Classifications

• • 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
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers 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
  • 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
  • C08F20/22—Esters containing halogen
• • 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
  • C08F220/22—Esters containing halogen
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • 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
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
• • 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

Definitions

• the present invention relates to a colored curable resin composition.
• Color filters used for display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from a colored resin composition.
• a squarylium dye is known as a colorant used in such a colored resin composition (Patent Documents 1 and 2).
• an object of the present invention is to provide a colored curable resin composition capable of forming a color filter having excellent heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness).
• the gist of the present invention is as follows.
• [1] contains a colorant, a resin, a polymerizable compound, and a polymerization initiator,
• the colorant is a colorant containing a squarylium dye
• a colored curable resin composition wherein the resin is a resin containing a structural unit derived from fluoroalkyl (meth)acrylate.
• [2] The colored curable resin composition according to [1], wherein the squarylium dye is a compound represented by the formula (I).
• R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
• R 5 to R 8 each independently represent a hydrogen atom or a hydroxy group.
• Ar 1 and Ar 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or a group represented by the formula (i).
• R 12 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent 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 the carbon atoms constituting the monovalent saturated hydrocarbon group.
• a plurality of R 12's may be the same or different.
• R 9 and R 10 each independently represent a monovalent 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 the carbon atoms constituting the monovalent saturated hydrocarbon group.
• [3] A color filter formed from the colored curable resin composition according to [1] or [2].
• [4] A display device including the color filter according to [3].
• the colored curable resin composition of the present invention can provide a color filter having excellent heat resistance (preferably heat resistance and absorbance retention, or heat resistance and lightness).
• the colored curable resin composition of the present invention includes a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, a polymerizable compound). (C) and a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)).
• Coloring agents include squarylium dyes.
• the resin contains structural units derived from fluoroalkyl (meth)acrylate.
• the colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as solvent (E)).
• the colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)).
• a leveling agent hereinafter sometimes referred to as a leveling agent (F)
• the compounds exemplified as the respective components can be used alone or in combination of two or more kinds unless otherwise specified.
• squarylium dye contained in the colorant (A) examples include compounds described in JP2013-76926A.
• the squarylium dye is preferably a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)).
• compound (I) the compound (I) will be described in detail.
• the compound (I) is a compound obtained by rotating the resonance structure of the formula (I) or each group in the formula (I) around the bond axis of a single bond. Will also be included.
• R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent 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 the carbon atoms constituting the monovalent saturated hydrocarbon group.
• R 5 to R 8 each independently represent a hydrogen atom or a hydroxy group.
• Ar 1 and Ar 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i), and preferably a group represented by the formula ( represents a group represented by i).
• R 12 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent 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 the carbon atoms constituting the monovalent saturated hydrocarbon group.
• R 9 and R 10 each independently represent a monovalent 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 the carbon atoms constituting the monovalent saturated hydrocarbon group.
• examples of the halogen atom for R 1 to R 4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 , R 9 , R 10 , R 12 , Ar 1 and Ar 2 include a methyl group, an ethyl group, a propyl group and a butyl group.
• Substituents for these saturated hydrocarbon groups include halogen atoms such as fluorine atom, chlorine atom and iodine; hydroxy group; carboxy group; -NR a R b (R a and R b are each independently a hydrogen atom or An alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group;
• Examples of the monovalent saturated hydrocarbon group of 20 include groups represented by the following formula. In the following formula, * represents a bond.
• Examples of groups in which an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting these saturated hydrocarbon groups include groups represented by the following formula.
• * represents a bond.
• Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms in R 12 include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group.
• a halogen atom such as a fluorine atom, a chlorine atom and iodine; a hydroxy group; a carboxy group; —NR c R d (R c and R d are each independently a hydrogen atom or A C1-C20 alkyl group); a nitro group; a C1-C10 alkoxy group such as a methoxy group and an ethoxy group; a C1-C10 alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; Etc.
• R 1 to R 4 a hydrogen atom, a hydroxy group and an alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom, a hydroxy group and a methyl group are more preferable, and a hydrogen atom is still more preferable.
• At least one of R 5 to R 8 is preferably a hydroxy group. More preferably, at least one of R 5 and R 6 is a hydroxy group, and at least one of R 7 and R 8 is a hydroxy group.
• an alkyl group having 3 to 14 carbon atoms which may have a substituent and a group represented by the formula (i) are preferable, and an alkyl group having 3 carbon atoms which may have a substituent.
• an alkyl group having 3 carbon atoms which may have a substituent eg, octyl group, nonyl group, decyl group, dodecyl group, 2 -Ethylhexyl group, etc.
• a linear alkyl group having a hydroxy group at a terminal and having 3 to 5 carbon atoms, and a group having a carboxy group at a terminal and having 3 to 5 carbon atoms A linear alkyl group and a 2-ethylhexyl group are more preferable.
• the saturated hydrocarbon group for R 12 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group.
• the unsaturated hydrocarbon group for R 12 is preferably an alkenyl group having 2 to 4 carbon atoms, more preferably a vinyl group or an allyl group.
• m is 2 or more
• at least one R 12 is preferably a saturated hydrocarbon group.
• m is 2 or more, an embodiment in which all R 12 are saturated hydrocarbon groups or an embodiment in which some R 12 are saturated hydrocarbon groups and some R 12 are unsaturated hydrocarbon groups is more preferable. preferable.
• n is preferably 1 to 5, more preferably 1 to 3.
• Examples of the group represented by the formula (i) include the following groups. * Represents a bond with the nitrogen atom.
• examples of the group represented by X 1 and X 2 include groups represented by formulas (A2-1) to (A2-9). * Represents a bond with a carbon atom.
• Examples of the compound (I) include the compounds (AII-1) to (AII-27) shown in Table 1.
• Compound (AII-10) to compound (AII-18) are more preferable.
• the compound represented by formula (I) can be produced by reacting the compound represented by formula (pt1) with the compound represented by formula (pt2) and the compound represented by formula (pt3). ..
• the amount of the compound represented by the formula (pt3) used is preferably 0.05 with respect to 1 mol in total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2).
• the amount is not less than 0.8 and not more than 0.8, and more preferably not less than 0.1 and not more than 0.6.
• R 1 to R 10 , Ar 1 and Ar 2 have the same meanings as described above.
• the reaction temperature is preferably 30°C to 180°C, more preferably 80°C to 140°C.
• the reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.
• Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl.
• hydrocarbon solvents such as toluene and xylene
• halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform
• alcohol solvents such as methanol, ethanol, isopropanol and butanol
• nitro hydrocarbon solvents such as nitrobenzene
• methyl isobutyl examples thereof include ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like, and these may be mixed and used.
• a mixed solvent of butanol and toluene is preferable.
• the amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 1 part by mass of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). Is 30 parts by mass or more and 150 parts by mass or less.
• the method for taking out the target compound (I) from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method may be mentioned in which the reaction mixture is cooled after completion of the reaction and the precipitated crystals are collected by filtration. The crystals collected by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.
• R 1 , R 2 , R 5 , R 6 , R 9 and Ar 1 each have the same meaning as described above.
• a compound represented by the formula (pt2) can be produced by using the same method as described above.
• the colorant (A) may contain a colorant different from the squarylium dye, in addition to the squarylium dye, and the colorant different from the squarylium dye is a dye (hereinafter sometimes referred to as dye (A1)). , And a pigment (hereinafter, sometimes referred to as a pigment (A2)), and the colorant different from the squarylium dye may include one or both of the dye (A1) and the pigment (A2). .
• the dye (A1) is not particularly limited as long as it does not include a squarylium dye, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes and mordant dyes.
• the dyes include compounds that are classified as having a hue other than pigment in the color index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Note (Shikisosha).
• azo dye cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, acridine dye, styryl dye, coumarin dye, quinoline dye.
• examples thereof include dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.
• C.I. I. Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only the numbers are shown), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. 117, 162, 163, 167, 189;
• Acid Green 1 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C. 104, 105, 106, 109, etc.
• Acid dyes C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C. I.
• I. C. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.
• I. Direct dye C. I. Disperse Yellow 51, 54, 76; C. I. Disperse Violet 26, 27; C. I. C. such as Disperse Blue 1, 14, 56, 60 and the like.
• I. Disperse dye 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. C. such as Basic Green 1 I. Basic dye, C. I. Reactive Yellow 2,76,116; C. I. Reactive Orange 16; C. I. C. such as Reactive Red 36 I. Reactive dye, C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C. I. Mordan tread 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.
• Modant dye such as Modern Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53.
• Modant dye C.I. I. C. such as Bat Green 1 I.
• examples include vat dyes and the like. These dyes may be appropriately selected according to the desired spectrum of the color filter.
• the pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments by Color Index (published by The Society of Dyers and Colorists).
• Examples of the pigment include C.I. 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, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C. I.
• the pigment may be rosin treated, surface treated with a pigment derivative having an acidic group or a basic group introduced therein, grafted on the surface of the pigment with a polymer compound, or atomized by a sulfuric acid atomization method, etc.
• a treatment, a cleaning treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.
• the pigment preferably has a uniform particle size.
• pigment dispersant examples include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more kinds.
• KP manufactured by Shin-Etsu Chemical Co., Ltd.
• Floren manufactured by Kyoeisha Chemical Co., Ltd.
• Sols Perth manufactured by Zeneca Co., Ltd.
• EFKA manufactured by CIBA
• Azisper Alignomoto Fine Co., Ltd.
• Techno Co., Ltd. Disperbyk (manufactured by Big Chemie), and the like.
• the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2).
• the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniform dispersed state tends to be obtained.
• the content of the colorant (A) in the colored curable resin composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass, based on the total amount of solids. It is not more than mass%, more preferably not less than 1 mass% and not more than 50 mass%.
• the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, the pattern having sufficient mechanical strength can be formed.
• total amount of solids in the present specification means the amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition.
• the total amount of solid content and the content of each component relative thereto can be measured by a known analysis 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% by mass or more, more preferably 3% by mass or more, and may be 100% by mass, or 90% by mass. It may be the following, 60% by mass or less, or 40% by mass or less.
• the resin contains a resin containing a structural unit derived from fluoroalkyl (meth)acrylate.
• (meth)acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid.
• the notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.
• the heat resistance of the color filter is improved.
• the structural unit derived from fluoroalkyl (meth)acrylate is preferably a structural unit represented by the following formula (Bf).
• R f1 represents a hydrogen atom or a methyl group.
• R f2 represents a fluoroalkyl group having 1 to 10 carbon atoms.
• fluoroalkyl group having 1 to 10 carbon atoms examples include a fluoroalkyl group having 1 carbon atom such as difluoromethyl group and trifluoromethyl group; 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2 2-trifluoroethyl group, perfluoroethyl group and other fluoroalkyl groups having 2 carbon atoms; 1,1,2,2-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1 , 2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, perfluoropropyl group, perfluoroisopropyl group, 1-(trifluoromethyl)-2,2,2-trifluoroethyl group, perfluoropropyl group C3 fluoroalkyl group such as fluoropropyl group: 1,1,2,2-tetrafluorobut
• R f2 is preferably a fluoroalkyl group having 2 to 6 carbon atoms, and more preferably a fluoroalkyl group having 4 to 6 carbon atoms.
• Structural units derived from fluoroalkyl (meth)acrylate include difluoromethyl (meth)acrylate, trifluoromethyl (meth)acrylate, 1,1-difluoroethyl (meth)acrylate, and 2,2-difluoroethyl (meth) Acrylate, 2,2,2-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, 1,1,2,2-tetrafluoropropyl (meth)acrylate, 2,2,3,3-tetrafluoro Propyl group (meth)acrylate, 1,1,2,2,3,3-hexafluoropropyl (meth)acrylate, perfluoroethylmethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluoroisopropyl (meth) Acrylate, 1-(trifluoromethyl)-2,2,2-trifluoroethyl (meth)acrylate
• the resin (B) is preferably an alkali-soluble resin.
• alkali-soluble resin (B) include the following resins [K1] to [K6].
• Resin [K1] a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides
• a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond hereinafter sometimes referred to as “(b)”
• (meth)acrylic acid fluoro a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides
• a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond hereinafter sometimes referred to as “(b)”
• (meth)acrylic acid fluoro
• a copolymer composed of structural units derived from alkyl (f) (hereinafter sometimes referred to as “(f)”); Resin [K2]; Structural unit derived from (a), Structural unit derived from (b), Structural unit derived from (f), Monomer (c) (copolymerizable with (a) ( However, it is different from (a), (b) and (f).) (hereinafter sometimes referred to as "(c)”), a copolymer composed of structural units; Resin [K3]; a copolymer comprising a structural unit derived from (a) and a structural unit derived from (f); Resin [K4]; a copolymer comprising a structural unit derived from (a), a structural unit derived from (f), and a structural unit derived from (c); Resin [K5]; a copolymer containing a structural unit derived from (a), a structural unit obtained by adding (a) to a structural
• the structural unit derived from (a) above it is preferable that the carboxy group or carboxylic acid anhydride contained in (a) remains unreacted. Further, in the resins [K1] and [K2], it is preferable that the structural unit derived from (b) has a cyclic ether structure having 2 to 4 carbon atoms, which is contained in (b), remaining unreacted.
• (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; 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, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethy
• (B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond.
• (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
• Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond.
• Examples include a monomer (b2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).
• Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)” And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
• Examples of (b1-1) include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p.
• Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by the formula (BI) and a formula (BII) And the like.
• vinylcyclohexene monooxide for example, 1,2-epoxy-4-vinylcyclohexane
• 3,4-epoxycyclohexylmethyl (meth)acrylate for example, Cyclomer A400; manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation
• R e and R f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
• X e and X f is a single bond, * - R g -, * - R g -O -, * - represents the R g -S- or * -R g -NH-.
• R g represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O.
• alkyl group having 1 to 4 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
• alkyl group having a hydrogen atom substituted with hydroxy examples include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group and a 1-hydroxy group.
• Examples thereof include a 1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.
• R e and R f a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.
• alkanediyl group examples include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group and the like can be mentioned.
• Examples of X e and X f include a single bond, a methylene group, an ethylene group, *—CH 2 —O— and *—CH 2 CH 2 —O—, and a more preferred single bond, *—CH 2 CH 2 —O— can be mentioned (* represents a bond with O).
• Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI-15) The compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15) is more preferred.
• Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (BII-1) to (BII-15). Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII-15)
• the compound represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15) is more preferable.
• the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of two or more kinds.
• the content ratio thereof [the compound represented by the formula (BI): the compound represented by the formula (BII)] is The molar ratio is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.
• (b2) a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable.
• Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane.
• (b3) a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.
• Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.
• (b1) is preferable because the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Further, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.
• 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, tricyclo[5.2.1.0 2, 6 ] Decane-8-yl(meth)acrylate (in the art, it is commonly called “dicyclopentanyl(meth)acrylate”.
• tricyclodecyl(meth)acrylate It may also be called “tricyclodecyl(meth)acrylate”. .), tricyclo[5.2.1.0 2,6 ]decen-8-yl(meth)acrylate (known in the art as a trivial name "dicyclopentenyl (meth)acrylate"), Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) ) (Meth)acrylic acid esters such as acrylates; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethy
• the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K1], Structural unit derived from (a); 2-55 mol% Structural unit derived from (b); 2 to 95 mol% Structural unit derived from (f): 1 to 55 mol% Is preferred, Structural unit derived from (a); 5 to 50 mol% Structural unit derived from (b); 5 to 80 mol% Structural unit derived from (f); 5 to 50 mol% Is more preferable.
• the ratio of the structural unit of the resin [K1] is in the above range, the heat resistance of the color filter obtained from the colored curable resin composition can be further improved.
• the resin [K1] is, for example, the method described in “Experimental Method for Polymer Synthesis” (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the literature. It can be manufactured by referring to the cited document described in.
• a predetermined amount of (a), (b) and (f), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and oxygen is replaced by, for example, nitrogen to create a deoxygenated atmosphere, Examples of the method include heating and keeping heat while stirring.
• the polymerization initiator, solvent and the like used here are not particularly limited, and those usually used in the relevant field can be used.
• the solvent may be any solvent that can dissolve each monomer, and examples thereof include the solvent described below as the solvent (E) of the colored curable resin composition of the present invention.
• the obtained copolymer may be used as the solution after the reaction as it is, or may be used as a concentrated or diluted solution, or taken out as a solid (powder) by a method such as reprecipitation. You may use the thing.
• the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.
• the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K2], Structural unit derived from (a); 2-55 mol% Structural unit derived from (b); 2 to 95 mol% Structural unit derived from (f): 1 to 55 mol% Structural unit derived from (c); 1 to 65 mol% Is preferred, Structural unit derived from (a); 5 to 50 mol% Structural unit derived from (b); 5 to 80 mol% Structural unit derived from (f); 5 to 50 mol% Structural unit derived from (c); 5 to 60 mol% Is more preferable.
• the ratio of the structural unit of the resin [K2] is within the above range, the heat resistance of the color filter obtained from the colored curable resin composition can be further improved.
• the resin [K2] can be manufactured, for example, in the same manner as the method described as the method for manufacturing the resin [K1].
• the ratio of the structural units derived from each is as follows: Structural unit derived from (a); 2-70 mol% Structural unit derived from (f); 30 to 98 mol% Is preferred, Structural unit derived from (a); 10 to 60 mol% Structural unit derived from (f); 40 to 90 mol% Is more preferable.
• the resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
• the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K4], Structural unit derived from (a); 2-55 mol% Structural unit derived from (f): 1 to 55 mol% Structural unit derived from (c); 1 to 65 mol% Is preferred, Structural unit derived from (a); 5 to 50 mol% Structural unit derived from (f); 5 to 50 mol% Structural unit derived from (c); 5 to 60 mol% Is more preferable.
• the resin [K4] can be manufactured, for example, in the same manner as the method described as the method for manufacturing the resin [K1].
• a copolymer of (a), (b) and (f) is obtained in the same manner as in the method for producing the resin [K1] described above.
• the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
• the ratios of the structural units derived from (a), (b) and (f) are, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
• the resin [K5] can be obtained by reacting the cyclic ether derived from (b) included in the copolymer with the carboxylic acid or carboxylic acid anhydride included in (a).
• the amount of (a) used to react with the above copolymer is preferably 5 to 80 mol per 100 mol of (b).
• (B1) is preferable as (b) used in the resin [K5] because the reactivity of the cyclic ether is high and the unreacted (b) hardly remains.
• the amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (f).
• the amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (f).
• Reaction conditions such as a charging method, reaction temperature and time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization and the like.
• the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.
• the resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride.
• the carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.
• carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and 1 2,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like.
• the amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.
• the resin (B) examples include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid/2,2,2-trifluoroethyl (meth)acrylate copolymer, 3,4- Epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth)acrylic acid/2,2,2-trifluoroethyl (meth)acrylate copolymer, 3,4-epoxycyclohexylmethyl (meth ) Acrylate/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.
• Reactive resin 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate copolymer reacted with (meth)acrylic acid
• a resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin thus obtained may be mentioned.
• resin (B) resins [K1] to resin [K4] are preferable, and resins [K1] and resin [K2] are more preferable.
• the polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. .. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed area in the developing solution is good, and the resolution of the colored pattern tends to be improved.
• the dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
• the acid value of the resin (B) is, in terms of solid content, preferably 40 mg-KOH/g or more, more preferably 50 mg-KOH/g or more, still more preferably 60 mg-KOH/g or more, preferably 180 mg-KOH. /G or less, more preferably 170 mg-KOH/g or less, still more preferably 160 mg-KOH/g or less.
• the acid value is a value measured as an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution. ..
• the content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, and further preferably 17 to 65% by mass, based on the total solid content.
• the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.
• the content of the resin (B) is preferably 10 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).
• the amount is 90 parts by mass or less, and more preferably 30 parts by mass or more and 85 parts by mass or less.
• the content of the resin (B) is within the above range, the heat resistance of the obtained color filter is further improved.
• the content of the resin (B) is 55 parts by mass or more and 95 parts by mass or less, preferably 60 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Is also preferable.
• the content of the resin (B) is 10 parts by mass or more and 60 parts by mass or less, preferably 20 parts by mass or more and 55 parts by mass or less based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). In some cases, the heat resistance and brightness of the resulting color filter are improved.
• the polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond, and preferably It is a (meth)acrylic acid ester compound.
• the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds.
• a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol 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
• the content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, further preferably 10 to 55% by mass, based on the total amount of the solid content. is there.
• the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.
• the polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
• Examples of polymerization initiators that generate active radicals include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.
• O-acyl oxime compound examples include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane.
• the O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6- ⁇ 2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl ⁇ -9H-carbazol-3-yl]ethane-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime At least one selected from the group is preferable. With these O-acyl oxime compounds, a color filter with high brightness tends to be obtained.
• alkylphenone compound examples include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane.
• triazine compound examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 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-methoxy Styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-Methylpheny
• acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• a commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.
• biimidazole compound examples include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl)- 4,4′,5,5′-Tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4 ,4',5,5'-Tetraphenylbiimidazole,2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole,2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trime
• Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate and 4-acetoxy.
• Onium salts such as phenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate and nitrobenzyl Examples thereof include tosylates and benzoin tosylates.
• benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
• the polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds.
• a polymerization initiator containing a vinyl 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). Parts by mass.
• the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.
• the solvent (E) is not particularly limited, and a solvent commonly used in this field can be used.
• a solvent commonly used in this field can be used.
• ester solvents solvents containing -COO- and not -O- in the molecule
• ether solvents solvents containing -O- and not -COO-
• ether ester solvents intramolecular
• a solvent containing -COO- and -O- solvent containing -CO- in the molecule but not -COO-
• an alcohol solvent containing OH in the molecule, -O-,- CO- and -COO--free solvents
• aromatic hydrocarbon solvents aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.
• Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, 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 ⁇ -butyrolactone.
• ether solvent ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl
• ether diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole.
• ether ester solvent examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxy.
• Ethyl propionate 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 Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
• Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.
• alcohol solvents examples include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
• aromatic hydrocarbon solvents examples include benzene, toluene, xylene, mesitylene and the like.
• amide solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
• organic solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferable from the viewpoints of coating properties and drying properties.
• the solvent propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N,N-dimethylformamide are preferred, 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.
• the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.
• Leveling agent (F) examples include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
• silicone-based surfactant examples include surfactants having a siloxane bond in the molecule.
• Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 manufactured by Toray Dow Corning Co., Ltd.
• KP321, KP322, KP323, KP324, KP326, Examples include KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 manufactured by Momentive Performance Materials Japan LLC.
• fluorine-based surfactant examples include surfactants having a fluorocarbon chain in the molecule.
• Florard (registered trademark) FC430, FC431 manufactured by Sumitomo 3M Limited
• Megafac registered trademark
• F142D F171, F172, F173, F177, F183, F554, and F543.
• R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).
• silicone-based surfactant having a fluorine atom examples include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
• the content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.02% by mass or less with respect to the total amount of the colored curable resin composition. It is 2% by mass or less, and more preferably 0.005% by mass or more and 0.2% by mass or less.
• the content of the dispersant is not included in this content.
• the colored curable resin composition of the present invention if necessary, a polymerization initiation auxiliary agent, a filler, another polymer compound, an adhesion promoter, a light stabilizer, a chain transfer agent, etc., which are known additives in the technical field.
• An agent may be included.
• Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiene.
• the colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary, It can be prepared by mixing the leveling agent (F) and other components.
• Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferable.
• the photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.
• a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not developing.
• the colored pattern or colored coating film thus formed is the color filter of the present invention.
• the film thickness of the color filter to be produced is not particularly limited and may be appropriately adjusted depending on the purpose and application. For example, it is 0.1 to 30 ⁇ m, preferably 0.1 to 20 ⁇ m, and more preferably 0.5. ⁇ 6 ⁇ m.
• each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions.
• it can be manufactured as follows.
• the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or vacuum drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.
• the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.
• the temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C.
• the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
• the thickness of the coloring composition layer is not particularly limited and may be appropriately selected according to the intended thickness of the color filter.
• the colored composition layer is exposed through a photomask for forming an intended colored pattern.
• the pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
• the light source used for exposure is preferably a light source that emits light having a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You may Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.
• Use an exposure device such as a mask aligner or stepper because it can irradiate parallel rays uniformly on the entire exposed surface and can perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred.
• a colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution for development.
• a developing solution for development By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developing solution.
• the developing solution for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable.
• the concentration of these alkaline 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 a paddle method, a dipping method, a spray method or the like.
• the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
• the post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C.
• the post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
• a mixed solution prepared by dissolving 15 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 100 parts of propylene glycol monomethyl ether acetate was put into the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 130 mPas and a solid content of 30.9% (resin (B-1 )) was obtained.
• the produced copolymer had a weight average molecular weight (Mw) of 8,800, a dispersity of 1.76, and an acid value in terms of solid content of 155 mg-KOH/g.
• the resin (B-1) has the following structural units.
• the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
• the polystyrene equivalent weight average molecular weight and number average molecular weight ratio (Mw/Mn) obtained above was taken as the dispersity.
• the produced copolymer had a weight average molecular weight (Mw) of 12,500, a dispersity of 2.14, and an acid value in terms of solid content of 154 mg-KOH/g.
• the resin (B-2) has the same constitutional unit as the resin (B-1).
• a solution of 171 parts of a mixture of 1.0 2,6 ]decane-9-yl acrylate (mixing ratio is 1:1) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours by using a dropping pump. ..
• a solution prepared by dissolving 26 parts of the polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was put into the flask for about 5 hours using another dropping pump. Dropped.
• the obtained resin (B-3) had a weight average molecular weight (Mw) of 8,000, a dispersity of 1.98 and an acid value in terms of solid content of 53 mg-KOH/g.
• the resin (B-3) has the following structural unit.
• each component represents the following compound.
• Colorant (A-1) Compound represented by Formula (AII-10)
• Colorant (A-2) Compound represented by Formula (AII-18)
• Resin (B-1) Resin (B-1) ) (Solid content conversion)
• Resin (B-2) Resin (B-2) (solid content conversion)
• Resin (B-3) Resin (B-3) (solid content conversion)
• Polymerization initiator (D-2): DFI-091 manufactured by Daito Chemix Co.; O-acyl oxime compound)
• Polymerization initiator (D-3) N-benzoyloxy-1-(4-phenylsul
• a colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method so that the film thickness after post-baking would be 2.0 ⁇ m, and then 3 at 100° C. It was prebaked for a minute to form a colored composition layer. After allowing to cool, the colored composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corp.) in an air atmosphere at an exposure dose of 100 mJ/cm 2 (365 nm standard). Then, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.
• a color filter having excellent heat resistance can be formed.

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