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
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
  • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
  • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
• • 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
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/47—Levelling agents

Definitions

• the present invention relates to a random copolymer, a coating composition and a resist composition containing the copolymer.
• Leveling agents are added to smooth the coating film obtained by applying a coating composition such as a paint composition or a resist composition. Specifically, by adding a leveling agent to a coating composition, the leveling agent orients itself on the coating film surface, reducing the surface tension of the coating film and smoothing the resulting coating film. A coating film with a smooth surface can reduce the occurrence of repelling and unevenness.
• Leveling agents are used, for example, in automotive paints.
• a coating composition containing a leveling agent can impart high smoothness to the resulting coating surface and can impart gloss to the exterior of the automobile.
• Silicone-based leveling agents have been proposed as leveling agents for use in automotive paints (Patent Document 1).
• Leveling agents are used in a variety of applications, including color resist compositions for use in the manufacture of color filters for liquid crystal displays.
• the manufacture of color filters generally involves the steps of applying a color resist composition onto a glass substrate by a coating method such as spin coating or slit coating, exposing the dried coating film using a mask, and then developing the film to form a colored pattern.
• a coating method such as spin coating or slit coating
• the coating film is not smooth and has uneven thickness, or if there is uneven coating or repelling, there is a risk of color unevenness occurring in pixels.
• the smoothness of the resulting coating film can be improved, and the surfaces of the red (R), green (G), and blue (B) pixels and the black matrix (BM) formed between these pixels can exhibit high smoothness, resulting in a color filter with little color unevenness.
• Patent Document 1 describes a silicone-based leveling agent synthesized by free radical polymerization. However, the silicone content in the leveling agent actually evaluated was low, and there was a problem that a sufficiently smooth coating film could not be obtained. Also, Patent Document 2 describes a silicone-based leveling agent that has good leveling properties and is synthesized by living polymerization. However, due to its block structure, the coating film has high liquid repellency and poor recoatability.
• the object of the present invention is to provide a copolymer that functions as a silicone-based leveling agent with leveling and recoating properties.
• the present invention relates to a polymerizable monomer (a1) having a functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n (n is an integer of 1 to 3, each R is independently an alkyl group having 1 to 3 carbon atoms, and each R' is independently an alkyl group having 1 to 3 carbon atoms) and a (meth)acryloyl group, and a structural unit B derived from a polymerizable monomer (a2) having one or more groups selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain, the content of the structural unit A relative to the total content of the structural units A and B is 50 to 80 mass %,
• the present invention relates to a random copolymer having a weight average molecular weight (Mw) of 10,000 or more.
• the present invention also relates to a coating composition containing the random copolymer.
• the present invention also relates to a resist composition containing the random copolymer.
• the present invention also relates to an article comprising the random copolymer described above.
• the present invention also relates to a method for producing a random copolymer by free radical polymerization of a compound represented by the following formula (a1-1) and at least one of a compound represented by the following formula (a2-1) and a compound represented by the following formula (a2-2) as reaction raw materials.
• a1-1 a compound represented by the following formula (a2-1) and (a2-2)
• Each R is independently an alkyl group having 1 to 3 carbon atoms; R1 is a hydrogen atom or a methyl group.
• L1 is a divalent organic group or a single bond;
• R21 is a hydrogen atom or a methyl group;
• R 22 is an alkyl group having 1 to 18 carbon atoms;
• R 23 is a hydrogen atom or a methyl group;
• R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms;
• n is an integer ranging from 1 to 4, and
• m is an integer ranging from 1 to 200.
• the present invention provides a copolymer that functions as a silicone-based leveling agent with leveling and recoating properties.
• x to y represents a numerical range of "not less than x and not more than y.”
• the upper and lower limit values described in relation to the numerical ranges can be combined in any combination.
• any combination of two or more of the individual aspects of the present invention described below is also an aspect of the present invention.
• (meth)acrylate refers to either or both of an acrylate and a methacrylate.
• a random copolymer comprises a structural unit A derived from a polymerizable monomer (a1) having a functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n (n is an integer of 1 to 3; each R is independently an alkyl group having 1 to 3 carbon atoms; each R' is independently an alkyl group having 1 to 3 carbon atoms) and an acryloyl group, and a structural unit B derived from a polymerizable monomer (a2) having one or more groups selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain.
• the content of the structural unit A relative to the total of the structural units A and B is 50 to 80 mass %, and the weight average molecular weight (Mw) is 10,000 or more.
• the content of the structural unit A is 50 to 80 mass % and the functional groups represented by -Si[OSi(R) 3 ] n [R'] 3-n are randomly arranged in the polymer chain, so that it is possible to achieve both leveling property and recoatability.
• the random copolymer of the present invention can be prepared, for example, by subjecting the above-mentioned polymerizable monomer (a1) and polymerizable monomer (a2) to free radical polymerization.
• the polymerizable monomer (a1) and the polymerizable monomer (a2) constituting the random copolymer of the present invention will be described below.
• the functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n is preferably a functional group represented by -Si[OSi(R) 3 ] 3 , and more preferably -Si[OSi(CH 3 ) 3 ] 3.
• the functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n is -Si[OSi(CH 3 ) 3 ] 3
• the copolymer of the present invention can have high surface segregation ability.
• polymerizable monomer refers to a compound having a polymerizable unsaturated group.
• the polymerizable unsaturated group of the polymerizable monomer (a1) may be a group containing a vinyl group, such as a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinyl ether group, an allyl group, a styryl group, a maleimide group, etc.
• a (meth)acryloyl group or a (meth)acryloyloxy group is preferred.
• the polymerizable monomer (a1) is preferably a compound represented by the following formula (a1-1).
• Each R is independently an alkyl group having 1 to 3 carbon atoms.
• R1 is a hydrogen atom or a methyl group.
• L1 is a divalent organic group or a single bond.
• the divalent organic group of L1 is preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• Examples of the alkylene group having 1 to 50 carbon atoms for L1 include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decylene group, an n-dodecylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.
• the alkylene group having 1 to 50 carbon atoms for L1 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group, an ethylene group, an n-propylene group, or an isopropylene group.
• the alkyleneoxy group having 1 to 50 carbon atoms for L 1 is, for example, a group in which one or more -CH 2 - in the alkylene group is substituted with -O-.
• the alkyleneoxy group having 1 to 50 carbon atoms for L1 is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and even more preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, a heptyleneoxy group, or an octyleneoxy group.
• the divalent organic group of L1 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms
• the functional group represented by —Si[OSi(R) 3 ] 3 of the compound represented by formula (a1-1) is preferably —Si[OSi(CH 3 ) 3 ] 3 , and the compound is represented by the following formula (a1-2).
• R 1 is a hydrogen atom or a methyl group
• L 1 is a divalent organic group or a single bond.
• the copolymer of the present invention may contain structural units A derived from two or more polymerizable monomers (a1) having structures different from each other.
• the polymerizable monomer (a1) is preferably a single polymerizable monomer.
• the polymerizable monomer (a1) can be produced by a known method, and a commercially available product may be used.
• a commercially available polymerizable monomer (a1) for example, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane is commercially available.
• the content of the structural unit A relative to the total of the structural units A and B is 50% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, and is 80% by mass or less, preferably 75% by mass or less.
• the content of the structural unit A can be adjusted by the raw material charge ratio of the polymerizable monomer (a1) when producing the copolymer of the present invention.
• the content of the functional group represented by -Si[OSi(R) 3 ] n [R'] 3-n in the copolymer of the present invention is, for example, in the range of more than 30 mass % to 60 mass % of the total amount of the copolymer, preferably in the range of 40 to 60 mass %, and more preferably in the range of 50 to 60 mass %.
• the content of the functional group represented by --Si[OSi(R) 3 ] n [R'] 3-n can be adjusted by the raw material charging ratio of the polymerizable monomer (a1) when producing the copolymer of the present invention.
• the polymerizable monomer (a2) is a polymerizable monomer having one or more groups selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group containing a polyoxyalkylene chain.
• the polymerizable unsaturated group of the polymerizable monomer (a2) may be any group containing a vinyl group, such as a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinyl ether group, an allyl group, a styryl group, a maleimide group, etc.
• a (meth)acryloyl group or a (meth)acryloyloxy group is preferred.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) may be any one of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, and a hexadecyl group.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) is preferably an alkyl group having 1 to 6 carbon atoms.
• aromatic groups having 6 to 18 carbon atoms contained in the polymerizable monomer (a2) include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.
• the group containing a (poly)oxyalkylene chain contained in the polymerizable monomer (a2) is a monovalent group containing a repeating oxyalkylene portion or a divalent linking group containing a repeating oxyalkylene portion.
• the polymerizable unsaturated group of the polymerizable monomer (a2) is a (meth)acryloyl group
• the polymerizable monomer having a group containing a (poly)oxyalkylene chain is, for example, a compound represented by the following general formula (a2-poa1) or (a2-poa2).
• R a21 independently represents a hydrogen atom or a methyl group.
• R a22 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• p is an integer of 0 or greater
• q is an integer of 0 or greater
• r is an integer of 0 or greater
• p+q+r is an integer of 1 or greater.
• X, Y, and Z are each independently an alkylene group having 1 to 6 carbon atoms.
• the group represented by -(XO) p- (YO) q- (ZO) r -R a22 and the group represented by -(XO) p- (YO) q- (ZO) r- correspond to a group containing a (poly)oxyalkylene chain.
• the alkylene groups having 1 to 6 carbon atoms for X, Y, and Z are preferably alkylene groups having 2 to 4 carbon atoms.
• Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and the like.
• alkyl esters examples include alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms, such as dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.
• alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms such as dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth
• Examples of polymerizable monomers (a2) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate.
• Examples of the polymerizable monomer (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a vinyl ether group include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; cycloalkyl vinyl ethers, etc.
• polymerizable monomers (a2) having an aromatic group with 6 to 18 carbon atoms examples include styrene, ⁇ -methylstyrene, p-methylstyrene, and p-methoxystyrene.
• Examples of the polymerizable monomer (a2) having an alkyl group with 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloylamide group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acroylmorpholine.
• Examples of the polymerizable monomer (a2) having an alkyl group with 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.
• Examples of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol.propylene glycol) mono(meth)acrylate, polyethylene glycol.polypropylene glycol mono(meth)acrylate, poly(ethylene glycol.tetramethylene glycol) mono(meth)acrylate, polyethylene glycol.polytetramethylene glycol Methylene glycol mono(meth)acrylate, poly(propylene glycol.tetramethylene glycol) mono(meth)acrylate, polypropylene glycol.polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol.polyt
• poly(ethylene glycol-propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
• polyethylene glycol-polypropylene glycol means a block copolymer of ethylene glycol and propylene glycol
• the polymerizable monomer (a2) is preferably at least one selected from the group consisting of compounds represented by the following formula (a2-1), compounds represented by the following formula (a2-2), and compounds represented by the following formula (a2-3), and more preferably at least one selected from the group consisting of compounds represented by the following formula (a2-1) and compounds represented by the following formula (a2-2). These compounds can exhibit high compatibility when the copolymer of the present invention is used as a leveling agent.
• R21 is a hydrogen atom or a methyl group
• R 22 is an alkyl group having 1 to 18 carbon atoms
• R 23 is a hydrogen atom or a methyl group
• R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
• R 25 is a hydrogen atom or a methyl group
• R 26 is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms
• n is an integer ranging from 1 to 4
• m is an integer ranging from 1 to 200
• l is an integer ranging from 0 to 5.
• R 21 , R 23 , R 25 and R 27 are each preferably a hydrogen atom.
• the polymerizable monomer (a2) can be produced by a known method.
• Commercially available products may be used as the polymerizable monomer (a2).
• commercially available products of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include "NK ESTER M-20G”, “NK ESTER M-40G”, “NK ESTER M-90G”, “NK ESTER M-230G”, “NK ESTER AM-90G”, “NK ESTER AMP-10G”, “NK ESTER AMP-20G", and “NK ESTER AMP-60G” manufactured by Shin-Nakamura Chemical Co., Ltd.; "BLEMMER PE-90", “BLEMMER PE-200", “BLEMMER PE-350”, and “BLEMMER PE-40G” manufactured by NOF Corporation; Examples of such polymers include “Blenmar PME-100", “Blenmar PME-200”, “Blenmar PME-
• the copolymer of the present invention may be composed of two or more polymerizable monomers (a2) having different structures.
• the polymerizable monomer (a2) is preferably a single polymerizable monomer.
• the content of the structural unit B relative to the total of the structural units A and B is 20% by mass or more, and 50% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less.
• the content of the structural unit B can be adjusted by the raw material charge ratio of the polymerizable monomer (a2) when producing the copolymer of the present invention.
• the copolymer of the present invention may contain the structural units A and B, and may also use, as a reaction raw material, polymerizable monomers other than the polymerizable monomer (a1) and the polymerizable monomer (a2) as long as the effects of the present invention are not impaired.
• the copolymer of the present invention is preferably a copolymer substantially composed of structural units A and B, and more preferably a copolymer composed only of structural units A and B.
• “substantially composed” refers to a case where the total content of structural units A and B in the copolymer of the present invention is 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.
• the copolymer of the present invention preferably does not contain fluorine atoms.
• the copolymer of the present invention comprises the polymerizable monomer (a1) and the polymerizable monomer (a2)
• the copolymer of the present invention can be a copolymer containing no fluorine atoms.
• the weight average molecular weight (Mw) of the copolymer of the present invention is 10,000 or more. It is preferably 15,000 or more, and more preferably 20,000 or more. It is also preferably 500,000 or less, more preferably 100,000 or less, and even more preferably 40,000 or less.
• the weight average molecular weight (Mw) is a value calculated in terms of polystyrene based on gel permeation chromatography (GPC).
• the weight average molecular weight (Mw) value is measured by the method described in the Examples.
• the method for producing the random copolymer of the present invention is not particularly limited, and the copolymer can be produced by any known method.
• the copolymer of the present invention can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, etc.
• a free radical polymerization method the copolymer of the present invention can be produced by charging a polymerizable monomer mixture in an organic solvent and adding a general-purpose radical polymerization initiator.
• initiators various types of initiators can be used, and examples thereof include peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane, and metal chelate compounds such as Mn(acac) 3 .
• peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide
• azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane
• metal chelate compounds such as Mn(acac) 3 .
• additives such as chain transfer agents, such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, and octyl thioglycolic acid, and thiol compounds having a coupling group, such as ⁇ -mercaptopropyltrimethoxysilane, may be used.
• chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, and octyl thioglycolic acid
• thiol compounds having a coupling group such as ⁇ -mercaptopropyltrimethoxysilane
• organic solvent examples include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; dimethylformamide, dimethyl sulfoxide, N-methyl
• the solvent include polar solvents such as pyrrol
• the polymerization temperature during the free radical polymerization is preferably in the range of room temperature to 120°C.
• the copolymer of the present invention can also be produced by subjecting the polymerization components to living polymerization, such as living radical polymerization or living anionic polymerization (living random copolymer).
• living polymerization such as living radical polymerization or living anionic polymerization (living random copolymer).
• a dormant species whose active polymerization terminal is protected by an atom or atomic group, reversibly generates radicals and reacts with a monomer, thereby progressing the propagation reaction. Even if the first monomer is consumed, the propagation terminal does not lose activity, and reacts with the second monomer that is added sequentially to obtain a block polymer.
• Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), and radical polymerization using organotellurium (TERP). Of these, there are no particular restrictions on which method is used, but ATRP is preferred because of ease of control. In ATRP, polymerization is carried out using an organic halide or a sulfonyl halide compound as a polymerization initiator and a metal complex consisting of a transition metal compound and a ligand as a catalyst.
• polymerization initiators that can be used in ATRP include 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, ⁇ , ⁇ '-dichloroxylene, ⁇ , ⁇ '-dibromoxylene, hexakis( ⁇ -bromomethyl)benzene, and alkyl esters having 1 to 6 carbon atoms of 2-halogenated carboxylic acids having 1 to 6 carbon atoms (e.g., 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.).
• alkyl ester having 1 to 6 carbon atoms of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.
• Transition metal compounds that can be used in ATRP are represented by M n+ X n .
• the transition metal Mn + of the transition metal compound represented by Mn + Xn can be selected from the group consisting of Cu + , Cu2+, Fe2 + , Fe3 + , Ru2 + , Ru3 + , Cr2 + , Cr3 + , Mo0 , Mo + , Mo2 + , Mo3 + , W2 + , W3 + , Rh3 + , Rh4 +, Co+ , Co2 + , Re2+, Re3 + , Ni0 , Ni + , Mn3 + , Mn4 + , V2 +, V3 + , Zn + , Zn2+ , Au + , Au2+ , Ag + , and Ag2 + .
• X in the transition metal compound represented by M n+ X n can be selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO 4 ) 1/2 , (PO 4 ) 1/3 , (HPO 4 ) 1/2 , (H 2 PO 4 ), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN, and R 12 COO, where R 11 represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 12 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted with 1 to 5 halogens (preferably 1 to 3 fluorines or chlorines).
• Examples of ligand compounds capable of forming coordinate bonds with the transition metals of the above transition metal compounds include compounds having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms that can be coordinated with the transition metal via a ⁇ bond, compounds having a ligand containing two or more carbon atoms that can be coordinated with the transition metal via a ⁇ bond, and compounds having a ligand that can be coordinated with the transition metal via a ⁇ bond or ⁇ bond.
• transition metal complexes are not particularly limited, but preferred ones are complexes of transition metals of Groups 7, 8, 9, 10 and 11, and more preferred ones are complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel.
• ligands such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives
• polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine when the central metal is copper.
• divalent ruthenium complexes examples include dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzeneruthenium, dichlorop-cymeneruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, and carbonylchlorohydridotris(triphenylphosphine)ruthenium.
• divalent iron complexes examples include bistriphenylphosphine complexes and triazacyclononane complexes.
• solvents used in living radical polymerization include ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether-based solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen-based solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
• ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate
• ether-based solvents
• the feed ratio of the polymerizable monomers can be the same as that in the free radical polymerization method described above.
• the polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.
• metals resulting from the transition metal compounds used in the polymerization may remain in the resulting polymer. Metals remaining in the resulting polymer may be removed using activated alumina or the like after the polymerization is completed.
• the copolymer of the present invention can be suitably used as a leveling agent for a coating composition, and the coating composition of the present invention contains the copolymer of the present invention.
• the copolymer of the present invention can be used as a fluorine atom-free leveling agent that does not contain fluorine atoms, and therefore is a leveling agent that has low environmental accumulation and low environmental load.
• the content of the copolymer of the present invention contained in the coating composition of the present invention varies depending on the type of base resin, the coating method, the desired film thickness, etc., but is preferably in the range of 0.0001 to 10 parts by mass, more preferably in the range of 0.001 to 5 parts by mass, and even more preferably in the range of 0.01 to 2 parts by mass, per 100 parts by mass of the solid content of the coating composition. If the content of the copolymer of the present invention is within this range, the surface tension can be sufficiently reduced, the desired leveling properties can be obtained, and the occurrence of problems such as foaming during coating can be suppressed.
• the application of the coating composition of the present invention is not particularly limited, and it can be used in any application that requires leveling properties.
• it can be used as a coating composition for displays such as color filters (color resists) and polarizing plate hard coats.
• the coating composition of the present invention can be used, for example, as various paint compositions or photosensitive resin compositions.
• examples of the paint composition include paints using natural resins such as petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, cashew resin paints, and oil-based vehicle paints; and paints using synthetic resins such as phenol resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints, and fluororesin paints.
• natural resins such as petroleum resin paints, shellac paints, rosin-based paints, cellulose-based paints, rubber-based paints, lacquer paints, cashew resin paints, and oil-based vehicle paints
• synthetic resins such as phenol resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone
• the paint composition may contain, as necessary, various additives such as colorants such as pigments, dyes, and carbon; inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; and light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.
• colorants such as pigments, dyes, and carbon
• inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate
• organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene
• light resistance improvers weather resistance improvers, heat resistance improvers, antioxidants, thickeners, and anti-settling agents.
• any known and commonly used coating method can be used to apply the coating composition, including, for example, roll coating, electrostatic coating, bar coating, gravure coating, knife coating, dipping coating, spray coating, etc.
• the photosensitive resin composition changes its physical properties, such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability, when irradiated with light such as visible light or ultraviolet light.
• photosensitive resin compositions resist compositions (photoresist compositions, color resist compositions for color filters, etc.) are required to have high leveling properties.
• the resist composition is usually applied by spin coating to a thickness of about 1 to 2 ⁇ m on a silicon wafer or a glass substrate on which various metals are deposited. In this case, if the applied film thickness fluctuates or unevenness occurs in the application, the linearity and reproducibility of the pattern decreases, and a problem occurs in which a resist pattern with the desired accuracy cannot be obtained.
• the coating composition of the present invention can solve the above problems when used as a resist composition, since the copolymer of the present invention exhibits high leveling properties and can form a uniform coating film (cured product).
• the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, etc. in addition to the copolymer of the present invention.
• the alkali-soluble resin contained in the photoresist composition is a resin that is soluble in an alkaline solution, which is the developer used when patterning the resist.
• the alkali-soluble resin include novolak resins obtained by condensing an aromatic hydroxy compound derivative such as phenol, cresol, xylenol, resorcinol, phloroglucinol, or hydroquinone with an aldehyde compound such as formaldehyde, acetaldehyde, or benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol, or ⁇ -methylvinylphenol; (meth)acrylic acid-based polymers or copolymers such as acrylic acid, methacrylic acid, or hydroxyethyl (meth)acrylate; polyvinyl alcohol; modified resins obtained by introducing a radioactive ray-sensitive group such as a
• the radiation-sensitive substance contained in the photoresist composition is a substance that changes the solubility of an alkali-soluble resin in a developer when irradiated with energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays.
• energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays.
• radiation-sensitive substances include quinone diazide compounds, diazo compounds, azide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and poly(olefin sulfone) compounds.
• the quinone diazide compounds include, for example, 1,2-benzoquinone azide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, and sulfonic acid chlorides of quinone diazide derivatives such as 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 2,1-naphthoquinone diazide-4-sulfonic acid chloride, and 2,1
• azide-based compounds examples include azidochalconic acid, diazidobenzalmethylcyclohexanones, azidocinnamylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.
• halogenated organic compound examples include halogen-containing oxadiazole-based compounds, halogen-containing triazine-based compounds, halogen-containing acetophenone-based compounds, halogen-containing benzophenone-based compounds, halogen-containing sulfoxide-based compounds, halogen-containing sulfone-based compounds, halogen-containing thiazole-based compounds, halogen-containing oxazole-based compounds, halogen-containing trizole-based compounds, halogen-containing 2-pyrone-based compounds, halogen-containing aliphatic hydrocarbon-based compounds, halogen-containing aromatic hydrocarbon-based compounds, halogen-containing heterocyclic compounds, and sulfenyl halide-based compounds.
• compounds used as halogen-based flame retardants such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether)tetrabromobisphenol A, bis(chloroethyl ether)tetrachlorobisphenol A, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxyethoxy-3,
• Examples of the organic acid ester include carboxylate ester and sulfonate ester.
• Examples of the organic acid amide include carboxylate amide and sulfonate amide.
• Examples of the organic acid imide include carboxylate imide and sulfonate imide.
• the radiation sensitive substance may be used alone or in combination of two or more kinds.
• the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by mass, and more preferably in the range of 50 to 150 parts by mass, per 100 parts by mass of the alkali-soluble resin.
• solvents for photoresist compositions include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; alcohol ethers such as ethyl formate, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propy
• the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant, etc. in addition to the copolymer of the present invention.
• the alkali-soluble resin contained in the color resist can be the same as the alkali-soluble resin contained in the photoresist composition described above.
• the polymerizable compound contained in the color resist composition is, for example, a compound having a photopolymerizable functional group that can polymerize or crosslink when irradiated with active energy rays such as ultraviolet rays.
• the polymerizable compound include unsaturated carboxylic acids such as (meth)acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification reactions of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polymerizable compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound, and polymerizable compounds having an acid group.
• the polymerizable compounds may be used alone or
• esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate.
• (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri
• examples of the (meth)acrylic acid portion of these acrylates include itaconic acid esters in which itaconic acid is substituted, crotonic acid esters in which crotonic acid is substituted, and maleic acid esters in which maleic acid is substituted.
• esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids examples include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, and pyrogallol tri(meth)acrylate.
• the ester obtained by the esterification reaction of the unsaturated carboxylic acid, the polycarboxylic acid, and the polyhydroxy compound may be a single substance or a mixture.
• esters examples include esters obtained from (meth)acrylic acid, phthalic acid, and ethylene glycol, esters obtained from (meth)acrylic acid, maleic acid, and diethylene glycol, esters obtained from (meth)acrylic acid, terephthalic acid, and pentaerythritol, and esters obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerin.
• Examples of polymerizable compounds having a urethane skeleton obtained by reacting the polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate with hydroxy compounds having a (meth)acryloyl group such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy[1,1,1-tri(meth)acryloyloxymethyl]propane.
• reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate
• alicyclic diisocyanates such as
• the polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyfunctional polymerizable compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride is preferable.
• the aliphatic polyhydroxy compound used for preparing the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol.
• the acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30, in order to improve developability, curability, etc.
• the acid value of the mixture of polymerizable compounds is set within the above range.
• polymerizable compounds having an acid group include a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which is commercially available as ARONIX TO-1382 (manufactured by Toagosei Co., Ltd.).
• polymerizable compounds include (meth)acrylamides such as ethylene bis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.
• the content of the polymerizable compound is preferably in the range of 5 to 80% by mass, more preferably in the range of 10 to 70% by mass, and even more preferably in the range of 20 to 50% by mass, of the total solid content of the color resist composition.
• the colorant for the color resist composition is not particularly limited as long as it is capable of imparting color, and may be, for example, a pigment or a dye.
• the pigment may be either an organic pigment or an inorganic pigment.
• the organic pigment pigments of various hues such as red pigments, green pigments, blue pigments, yellow pigments, purple pigments, orange pigments, and brown pigments may be used.
• examples of the chemical structure of the organic pigment include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments.
• examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.
• C.I stands for color index.
• the red pigment may be, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1 , 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 16 6, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193,
• C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferable, and C.I. Pigment Red 177, 209, 224 or 254 is more preferable.
• Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Among these, C.I. Pigment Green 7, 36, and 58 are preferred.
• Examples of the blue pigment include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.
• C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and C.I. Pigment Blue 15:6 is more preferred.
• the yellow pigment may be, for example, C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 1 38, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183,
• C.I. C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferred, and C.I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferred.
• Examples of the purple pigment include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
• C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.
• orange pigment examples include C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79.
• C.I. Pigment Orange 38 or 71 is preferred.
• the three primary color pixels of color filters used in liquid crystal display devices and organic EL display devices are red (R), green (G), and blue (B), so the red, green, and blue pigments are the main components, and organic pigments of colors such as yellow, purple, and orange may be used to adjust the hue in order to improve color reproducibility.
• the average particle size of the organic pigment is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.3 ⁇ m or less. It is preferable to use the organic pigment after dispersing it so that the average particle size falls within the above range.
• the average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm.
• the average particle size of the organic pigment is measured by a dynamic light scattering particle size distribution meter, and can be measured by, for example, a Nanotrac particle size distribution measuring device "UPA-EX150” or “UPA-EX250” manufactured by Nikkiso Co., Ltd.
• the colorant is not particularly limited as long as it is black, and examples thereof include carbon black, lamp black, acetylene black, bone black, thermal black, channel black, furnace black, graphite, iron black, titanium black, etc. Among these, carbon black and titanium black are preferred from the viewpoints of light shielding rate and image characteristics.
• two or more organic pigments may be mixed to produce a black color.
• carbon black products include, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, and #980 manufactured by Mitsubishi Chemical Corporation. #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, and the like.
• Printex3, Printex3OP, Printex4OP, Printex5OP, and Printex6OP are manufactured by Evonik Degussa Japan Ltd. tex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, S Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW1 8, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc., manufactured by Cabot Japan Co., Ltd., Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, etc.
• resin-coated carbon black is preferred as it has the high optical density and high surface resistivity required for the black matrix of a color filter.
• titanium black products include, for example, titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.
• BM black matrix
• two or more kinds of organic pigments may be mixed to produce a black color
• examples of the black pigment include a mixture of three color pigments, red, green, and blue.
• Colorants that can be mixed to prepare black pigments include Victoria Pure Blue (C.I. 42595), Auramine O (C.I. 41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (C.I. 45160), Rhodamine B (C.I. 45170), Safranin OK70:100 (C.I. 50240), Erioglaucine X (C.I. 42080), No. 120/Lionol Yellow (C.I.
• the average primary particle size of the carbon black is preferably in the range of 0.01 to 0.08 ⁇ m, and more preferably in the range of 0.02 to 0.05 ⁇ m due to its good developability.
• Carbon black has a particle shape different from that of organic pigments, etc., and exists in a state called a structure in which primary particles are fused to each other, and fine pores may be formed on the particle surface by post-treatment. Therefore, in order to express the particle shape of carbon black, it is generally preferable to measure the DBP absorption (JIS K6221) and the specific surface area by the BET method (JIS K6217) in addition to the average particle size of the primary particles obtained by the same method as for the organic pigments, and use these as indicators of the structure and the amount of pores.
• DBP absorption JIS K6221
• JIS K6217 BET method
• the dibutyl phthalate (DBP) absorption of carbon black is preferably in the range of 40 to 100 cm3 /100g, more preferably in the range of 50 to 80 cm3 /100g due to good dispersibility and developability.
• the specific surface area of carbon black measured by the BET method is preferably in the range of 50 to 120 m2 /g, more preferably in the range of 60 to 95 m2 /g due to good dispersion stability.
• the azo dyes include, for example, C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Examples include Mordant Red 7, C.I. Mordant Yellow 5, and C.I. Mordant Black 7.
• anthraquinone dyes examples include C.I. Bat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60.
• Examples of the phthalocyanine dyes include C.I. Pad Blue 5, and examples of the quinoneimine dyes include C.I. Basic Blue 3 and C.I. Basic Blue 9, and examples of the quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3 and C.I. Disperse Yellow 64, and examples of the nitro dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3 and C.I. Disperse Yellow 42.
• a pigment as the colorant for the color resist composition, since the resulting coating film has excellent light resistance, weather resistance, and fastness, but a dye may be used in combination with the pigment as necessary to adjust the hue.
• the content of the colorant is preferably 1% by mass or more of the total solid content of the color resist composition, more preferably in the range of 5 to 80% by mass, and even more preferably in the range of 5 to 70% by mass.
• the content of the colorant in the color resist composition is preferably in the range of 5 to 60 mass % of the total solid content of the color resist composition, and more preferably in the range of 10 to 50 mass %.
• the content of the colorant in the color resist composition is preferably in the range of 20 to 80 mass % of the total solid content of the color resist composition, and more preferably in the range of 30 to 70 mass %.
• the colorant when the colorant is a pigment, it is preferable to use the pigment as a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant.
• the dispersant include surfactants, pigment intermediates or derivatives, dye intermediates or derivatives, and resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins.
• resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins.
• graft copolymers having nitrogen atoms, acrylic block copolymers having nitrogen atoms, and urethane resin dispersants are preferred.
• these dispersants have nitrogen atoms, the nitrogen atoms have affinity for the pigment surface, and the portions other than the nitrogen atoms increase the affinity for the medium, thereby improving the dispersion stability.
• These dispersants may be used alone or in combination of two or more kinds.
• dispersants include the "Efka” series (Efka 46, etc.) manufactured by BASF; the “Disperbyk” series and “BYK” series (BYK-160, BYK-161, BYK-2001, etc.) manufactured by BYK Japan; the “Solsperse” series manufactured by Lubrizol Japan; the "KP” series manufactured by Shin-Etsu Chemical Co., Ltd., the “Polyflow” series manufactured by Kyoeisha Chemical Co., Ltd.; the "Disparlon” series manufactured by Kusumoto Chemicals Co., Ltd.; and the "Ajisper” series manufactured by Ajinomoto Fine-Techno Co., Ltd. (Ajisper PB-814, etc.).
• organic solvent used in preparing the pigment dispersion examples include acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate-based solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene, and methoxybenzene; ether-based solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon-based solvents such as hexane; nitrogen compound-based solvents such as N,N-dimethylformamide, ⁇ -butyrolactam, and N-methyl-2-pyrrolidone; lactone-based solvents such as ⁇ -butyrolactone
• the method for preparing the pigment dispersion liquid includes a method that includes a colorant kneading/dispersing step and a fine-dispersing step, and a method that includes only the fine-dispersing step.
• the colorant, a part of the alkali-soluble resin, and optionally the dispersant are mixed and kneaded.
• the colorant can be dispersed by dispersing while applying a strong shear force using a kneader.
• Examples of machines used for kneading include two-roll machines, three-roll machines, ball mills, tron mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, and single- or twin-screw extruders. It is preferable that the colorant be reduced in particle size by a salt milling method or the like before the above kneading is carried out.
• a solvent is added to the colorant-containing composition obtained in the kneading and dispersion process, or a mixture of a colorant, an alkali-soluble resin, a solvent, and, if necessary, the dispersant is mixed together with fine dispersion media such as glass, zirconia, or ceramic, and then mixed and dispersed using a disperser, thereby dispersing the colorant particles to a minute state close to primary particles.
• the average particle size of the primary particles of the colorant is preferably from 10 to 100 nm, and more preferably from 10 to 60 nm.
• the average particle size of the colorant is measured by a dynamic light scattering particle size distribution meter, and can be measured by, for example, a Nanotrac particle size distribution measuring device "UPA-EX150" or “UPA-EX250” manufactured by Nikkiso Co., Ltd.
• the weight average molecular weight (Mw) of the synthesized resin was measured under the following GPC measurement conditions.
• Measurement equipment Tosoh Corporation's high-speed GPC equipment "HLC-8420GPC”
• Data processing Tosoh Corporation's "EcoSEC Data Analysis Version 1.07"
• Developing solvent tetrahydrofuran Flow rate: 0.35 mL/min
• Measurement sample 7.5 mg of a sample
• Example 1 In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 100.0 g of butyl acetate was charged as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream. Next, 67.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (forming structural unit A), 33.0 g of propylene glycol-polybutylene glycol-monomethacrylate (forming structural unit B: NOF Corp., Blemmer 10PPB-500B), and 70.0 g of butyl acetate as a solvent were mixed to obtain a mixed solution A.
• Comparative Example 1 A glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device was charged with 100.0 g of butyl acetate as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream. Next, 33.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane, 67.0 g of propylene glycol-polybutylene glycol-monomethacrylate, and 70.0 g of butyl acetate as a solvent were mixed to obtain mixed solution A. Furthermore, 3.0 g of an initiator (Perbutyl O) and 63.3 g of butyl acetate as a solvent were mixed to obtain mixed solution B.
• an initiator Perbutyl O
• 63.3 g of butyl acetate as a solvent were mixed to obtain mixed solution B.
• Comparative Example 2 A nitrogen-purged flask was charged with 75.0 g of methyl ethyl ketone as a solvent and 33.5 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane, and the temperature was raised to 50° C. while stirring under a nitrogen stream. Next, 4.2 g of 2,2'-bipyridyl and 1.5 g of cuprous chloride were charged, and the flask was stirred for 30 minutes while maintaining the temperature at 50° C. Thereafter, 2.7 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted for 4 hours at 50° C.
• the dried coating film was irradiated with ultraviolet (UV) rays using an ultraviolet curing device (in an air atmosphere, high-pressure mercury lamp, ultraviolet radiation dose of 0.5 kJ/ m2 ) to be cured, and then developed using a 0.5% KOH-based developer, and further heat-treated at 230°C for 20 minutes to obtain a cured film.
• the contact angle of PGMEA on the surface of the cured film was measured using a contact angle measuring device ("MODEL CA-W701" manufactured by Kyowa Interface Science Co., Ltd.).
• a small contact angle means that the recoatability of the cured film is good.
• the recoatability was evaluated based on the contact angle according to the following criteria.
• ⁇ : PGMEA contact angle is 20 degrees or less
• PGMEA contact angle is more than 20 degrees and less than 30 degrees
• PGMEA contact angle is more than 30 degrees

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