether with a carboxylic acid or carboxylic anhydride with a 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 mol based on 1 mol of the hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride.
Specific examples of the resin (B) include 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer and 3, 4-epoxytricyclo [5.2.1.0 ] acrylate 2.6 ]Decyl ester/(meth) acrylic acid copolymer and other resins [ K1 ] ]The method comprises the steps of carrying out a first treatment on the surface of the Glycidyl (meth) acrylate/(meth) acrylic acid benzyl/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Resin [ K2 ] such as decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyl oxetane/(meth) acrylic acid/styrene copolymer]The method comprises the steps of carrying out a first treatment on the surface of the Resins [ K3 ] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer and styrene/(meth) acrylic acid copolymer]The method comprises the steps of carrying out a first treatment on the surface of the Resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate/(meth) acrylic acid copolymer, resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and copolymer of glycidyl (meth) acrylate and tricyclodecyl (meth) acrylate/(meth) benzyl (meth) acrylate/(meth) acrylic acidResins [ K4 ] such as resins obtained by addition]The method comprises the steps of carrying out a first treatment on the surface of the Resins [ K5 ] such as resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/(meth) acrylic acid glycidyl ester and resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/(meth) acrylic acid/styrene/(meth) acrylic acid glycidyl ester ]The method comprises the steps of carrying out a first treatment on the surface of the Resins such as resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/(meth) acrylic acid glycidyl ester and further reacting with tetrahydrophthalic anhydride [ K6]]Etc.
Among them, as the resin (B), the resin [ K1] and the resin [ K2] are preferable.
The resin (B) may be mixed with 2 or more kinds of resins, for example, 2 or more kinds selected from the resins [ K1] to [ K6] may be mixed.
The polystyrene-equivalent weight average molecular weight of the resin (B) 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 total acid value of the resin (B) is 100 to 200mg-KOH/g, preferably 105mg-KOH/g or more, more preferably 110mg-KOH/g or more, preferably 195mg-KOH/g or less, more preferably 190mg-KOH/g or less, in terms of solid content. 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 closer the value of the acid value is to the preferable range, the more the absorbance retention, pattern developability, and heat resistance of the color filter obtained from the colored curable resin composition can be improved.
When the resin (B) is a resin obtained by mixing 2 or more kinds of resins, the acid value of the resin (B) is calculated using the acid value and the mixing ratio of each resin. For example, when 50 parts by mass of a resin having an acid value of 200mg-KOH/g is mixed with 50 parts by mass of a resin having an acid value of 100mg-KOH/g, the acid value of the resulting resin is 150mg-KOH/g.
The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, 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.
< 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 a colored pattern and the chemical resistance of the color filter tend to be improved.
Polymerization initiator (D) >)
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of 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-acetyl oxime and the like. 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. Commercially available products such as Irgacure (registered trademark) 819 (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, reference is made to Japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenylbisimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent application laid-open No. 48-38403, japanese patent application laid-open No. 62-174204, etc.), biimidazole compounds in which the phenyl group at the 4,4', 5' -position is substituted with a carboalkoxy group (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 onium salts such as 4-hydroxyphenyldimethyl sulfonium p-toluene sulfonate, 4-hydroxyphenyldimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluene sulfonate, 4-acetoxyphenyl methylbenzyl sulfonium hexafluoroantimonate, triphenylsulfonium p-toluene sulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene sulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl toluene sulfonates, benzoin toluene sulfonates, 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, etc.; 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, and propylene glycol monopropyl ether Ethers, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl butanol, tetrahydrofuran, tetrahydropyran, 1, 4-di-butanolAlkyl, 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 DC11PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicone SH PA, toray Silicone SH8400 (trade name: dow Corning Toray, manufactured by Mitsui chemical Co., ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Xinyue chemical Co., ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan contract 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-mercaptopropyl 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 a colorant (a), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and if necessary, a solvent (E), a 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, and exposing and developing the colored composition layer through a photomask. 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 solvents and drying to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit coating method, and a slit spin coating method.
The temperature 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 to form 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 to develop, thereby forming a coloring pattern on the substrate. The unexposed portions of the colored composition layer are removed by development by dissolution in a developer. 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 alkali 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 developing method may be any of spin-coating immersing method, spraying method, 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, the compounds were confirmed 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).
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 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).
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).
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 287.0
The precise molecular weight is +286.0
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 328.3
The precise molecular weight is +327.2
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 compound represented by the formula (a-5) was separated and purified by silica gel chromatography to obtain 15 parts.
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 442.3
The precise molecular weight is +441.2
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 328.2
The precise molecular weight is +327.2
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 314.2
The precise molecular weight is +313.2
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 300.2
The precise molecular weight is +299.2
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 677.3
The exact molecular weight: +676.3
(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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 242.3
The precise molecular weight is +241.2
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 356.2
The precise molecular weight is +355.2
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.
Identification of ionization Pattern =ESI +: M/z = [ M+H ] ] + 342.2
The precise molecular weight is +341.2
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 328.1
The precise molecular weight is +327.2
A solution of 13.2 parts of thionyl chloride (manufactured by Tokyo chemical Co., ltd.) dissolved in 72 parts of methanol (manufactured by Kabushiki Kaisha chemical Co., ltd.) was cooled to 0℃and 9.1 parts of a crude product comprising the compound represented by the above-obtained formula (a-11) and the compound represented by the formula (a-12) was introduced while 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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 342.2
The precise molecular weight is +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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 300.2
The precise molecular weight is +299.2
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).
Identification of ionization Pattern =ESI +: M/z = [ M+H ]] + 677.4
The precise molecular weight is +676.4
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, 288 parts of ethyl lactate was charged, and the mixture was heated to 85 ℃ while stirring. Next, 3, 4-epoxytricyclo [5.2.1.0 ] acrylate was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]A mixed solution of 208 parts of a mixture of decane-9-yl esters (mixing ratio: 1:1), 42 parts of acrylic acid and 200 parts of ethyl lactate.
On the other hand, a mixed solution obtained by dissolving 8 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator in 254 parts of ethyl lactate 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 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) having a B-type viscosity (23 ℃) of 44mPas and a solid content of 26.2%. The weight average molecular weight (Mw) of the resulting copolymer was 10300, the acid value in terms of solid content was 134mg-KOH/g, and the dispersity was 2.27. The resin (B-1) has the following structural units.
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.
A device; HLC-8120GPC (manufactured by Tosoh Co., ltd.)
A column; TSK-GELG2000HXL
Column temperature; 40 DEG C
A solvent; THF (tetrahydrofuran)
A flow rate; 1.0mL/min
Detecting the concentration of the solid component of the liquid; 0.001 to 0.01 mass%
Sample injection amount; 50 mu L
A detector; RI (RI)
A 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 324 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 ] acrylate was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]A mixed solution of 135 parts of a mixture of decane-9-yl esters (mixing ratio of 1:1), 45 parts of acrylic acid, 120 parts of phenyl methacrylate and 203 parts of propylene glycol monomethyl ether.
On the other hand, a mixed solution obtained by dissolving 18 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, in 155 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 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-2)) solution having a type B viscosity (23 ℃) of 141mPas and a solid content of 31.6%. The weight average molecular weight (Mw) of the resulting copolymer was 17300, the acid value in terms of solid content was 112mg-KOH/g, and the dispersity was 2.44. The resin (B-2) has the following structural units.
(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 250 parts of propylene glycol monomethyl ether acetate and 100 parts of propylene glycol monomethyl ether were added thereto, followed by stirring and heating to 80 ℃. Next, 3, 4-epoxytricyclo [5.2.1.0 ] acrylate was added dropwise to the flask using a dropping pump for 4 hours 2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]225 parts of decane-9-yl ester (mixing ratio 1:1), 75 parts of acrylic acid and 145 parts of propylene glycol monomethyl ether.
On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator in 200 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 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-3)) having a B-type viscosity (23 ℃) of 122mPas and a solid content of 32.0%. The weight average molecular weight (Mw) of the resulting copolymer was 21500, the acid value in terms of solid content was 187mg-KOH/g, and the dispersity was 2.85. The resin (B-3) has the same structural unit as the resin (B-1).
(Synthesis example 4 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 232 parts of propylene glycol monomethyl ether acetate and 162 parts of ethyl lactate were added thereto, followed by heating to 85 ℃ while stirring. Next, 3, 4-epoxytricyclo [5.2.1.0 ] acrylate was added dropwise to the flask using a dropping pump for 5 hours 2,6 ]Decane-8-esters and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]180 parts of a mixture of decane-9-yl esters (mixing ratio 1:1), 60 parts of acrylic acid, 60 parts of 2-hydroxyethyl methacrylate, 148 parts of ethyl lactate and 54 parts of propylene glycol monomethyl ether acetate.
On the other hand, a mixed solution obtained by dissolving 10 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, in 100 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 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 103mPas and a solid content of 31.0%. The weight average molecular weight (Mw) of the resulting copolymer was 9800, the acid value in terms of solid content was 153mg-KOH/g, and the dispersity was 2.43. The resin (B-4) has the following structural units.
(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 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 of acrylic acid were added dropwise to the flask using a dropping pump over about 5 hours 2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]171 parts of decane-9-yl ester mixture (mixing ratio: 1:1) was dissolved in 40 parts of propylene glycol monomethyl ether acetate.
On the other hand, a solution obtained by dissolving 26 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator 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-5)) having a solid content of 43.5%. The weight average molecular weight (Mw) of the obtained resin (B-5) was 8000, the dispersity was 1.98, and the acid value in terms of solid content was 53mg-KOH/g. The resin (B-5) has the following structural units.
(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, 280 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 80℃with stirring. Next, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 of acrylic acid were added dropwise over 5 hours using a dropping pump 2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decane-9-yl ester (mixing ratio: 1:1) 289 parts, propylene glycol monomethyl ether acetate 125 parts.
On the other hand, a mixed solution obtained by dissolving 33 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise using another dropping pump for 6 hours. After completion of the dropwise addition, the flask was kept at 80℃for 4 hours, and then cooled to room temperature, whereby a copolymer (resin (B-6)) solution having a type B viscosity (23 ℃) of 108mPas and a solid content of 35.0% was obtained. The weight average molecular weight (Mw) of the resulting copolymer was 9100, the dispersity was 2.19, and the acid value in terms of solid content was 81mg-KOH/g. The resin (B-6) has the same structural unit as the resin (B-1).
(Synthesis example 7 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 245 parts of propylene glycol monomethyl ether acetate and 171 parts of propylene glycol monomethyl ether were added thereto, followed by stirring and heating to 85 ℃. Next, 3, 4-epoxytricyclo [5.2.1.0 ] acrylate was added dropwise to the flask using a dropping pump for 4 hours 2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]210 parts of a mixture of decane-9-yl esters (mixing ratio: 1:1), 90 parts of acrylic acid and 64 parts of propylene glycol monomethyl ether.
On the other hand, a mixed solution obtained by dissolving 20 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, in 200 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 3 hours and then cooled to room temperature, whereby a solution of a copolymer (resin (B-7)) having a B-type viscosity (23 ℃) of 69mPas and a solid content of 33.3% was obtained. The weight average molecular weight (Mw) of the resulting copolymer was 9200, the acid value in terms of solid content was 213mg-KOH/g, and the dispersity was 2.26. The resin (B-7) has the same structural unit as the resin (B-1).
Examples 1 to 9 and comparative examples 1 to 4
[ 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.
TABLE 2
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) (solid content conversion)
Resin (B-2) (solid content conversion)
Resin (B-3) (solid content conversion)
Resin (B-4) (solid content conversion)
Resin (B-5) (solid content conversion)
Resin (B-6) (solid content conversion)
Resin (B-7) (solid content conversion)
The polymerizable compound (C-1) was dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Japanese chemical Co., ltd.)
Polymerization initiator (D-1) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF corporation; O-acyl oxime Compound)
Polymerization initiator (D-2) DFI-091 (Daito Chemix Co., ltd.; O-acyl oxime Compound)
Solvent (E-1) 4-hydroxy-4-methyl-2-pentanone
Solvent (E-2) propylene glycol monomethyl ether acetate
Solvent (E-3) ethyl lactate
Solvent (E-4) propylene glycol monomethyl ether
Leveling agent (F-1) polyether-modified silicone oil (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., ltd.)
[ production of colored coating film ]
The colored curable resin composition was applied to a 5cm square glass substrate (EAGLE XG; 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 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 according to the following formula. The results are shown in tables 3 to 5.
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.
2. Heat resistance (Δeab)
After the preliminary baking and after the post baking, chromaticity was measured, and a color difference Δeab was calculated from the measured value by a method described in JIS Z8730:2009 (calculation method of color difference). The results are shown in Table 5. The smaller Δeab means the smaller the color change.
[ production of Pattern ]
The colored curable resin composition was applied to a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) by spin coating so that the film thickness after pre-baking was 2.0. Mu.m, and then pre-baked at 100℃for 3 minutes to form a colored composition layer. After cooling, the composition layer-formed substrate and the quartz glass photomask were separated by a distance of 100. Mu.m, and an exposure machine (TME-150 RSK; TOPCON, manufactured by TOPCON Co., ltd.) was used at a rate of 60mJ/cm in the atmosphere 2 The exposure amount (365 nm reference) of the substrate was irradiated with light. As the photomask, a photomask having 100 μm lines and space patterns formed therein was used. The composition layer after the irradiation with light was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23℃for 90 seconds to develop the composition layer.
3. Evaluation of Pattern developability
After development, the substrate washed with water was observed with a microscope (magnification: 500 times; VF-7510 (manufactured by Kyolce.), and the pattern formability of the colored curable resin composition layer was evaluated according to the following evaluation criteria. The results are shown in Table 5.
Pattern with a predetermined line width is formed.
And X, the pattern with the specified line width is not formed, the unexposed part is not dissolved and removed by the developing solution, or a part of the pattern exists in the unexposed part.
The state in which a part of the pattern exists in the unexposed portion includes a state in which a part of the pattern formed in the unexposed portion dissolved and removed by the developer is dissolved and eroded by the developer,
i) The dissolved pattern expands to the state of the unexposed portion;
ii) a state in which the pattern once peeled off from the substrate is attached again to the unexposed portion, and the like.
TABLE 3
TABLE 4
TABLE 5
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 an onium squarate dye represented by the formula (I),
the acid value of the resin is 100-200 mg-KOH/g in terms of solid content,
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),
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 Each of which may be the same or different, represents a bonding site to a nitrogen atom,
R 9 and R is 10 Each independently represents a linear alkyl group having 3 to 5 carbon atoms and having a hydroxyl group at the end or a linear alkyl group having 3 to 5 carbon atoms and having a carboxyl group at the end.
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.
CN201980091164.0A 2019-02-08 2019-12-03 Colored curable resin composition Active CN113383021B (en)

Applications Claiming Priority (3)

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