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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • 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
  • 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
  • C08F220/287—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 and containing polypropylene oxide 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
  • C08F290/068—Polysiloxanes
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
  • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
• • 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
  • C09D151/085—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 on to polysiloxanes
• • 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
  • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2150/00—Compositions for coatings

Definitions

• the present invention relates to a silicone chain-containing polymer, a method for producing a silicone chain-containing polymer, a coating composition, a resist composition, and an article.
• a leveling agent is added to smooth the coating film obtained by applying a coating composition such as a coating composition or a resist composition. Specifically, by adding a leveling agent to the coating composition, the leveling agent is oriented on the surface of the coating film to lower the surface tension of the coating film, thereby smoothing the resulting coating film.
• a coating film having a smooth surface can improve repellency and unevenness.
• Leveling agents are used, for example, in automotive paints, and a coating composition containing a leveling agent can impart high smoothness to the resulting coating film surface and can impart gloss to the appearance of automobiles.
• a silicone-based leveling agent has been proposed, and a leveling agent having a relatively short silicone chain (for example, Patent Document 1) and a leveling agent having a relatively long silicone chain (for example, Patent Document 2) have also been proposed.
• leveling agents are diverse, and they are also used, for example, in color resist compositions used in the production of color filters for liquid crystal displays.
• the production of color filters generally includes 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 to light using a mask, and then developing to form a colored pattern. At this time, when the smoothness of the coating film is not good and the film thickness is uneven, or when there is coating unevenness, cissing, etc., color unevenness may occur in the pixels.
• the smoothness of the resulting coating film is improved, and the surface of the red (R), green (G), and blue (B) pixels and the black matrix (BM) formed between these pixels can exhibit high smoothness, and a color filter with little color unevenness can be obtained.
• a coating film obtained by coating a substrate with a coating composition containing a leveling agent can exhibit high smoothness.
• the coating film is generally dried in a vacuum drying device to evaporate the solvent in the coating film, and the coating film on the substrate is dried in the drying device chamber supported by support pins.
• a temperature difference occurs between the portion where the support pins and the base material are in contact with each other and the other portion, and there is a problem that uneven drying occurs due to the difference in drying rate. This pin unevenness was difficult to solve even when a leveling agent was added.
• the problem to be solved by the present invention is to provide a silicone chain-containing polymer that functions as a leveling agent that imparts high smoothness to the coating film and an effect of suppressing uneven pinning.
• the inventors of the present invention have found that, with regard to a silicone chain-containing polymer containing a polymerizable monomer having a specific silicone chain as a polymerization component, by setting the ratio of the polymerizable monomer having a silicone chain in the polymerization component to a specific range and setting the weight average molecular weight of the silicone chain-containing polymer to a specific range, the silicone chain-containing polymer imparts high smoothness and an effect of suppressing uneven pinning to the coating film, and completed the present invention.
• the present invention provides a silicone chain-containing polymer comprising, as polymerization components, a polymerizable monomer (1) having a group containing a structure represented by the following general formula (A), and a polymerizable monomer (2) having at least one 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, wherein the proportion of the polymerizable monomer (1) in the polymerization components is 20% by weight or less, and the weight average molecular weight is 1. It relates to a silicone chain-containing polymer having a molecular weight of 5,000 or more.
• each R 11 is independently an alkyl group having 1 to 6 carbon atoms; x indicates the number of repetitions, and the number average value is 20 or more.
• silicone chain-containing polymer that functions as a leveling agent that imparts high smoothness and an anti-cratering effect to coating films.
• (meth)acrylic acid means one or both of acrylic acid and methacrylic acid.
• the silicone chain-containing polymer of the present invention (hereinafter sometimes simply referred to as "the polymer of the present invention") is a silicone chain-containing polymer comprising, as polymerization components, a polymerizable monomer (1) having a group containing a structure represented by the following general formula (A), and a polymerizable monomer (2) having at least one 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, wherein the polymerizable monomer (1) accounts for the polymerizable components. is 20% by weight or less, and the weight average molecular weight is 15,000 or more.
• each R 11 is independently an alkyl group having 1 to 6 carbon atoms; x indicates the number of repetitions, and the number average value is 20 or more.
• polymerizable monomer means a compound having a polymerizable unsaturated group
• C C-containing groups
• a (meth)acryloyl group and a (meth)acryloyloxy group are preferable because of the availability of raw materials and favorable polymerization reactivity.
• the number of polymerizable unsaturated groups possessed by the polymerizable monomer may be one, or two or more.
• polymerization component means a component that constitutes a polymer, and does not include solvents, polymerization initiators, etc. that do not constitute a polymer.
• the group containing the structure represented by the general formula (A) is preferably a group represented by the following general formula (A1).
• each R 11 is independently an alkyl group having 1 to 6 carbon atoms
• each R 12 is independently an alkyl group having 1 to 6 carbon atoms
• R 13 is an alkyl group having 1 to 6 carbon atoms
• x indicates the number of repetitions, and the number average value is 20 or more.
• R 11 , R 12 and R 13 are preferably methyl groups.
• the number average value of x in the polymer of the present invention is 20 or more, preferably in the range of 30 to 300, more preferably in the range of 40 to 200, still more preferably in the range of 50 to 150.
• the "number average value of x" means the average number of repeating units of siloxane bonds per polymerizable monomer (1) constituting the polymer of the present invention.
• the number average value of x in the polymer of the invention can be calculated from the number average molecular weight of the polymer of the invention.
• the polymer of the present invention by setting the lower limit of the number average value of x in the polymer of the present invention to 20 or more, even if the proportion of the polymerizable monomer (1) is 20% by weight or less, the polymer of the present invention can exhibit a high surface tension-reducing ability, uniformly evaporate the solvent contained in the coating liquid, and suppress uneven pinning.
• the polymerizable monomer (1) is preferably a compound represented by the following general formula (1-1).
• R 11 , R 12 , R 13 and x are respectively the same as R 11 , R 12 , R 13 and x in the general formulas (A) and (A1);
• R 15 is a hydrogen atom or a methyl group,
• L 1 is a divalent organic group.
• the divalent organic group of L 1 is preferably a single bond, an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• alkylene group having 1 to 50 carbon atoms for L 1 examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, isopropylene group, 2-methylpropylene group, 2-methylhexylene group and tetramethylethylene group.
• the alkylene group having 1 to 50 carbon atoms of L 1 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still 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 in L 1 is, for example, a group in which one —CH 2 — in the alkylene group is substituted with —O—.
• the alkyleneoxy group having 1 to 50 carbon atoms in L 1 is preferably an alkyleneoxy group having 1 to 15 carbon atoms, more preferably an alkyleneoxy group having 1 to 8 carbon atoms, and still 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 L 1 is an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms
• the polymerizable monomer (1) can be produced by a known method, and commercially available products may be used.
• the polymerizable monomer (2) having one or more 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, which is a polymerization component of the polymer of the present invention, has a function of ensuring compatibility, for example.
• the alkyl group having 1 to 18 carbon atoms possessed by the polymerizable monomer (2) may be any 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 of the polymerizable monomer (2) may be substituted with one or more substituents such as hydroxyl group, phenyl group and phenoxy group.
• the alkyl group having 1 to 18 carbon atoms possessed by the polymerizable monomer (2) includes, for example, a hydroxyalkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 18 carbon atoms, and a phenoxyalkyl group having 7 to 18 carbon atoms.
• the alkyl group having 1 to 18 carbon atoms possessed by the polymerizable monomer (2) is preferably an alkyl group having 1 to 8 carbon atoms.
• Examples of the aromatic group having 6 to 18 carbon atoms possessed by the polymerizable monomer (2) include phenyl group, naphthyl group, anthracen-1-yl group, phenanthren-1-yl group and the like.
• the aromatic group having 6 to 18 carbon atoms in the polymerizable monomer (2) may be further substituted with a substituent such as a hydroxyl group, an alkyl group, or an alkoxy group, and includes a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms.
• the group containing a polyoxyalkylene chain possessed by the polymerizable monomer (2) is a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety.
• the polymerizable monomer (2) may be one or more selected from, for example, a polymerizable monomer having an alkyl group having 1 to 18 carbon atoms, a polymerizable monomer having an aromatic group having 6 to 18 carbon atoms, and a polymerizable monomer having a group containing a polyoxyalkylene chain.
• the polymerizable monomer (2) essentially contains a polymerizable monomer having a group containing a polyoxyalkylene chain.
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having a (meth)acryloyl group as the polymerizable unsaturated 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, dodecyl (meth)acrylate, steary
• Examples of the polymerizable monomer (2) having a hydroxyalkyl group having 1 to 18 carbon atoms and having a (meth)acryloyl group as the polymerizable unsaturated group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxy (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and the like.
• Examples of the polymerizable monomer (2) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and having a (meth)acryloyl group as the polymerizable unsaturated group include benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.
• Examples of the polymerizable monomer (2) having a group containing a polyoxyalkylene chain and having a (meth)acryloyl group as the polymerizable unsaturated 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).
• 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
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having a vinyl ether group as the polymerizable unsaturated group include 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, cyclohexyl vinyl ether, and the like.
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having an allyl group as the polymerizable unsaturated group include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.
• Examples of the polymerizable monomer (2) having an aromatic group having 6 to 18 carbon atoms include styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene and the like.
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having a (meth)acryloylamino group as the polymerizable unsaturated group include N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, and acryloylmorpholine.
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having a maleimide group as the polymerizable unsaturated group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.
• the polymerizable monomer (2) is preferably a compound represented by the following general formula (2-1) and/or a compound represented by (2-2). These compounds can impart compatibility when the polymer of the present invention is used as a leveling agent.
• R 21 is an alkyl group having 1 to 18 carbon atoms
• R 22 is a hydrogen atom or a methyl group
• R 23 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
• R 24 is a hydrogen atom or a methyl group
• n is an integer in the range 1-4 and m is an integer in the range 1-200.
• n in parenthesized C n H 2n O may be the same or different for each repeating unit. Moreover, when n is 2 or more types, 2 or more types of repeating units may be random polymerization or block polymerization.
• the alkyl group having 1 to 18 carbon atoms for R 21 and R 23 is preferably an alkyl group having 1 to 8 carbon atoms.
• m is preferably an integer in the range of 2-50, more preferably an integer in the range of 3-20.
• the polymerizable monomer (2) is preferably a compound represented by the following general formula (2-3).
• each R 25 is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms;
• R 26 is a hydrogen atom or a methyl group, l is an integer from 0 to 5;
• Polymerizable monomer (2) can be produced by a known method. Moreover, a commercial item may be used for the polymerizable monomer (2).
• commercially available polymerizable monomers (3-2) having a group containing a polyoxyalkylene chain and having a (meth)acryloyl group as the polymerizable unsaturated 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”, and "NK” manufactured by Shin-Nakamura Chemical Co., Ltd.
• the polymer of the present invention may be any polymer containing the polymerizable monomer (1) and the polymerizable monomer (2) as polymerization components, and the polymerization method is not particularly limited.
• the polymer of the present invention may be a random copolymer of the polymerizable monomer (1) and the polymerizable monomer (2), or may be a block copolymer of the polymerizable monomer (1) and the polymerizable monomer (2), preferably a block copolymer of the polymerizable monomer (1) and the polymerizable monomer (2).
• the polymer of the present invention is a block copolymer of the polymerizable monomer (1) and the polymerizable monomer (2)
• the number and bonding order of the polymer block of the polymerizable monomer (1) and the polymer block of the polymerizable monomer (2) are not particularly limited.
• the polymerizable monomer (1) may be a single polymerizable monomer (1) or two or more polymerizable monomers (1) having different structures.
• the polymerizable monomer (2) in the polymerization component may be a single polymerizable monomer (2) or two or more polymerizable monomers (2) having different structures.
• the content of the polymerizable monomer (1) in the polymerizable component may be 20% by weight or less, preferably 18% by weight or less, more preferably 15% by weight or less, and still more preferably 12% by weight or less. When the content of the polymerizable monomer (1) in the polymerization component is within this range, excellent leveling properties can be obtained.
• the lower limit of the content of the polymerizable monomer (1) in the polymerization component is not particularly limited, it is, for example, 3% by weight or more, preferably 4% by weight or more, and more preferably 5% by weight or more.
• the content of the polymerizable monomer (1) can be adjusted by adjusting the raw material charging ratio of the polymerizable monomer (1) when producing the polymer of the present invention.
• the content ratio of the groups represented by general formula (A) in the polymer of the present invention is, for example, 3 to 20% by mass, preferably 3 to 18% by mass, more preferably 5 to 15% by mass, still more preferably 5 to 12% by mass, particularly preferably 7 to 10% by mass.
• the content ratio of the group represented by the general formula (A) can be adjusted by adjusting the raw material charging ratio of the polymerizable monomer (1) used when producing the polymer of the present invention.
• the polymerizable component may contain the polymerizable monomer (1) and the polymerizable monomer (2), may consist essentially of the polymerizable monomer (1) and the polymerizable monomer (2), or may consist only of the polymerizable monomer (1) and the polymerizable monomer (2).
• substantially means that the total content of the polymerizable monomer (1) and the polymerizable monomer (2) in the polymerization component is, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 98% by mass or more.
• the polymer of the present invention preferably does not contain fluorine atoms.
• the polymer of the present invention preferably does not contain fluorine atoms.
• the polymers of the invention preferably do not contain reactive functional groups.
• the "reactive functional group” is a functional group capable of forming a crosslinked structure or the like by reacting with another functional group, and examples thereof include an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic acid anhydride group.
• the weight average molecular weight (Mw) of the polymer of the present invention is 15,000 or more, preferably 20,000 or more, more preferably 20,500 or more.
• the upper limit of the polymer average molecular weight (Mw) of the polymer of the present invention is not particularly limited, and is preferably 100,000 or less, 90,000 or less, 70,000 or less, and 50,000 or less, in that order.
• the value of the weight average molecular weight (Mw) of the polymer of the present invention is measured by the method described in Examples.
• the method for producing the polymer of the present invention is not particularly limited, and the polymer can be produced by a known method.
• the polymer of the present invention can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, or the like.
• a radical polymerization method the polymer of the present invention can be produced by adding polymerization components to an organic solvent and adding a general-purpose radical polymerization initiator.
• the polymer obtained above is a random copolymer.
• Various polymerization 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 .
• a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a thiol compound having a coupling group such as ⁇ -mercaptopropyltrimethoxysilane may be used as an additive such as a chain transfer agent.
• 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 phosphate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; polar solvents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone; ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, and ethyl cellosolv
• the polymer of the present invention preferably starts adding the polymerizable monomer (1) to the reaction system, and after starting the addition of the polymerizable monomer (1), the polymerizable monomer (2) and a polymerization initiator are added to the reaction system to start polymerization, and the addition of the polymerizable monomer (1) is completed before the polymerizable monomer (2) and the polymerization initiator.
• the polymerizable monomer (1) may contain an impurity of a compound having a cyclic siloxane structure, and the compound having a cyclic siloxane structure should be removed by distilling the polymerizable monomer (1) before adding it to the reaction system, distilling the polymer after the reaction, or the like. Distillation can be carried out by known methods, such as thin film distillation.
• the polymer of the present invention can also be produced by subjecting polymerization components to living polymerization such as living radical polymerization and living anion polymerization.
• a dormant species whose active polymerization terminal is protected by an atom or an atomic group reversibly generates a radical and reacts with a monomer to proceed with the propagating reaction. Even if the first monomer is consumed, the propagating terminal does not lose activity and reacts with the sequentially added second monomer 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), radical polymerization using organotellurium (TERP), and the like.
• ATRP is preferred because of ease of control and the like.
• ATRP is polymerized using an organic halide, a sulfonyl halide compound, or the like as a polymerization initiator and a metal complex composed 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, 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.) and alkyl esters having 1 to 6 carbon atoms.
• alkyl esters having 1 to 6 carbon atoms of 2-halogenated carboxylic acids having 1 to 6 carbon atoms include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate.
• Transition metal compounds that can be used in ATRP are those represented by Mn + Xn .
• the transition metal Mn+ of the transition metal compound represented by Mn + Xn includes Cu + , Cu2+, Fe2 + , Fe3+, Ru2+, Ru3+ , Cr2 + , Cr3+ , Mo0 , Mo + , Mo2+, Mo3 + , W2 +, W3+, Rh3+, R h4+, 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 is 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.
• R 11 represents an aryl group or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms)
• 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 1 to 5 times with halogen (preferably 1 to 3 times with fluorine or chlorine).
• halogen preferably 1 to 3 times with fluorine or chlorine
• Examples of ligand compounds of the above transition metal compounds capable of coordinating to the transition metal include compounds having ligands containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms or sulfur atoms that can coordinate with the transition metal via ⁇ bonds, compounds containing ligands containing two or more carbon atoms that can coordinate with the transition metal via ⁇ bonds, and compounds having ligands that can coordinate with the transition metal via ⁇ bonds or ⁇ bonds.
• transition metal complex is not particularly limited, preferred ones are transition metal complexes of Groups 7, 8, 9, 10, and 11, and more preferred ones are zerovalent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel complexes.
• 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 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, carbonyl chlorohydrid tris(triphenylphosphine) ruthenium and the like.
• bivalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.
• a solvent is preferably used in the living radical polymerization.
• solvents used in living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; aprotic polar solvents such as The above solvents may be used singly or in combination of two or more.
• Method 1 A method of subjecting polymerizable monomer (1) and polymerizable monomer (2) to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of coordinating with the transition metal, and a solvent.
• living radical polymerization preferably atom transfer radical polymerization
• Method 2 A method in which the polymerizable monomer (1) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of coordinating with the transition metal, and a solvent to obtain a polymer block of the polymerizable monomer (1), and then the polymerizable monomer (2) is added to the reaction system, and the polymer block of the polymerizable monomer (1) is further subjected to living radical polymerization (preferably atom transfer radical polymerization) of the polymerizable monomer (2).
• living radical polymerization preferably atom transfer radical polymerization
• Method 3 A method in which the polymerizable monomer (2) is subjected to living radical polymerization (preferably atom transfer radical polymerization) in the presence of a polymerization initiator, a transition metal compound, a ligand compound capable of coordinating with the transition metal, and a solvent.
• living radical polymerization preferably atom transfer radical polymerization
• the polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120°C.
• metals derived from the transition metal compound 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 completion of the polymerization.
• the polymer of the present invention can be suitably used as a leveling agent for coating compositions, and the coating composition of the present invention contains the polymer of the present invention. Since the polymer of the present invention can be used as a fluorine atom-free leveling agent that does not contain fluorine atoms, it is a leveling agent with low environmental load and low accumulation in the environment.
• the content of the polymer of the present invention contained in the coating composition of the present invention varies depending on the type of base resin, coating method, desired film thickness, etc., but is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and even more preferably 0.01 to 2 parts by mass based on 100 parts by mass of the solid content (eg, base resin) of the coating composition. If the content of the polymer of the present invention is within the above range, the surface tension can be sufficiently lowered, the desired leveling property can be obtained, and the occurrence of defects 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 for any application that requires leveling properties.
• the coating composition of the present invention can be used, for example, as various coating compositions and photosensitive resin compositions.
• the paint composition of the present invention when used as a composition for paint, the paint composition, for example, paint using natural resin, such as petroleum resin paint, cellac paint, cellulose paint, rubber paint, lacquer paint, cashew the paint, and oil -based beigl paint; phenol. Resin paint, alquid resin paint, unsaturated polyester resin paint, amino resin paint, epoxy resin paint, vinyl resin paint, acrylic resin paint, polyurethane resin paint, silicone resin paint, fluorine resin paint, etc. It is listed. By adding the polymer of the present invention to the coating composition, smoothness can be imparted to the resulting coating film.
• natural resin such as petroleum resin paint, cellac paint, cellulose paint, rubber paint, lacquer paint, cashew the paint, and oil -based beigl paint
• Resin paint alquid resin paint, unsaturated polyester resin paint, amino resin paint, epoxy resin paint, vinyl resin paint, acrylic resin paint, polyurethane resin paint, silicone resin paint, fluorine resin paint, etc. It is listed.
• Coloring agents 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
• any method can be used as long as it is a known and publicly used coating method.
• examples include methods such as slit coater, slit & spin coater, spin coater, roll coater, electrostatic coating, bar coater, gravure coater, die coater, knife coater, inkjet, dipping coating, spray coating, shower coating, screen printing, gravure printing, offset printing, and reverse coating.
• 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 deposited with various metals. At this time, if the coating film thickness fluctuates or coating unevenness occurs, the linearity and reproducibility of the pattern are degraded, resulting in a problem that a resist pattern having the desired accuracy cannot be obtained.
• the coating composition of the present invention can form a uniform coating film (cured product) with the polymer of the present invention exhibiting a high leveling property, so that the above problems can be solved when used as a resist composition.
• the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent, etc. in addition to the polymer 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 a developer used when patterning the resist.
• Alkali-soluble resins include, for example, novolak resins obtained by condensing aromatic hydroxy compound derivatives such as phenol, cresol, xylenol, resorcinol, phlorogricinol and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde and benzaldehyde; polymers or copolymers of vinylphenol compound derivatives such as o-vinylphenol, m-vinylphenol, p-vinylphenol and ⁇ -methylvinylphenol; (meth)acrylic acid polymers such as acrylic acid, methacrylic acid and hydroxyethyl (meth)acrylate.
• alkali-soluble resins may be used singly or in combination of two or more.
• the radiation-sensitive substance contained in the photoresist composition is a substance that changes the solubility of an alkali-soluble resin in a developer upon exposure to energy rays such as ultraviolet rays, deep ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays.
• energy rays such as ultraviolet rays, deep ultraviolet rays, excimer laser light, X-rays, electron beams, ion beams, molecular beams, and gamma rays.
• radiation-sensitive substances include quinonediazide 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, poly(olefin sulfone) compounds, and the like.
• Examples of the quinonediazide compounds include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, and other 1,2-benzoquinonediazide-4-sulfonic acid esters.
• quinonediazide derivatives such as chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, and 2,1-naphthoquinonediazide-5-sulfonic acid chloride.
• diazo-based compound examples include a salt of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, a diazo resin inorganic salt that is a reaction product between hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the condensate, and a diazo resin organic salt that is a reaction product of the condensate and sulfonic acids as described in USP 3,300,309.
• azide compounds examples include azido chalconic 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 trizol-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 sulphenyl halide-based compounds.
• 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, 2,2-bis(4-hydroxyethoxy-3,5-dibromophen
• organic acid esters include carboxylic acid esters and sulfonic acid esters.
• organic acid amides include carboxylic acid amides and sulfonic acid amides.
• organic acid imides include carboxylic acid imides, sulfonic acid imides, and the like.
• the radiation-sensitive substances may be used singly or in combination of two or more.
• the content of the radiation-sensitive substance is preferably in the range of 10 to 200 parts by mass, more preferably in the range of 50 to 150 parts by mass, with respect to 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, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol and decanol; ethylene glycol dimethyl ether and ethylene.
• ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone and butyrolactone
• alcohols such as methanol, ethanol, n-propy
• Ethers such as glycol diethyl ether and dioxane; Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; 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, butyl 2-methoxypropionate; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl Cellosolve esters such as cellosolve acetate; Propylene glycols such
• the coating composition of the present invention When the coating composition of the present invention is used as a color resist composition, the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant, etc. in addition to the polymer of the present invention.
• the same alkali-soluble resin as contained in the photoresist composition can be used.
• the polymerizable compound contained in the color resist composition is, for example, a compound having a photopolymerizable functional group capable of polymerizing or cross-linking reaction upon exposure to 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 polyhydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and esters obtained by reacting polyisocyanate compounds with (meth)acryloyl group-containing hydroxy compounds.
• a polymerizable compound having a urethane skeleton, a polymerizable compound having an acid group, and the like are included.
• a polymerizable compound may be used individually by
• esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include 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, and dipentaerythritol.
• (Meth)acrylic acid esters such as tall hexa(meth)acrylate and glycerol (meth)acrylate can be mentioned.
• the (meth)acrylic acid portion of these acrylates may be replaced with itaconic acid esters, crotonic acid esters replaced with crotonic acid, or maleic acid esters replaced with maleic acid.
• esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, pyrogallol tri(meth)acrylate and the like.
• the ester obtained by the esterification reaction of unsaturated carboxylic acid, polyvalent carboxylic acid and polyvalent hydroxy 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.
• the polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with the (meth)acryloyl group-containing hydroxy compound includes aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; reaction products with hydroxy compounds having a (meth)acryloyl group such as yloxymethyl]propane;
• the polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a polyfunctional polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Pentaerythritol or dipentaerythritol is preferable as the aliphatic polyhydroxy compound used for preparing the polyfunctional polymerizable compound.
• 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, because good developability, curability and the like are obtained.
• the acid value of the mixture of the polymerizable compounds is preferably within the above range.
• polymerizable compound having an acid group examples include a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinic acid ester of dipentaerythritol pentaacrylate as a main component, and the mixture is commercially available as Aronix TO-1382 (manufactured by Toagosei Co., Ltd.).
• polymerizable compounds other than the above examples include (meth)acrylamides such as ethylenebis(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, based on the total solid content of the color resist composition.
• the coloring agent for the color resist composition is not particularly limited as long as it can be colored, and may be, for example, a pigment or a dye.
• Either an organic pigment or an inorganic pigment can be used as the pigment.
• the organic pigments pigments of various hues such as red pigments, green pigments, blue pigments, yellow pigments, purple pigments, orange pigments and brown pigments can be used.
• Examples of chemical structures of organic pigments include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments.
• the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.
• C.I means a color index.
• red pigment for example, C.I. 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: 1,53:2,53:3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,1 12, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210
• C.I. I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferred, C.I. I. Pigment Red 177, 209, 224 or 254 is more preferred.
• C.I. I. Pigment Green 1 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like.
• C.I. I. Pigment Green 7, 36 or 58 are preferred.
• C.I. 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, 79 and the like.
• C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and C.I. I. Pigment Blue 15:6 is more preferred.
• C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferred, and C.I. I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferred.
• C.I. 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, 50 and the like.
• C.I. I. Pigment Violet 19 or 23 are preferred, C.I. I. Pigment Violet 23 is more preferred.
• C.I. 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, 79 and the like.
• C.I. I. Pigment Orange 38 or 71 are preferred.
• red (R), green (G), and blue (B) the red pigment, green pigment, and blue pigment are the main components, and for the purpose of improving color reproducibility, organic pigments of colors such as yellow, purple, and orange may be used for hue adjustment.
• 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, in order to increase the luminance of color liquid crystal display devices and organic EL display devices. It is preferable to disperse and use the organic pigment so as to obtain these average particle diameters.
• the average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, still 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 with a dynamic light scattering particle size distribution meter, for example, Nanotrac particle size distribution measuring device "UPA-EX150” and “UPA-EX250” manufactured by Nikkiso Co., Ltd. It can be measured.
• a dynamic light scattering particle size distribution meter for example, Nanotrac particle size distribution measuring device "UPA-EX150” and “UPA-EX250” manufactured by Nikkiso Co., Ltd. It can be measured.
• 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, and titanium black.
• carbon black and titanium black are preferable from the viewpoint of light shielding rate and image characteristics.
• two or more kinds of organic pigments may be mixed to obtain a black color by mixing the colors.
• Examples of commercially available carbon black products include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, and #85 manufactured by Mitsubishi Chemical Corporation.
• resin-coated carbon black is preferable as it has a high optical density and a high surface resistivity required for the black matrix of color filters.
• titanium black products examples include titanium black 10S, 12S, 13R, 13M, 13M-C manufactured by Mitsubishi Materials Corporation.
• BM black matrix
• two or more organic pigments may be mixed to obtain black by color mixing, and a black pigment obtained by mixing red, green, and blue three-color pigments may be mentioned.
• Colorants that can be mixed to prepare black pigments include Victoria Pure Blue (CI 42595), Auramine O (CI 41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (CI 45160), Rhodamine B (CI 45170), Safranin OK 70:100 (CI 50240), Eriograu. Shin X (C.I. 42080), No.
• 120/Lionol Yellow (CI 21090), Lionol Yellow GRO (CI 21090), Shimla Fast Yellow 8GF (CI 21105), Benzidine Yellow 4T-564D (CI 21095), Shimla Fast Red 4015 (CI 12355), Lionor Red 7B4401 (CI 15850) , First Gen Blue TGR-L (CI 74160), Lionol Blue SM (CI 26150), Lionol Blue ES (CI Pigment Blue 15:6), Lionogen Red GD (CI Pigment Red 168), Lionor Green 2YS (CI Pigment Green 36) and the like.
• coloring materials that can be mixed to prepare black pigments include, for example, C.I. I. yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. orange pigments 36, 43, 51, 55, 59, 61, C.I. I. red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. blue pigment 15, 15:1, 15:4, 22, 60, 64, C.I. I. green pigment 7, C.I. I. brown pigments 23, 25, 26 and the like;
• the average primary particle size of carbon black is preferably in the range of 0.01 to 0.08 ⁇ m, more preferably in the range of 0.02 to 0.05 ⁇ m because of good developability.
• Carbon black has a particle shape different from that of organic pigments, 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 diameter of the primary particles obtained by the same method as the organic pigment, and use them as indicators of the structure and pore volume.
• DBP absorption JIS K6221
• JIS K6217 BET method
• Carbon black absorbs dibutyl phthalate (hereinafter abbreviated as "DBP") preferably in the range of 40 to 100 cm 3 /100 g, more preferably in the range of 50 to 80 cm 3 /100 g because of good dispersibility and developability.
• the BET specific surface area of carbon black is preferably in the range of 50 to 120 m 2 /g, more preferably in the range of 60 to 95 m 2 /g because of good dispersion stability.
• dyes used as colorants in color resist compositions include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
• azo dye for example, C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. mordant black 7 and the like.
• anthraquinone-based dyes examples include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like can be mentioned.
• Examples of the phthalocyanine dyes include C.I. I. Pad Blue 5 and the like, and examples of the quinone imine dyes include C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like, and examples of the quinoline dye include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like, and examples of the nitro-based dye include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include Disperse Yellow 42 and the like.
• a pigment is preferably used as the colorant of the color resist composition because the resulting coating film has excellent light resistance, weather resistance, and fastness.
• 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, more preferably in the range of 5 to 80% by mass, and even more preferably in the range of 5 to 70% by mass, based on the total solid content of the color resist composition.
• the content of the coloring agent in the color resist composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass, based on the total solid content of the color resist composition.
• the content of the colorant in the color resist composition is preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 70% by mass, based on the total solid content of the color resist composition.
• the colorant when it is a pigment, it is preferably used as a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant.
• the dispersant include surfactants; intermediates or derivatives of pigments; intermediates or derivatives of dyes; 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.
• a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer, a urethane resin dispersant, and the like are preferable.
• these dispersants have nitrogen atoms, the nitrogen atoms have an affinity for the pigment surface, and the portion other than the nitrogen atoms increases the affinity for the medium, thereby improving the dispersion stability.
• These dispersants may be used singly or in combination of two or more.
• organic solvent used in preparing the pigment dispersion examples include acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatic solvents such as toluene, xylene and methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether; Solvents; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, ⁇ -butyrolactam and N-methyl-2-pyrrolidone; lactone solvents such as ⁇ -butyrolactone; These solvents may be used singly or in combination of two or more.
• acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoe
• Examples of the method for preparing the pigment dispersion include a method in which a colorant is kneaded and dispersed and a fine dispersion step, and a method in which only a fine dispersion step is performed.
• the colorant, part of the alkali-soluble resin, and, if necessary, the dispersant are mixed and kneaded.
• the colorant can be dispersed by using a kneader to disperse while applying a strong shearing force.
• Machines used for kneading include two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, co-kneaders, homogenizers, blenders, single-screw or twin-screw extruders, and the like. It is preferable that the particle size of the coloring agent is made fine by salt milling or the like before kneading.
• a solvent is added to the composition containing the colorant obtained in the kneading and dispersion step, or a mixture of the colorant, the alkali-soluble resin, the solvent, and, if necessary, the dispersant is mixed and dispersed together with a dispersion medium for fine particles of glass, zirconia, or ceramic using a disperser, whereby the particles of the colorant can be dispersed to a fine state close to primary particles.
• the average particle size of the primary particles of the colorant is preferably 10 to 100 nm, more preferably 10 to 60 nm.
• the average particle diameter of the colorant is measured with a dynamic light scattering particle size distribution meter, and can be measured with, for example, Nanotrac particle size distribution measuring devices "UPA-EX150” and “UPA-EX250” manufactured by Nikkiso Co., Ltd.
• coating compositions As described above, coating compositions, photoresist compositions, and color resist compositions have been exemplified as coating compositions, but are not limited to these.
• coating composition of the present invention examples include anti-glare (AG) hard coating materials, anti-reflection (LR) coating materials, low refractive index layer coating materials, and high refractive index coating materials for various display screens such as liquid crystal displays (hereinafter abbreviated as “LCD”), plasma displays (hereinafter abbreviated as “PDP”), organic EL displays (hereinafter abbreviated as “OLED”), and quantum dot displays (hereinafter abbreviated as "QDD”).
• LCD liquid crystal displays
• PDP plasma displays
• OLED organic EL displays
• QDD quantum dot displays
• Layer coating materials clear hard coating materials, polymerizable liquid crystal coating materials; Color resists, inkjet inks, printing inks or paints for forming each pixel such as RGB of a color filter (hereinafter abbreviated as "CF") of LCDs, etc.; Black resists, inkjet inks, printing inks or paints for forming black matrixes, black column spacers, and black photospacers of CFs such as LCDs; Photospacer resin composition; LCD, PDP, OLED, QDD pixel partition resin composition, electrode-forming positive photoresist, protective film, insulating film, plastic housing, plastic housing paint, bezel (frame) ink; LCD backlight member prism sheet, light diffusion film; LCD liquid crystal TFT array organic insulating film paint; LCD internal polarizing plate surface protective coating material; QDD quantum dot ink, encapsulant, protective film; high refractive index lens, low refractive index encapsulation, LED pixel of micro (mini) LED display; positive photoresist,
• the polymer of the present invention Since the polymer of the present invention has an excellent ability to reduce surface tension, it can be expected to have not only leveling properties, but also wettability, penetrability, washability, water repellency, oil repellency, antifouling properties, lubricity, antiblocking properties, and releasability. Further, when the polymer of the present invention is blended in a paint or coating agent containing fine particles, it can be expected to improve the dispersibility of the fine particles and not only provide leveling properties but also function as a fine particle dispersant.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene-equivalent values based on gel permeation chromatography (GPC) measurement.
• GPC gel permeation chromatography
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of butyl acetate as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A1 at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A1, the dropping of the mixed liquid B1 and the mixed liquid C1 at 90° C. was started.
• Dropping of mixed liquid C1 was completed 120 minutes after the start of dropping, and dropping of mixed liquids A1 and B1 was completed 10 minutes after the completion of dropping of mixed liquid C1 (135 minutes after the start of dropping of mixed liquid A1).
• the mixture was stirred at 90°C for 10 hours.
• the solvent was distilled off to obtain a silicone chain-containing polymer (1).
• the molecular weight of the obtained silicone chain-containing polymer (1) was measured by GPC, and the weight average molecular weight (Mw) was 38,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (1) was 10% by mass based on the raw material charging ratio.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 130.0 g of butyl acetate as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A2 at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A2, the dropping of the mixed liquid B2 and the mixed liquid C2 at 90° C. was started.
• Dropping of mixed liquid C2 was completed 120 minutes after the start of dropping, and dropping of mixed liquids A2 and B2 was completed 30 minutes after the completion of dropping of mixed liquid C2 (155 minutes after the start of dropping of mixed liquid A2).
• the mixture was stirred at 90°C for 10 hours.
• the solvent was distilled off to obtain a silicone chain-containing polymer (2).
• the weight average molecular weight (Mw) of the resulting silicone chain-containing polymer (2) measured by GPC was 62,000.
• the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (2) was 10% by mass based on the raw material charging ratio.
• Synthesis Example 3 Synthesis of silicone chain-containing polymer (3)
• Mixture A3 was prepared by mixing 180.0 g of polypropylene glycol monomethacrylate (the average number of repetitions of propylene glycol is 4 to 6) and 61.4 g of butyl acetate as a solvent.
• Mixture B3 was prepared by mixing 6.0 g of initiator Perbutyl O (manufactured by NOF Corporation) and 50.0 g of butyl acetate as a solvent.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of butyl acetate as a solvent, and the temperature was raised to 85° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A3 at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A3, the dropping of the mixed liquid B3 and the mixed liquid C3 at 90° C. was started.
• Dropping of mixed liquid C3 was completed 120 minutes after the start of dropping, and dropping of mixed liquids A3 and B3 was completed 30 minutes after the completion of dropping of mixed liquid C3 (155 minutes after the start of dropping of mixed liquid A3).
• the mixture was stirred at 95°C for 10 hours.
• the solvent was distilled off to obtain a silicone chain-containing polymer (3).
• the molecular weight of the obtained silicone chain-containing polymer (3) was measured by GPC, and the weight average molecular weight (Mw) was 62,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (3) was 10% by mass based on the raw material charging ratio.
• Synthesis Example 4 Synthesis of silicone chain-containing polymer (4)
• Mixture A1 was prepared by mixing 180.0 g of polypropylene glycol monomethacrylate (average repetition number of propylene glycol: 4 to 6) and 30.0 g of butyl acetate as a solvent.
• Mixture B4 was prepared by mixing 6.0 g of t-butyl peroxy-2-ethylhexanoate as an initiator and 20.0 g of butyl acetate as a solvent. .
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 130.0 g of butyl acetate as a solvent, and the temperature was raised to 95° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A4 at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A4, the dropping of the mixed liquids B4 and C4 at 90° C. was started.
• Dropping of the mixed liquid C4 was completed 120 minutes after the start of dropping, and the dropping of the mixed liquids A4 and B4 was completed 30 minutes after the completion of the dropping of the mixed liquid C4 (155 minutes after the start of dropping of the mixed liquid A4).
• the mixture was stirred at 95°C for 10 hours.
• the solvent was distilled off to obtain a silicone chain-containing polymer (4).
• the molecular weight of the obtained silicone chain-containing polymer (4) was measured by GPC, and the weight average molecular weight (Mw) was 51,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (4) was 10% by mass based on the ratio of raw materials charged.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of PGMEA as a solvent, and the temperature was raised to 85° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A5 at 85° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A5, the dropping of the mixed liquid B5 and the mixed liquid C5 at 85° C. was started.
• Dropping of the mixed liquid C5 was completed 120 minutes after the start of dropping, and the dropping of the mixed liquids A5 and B5 was completed 10 minutes after the completion of the dropping of the mixed liquid C5 (135 minutes after the start of dropping of the mixed liquid A5).
• the mixture was stirred at 85°C for 5 hours, and then stirred at 110°C for 1 hour.
• the solvent was distilled off to obtain a silicone chain-containing polymer (5).
• the molecular weight of the obtained silicone chain-containing polymer (5) was measured by GPC, and the weight average molecular weight (Mw) was 21,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (5) was 10% by mass based on the ratio of raw materials charged.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of PGMEA as a solvent, and the temperature was raised to 85° C. while stirring under a nitrogen stream.
• the molecular weight of the obtained silicone chain-containing polymer (6) was measured by GPC, and the weight average molecular weight (Mw) was 21,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (6) was 20% by mass based on the raw material charging ratio.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of butyl acetate as a solvent, and the temperature was raised to 85° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A7 at 85° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A7, the dropping of the mixed liquid B7 and the mixed liquid C7 at 85° C. was started. Dropping of mixed liquid C7 was completed 120 minutes after the start of dropping, and dropping of mixed liquids A7 and B7 was completed 10 minutes after the completion of dropping of mixed liquid C7 (135 minutes after the start of dropping of mixed liquid A7). After completion of dropping, the mixture was stirred at 85°C for 5 hours, and then stirred at 110°C for 1 hour. After completion of the reaction, the solvent was distilled off to obtain a silicone chain-containing polymer (7).
• the molecular weight of the obtained silicone chain-containing polymer (7) was measured by GPC, and the weight average molecular weight (Mw) was 25,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (7) was found to be 10% by mass based on the raw material charging ratio.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 100.0 g of PGMEA as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A8 at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A8, the dropping of the mixed liquid B8 and the mixed liquid C8 at 90° C. was started.
• Dropping of the mixed liquid C8 was completed 120 minutes after the start of dropping, and the dropping of the mixed liquids A8 and B8 was completed 10 minutes after the completion of the dropping of the mixed liquid C8 (135 minutes after the start of dropping of the mixed liquid A8).
• the mixture was stirred at 90°C for 5 hours and then at 110°C for 1 hour.
• the solvent was distilled off to obtain a silicone chain-containing polymer (8).
• the molecular weight of the obtained silicone chain-containing polymer (8) was measured by GPC, and the weight average molecular weight (Mw) was 26,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (8) was 20% by mass based on the raw material charging ratio.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 300 g of PGMEA as a solvent, and the temperature was raised to 100° C. while stirring under a nitrogen stream.
• the molecular weight of the obtained silicone chain-containing polymer (9) was measured by GPC, and the weight average molecular weight (Mw) was 35,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (9) was found to be 10% by mass based on the raw material charging ratio.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of butyl acetate as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream. Dropping of the mixed liquid A1′ at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A1′, the dropping of the mixed liquid B1′ and the mixed liquid C1′ at 90° C. were started.
• the weight-average molecular weight (Mw) of the resulting silicone chain-containing polymer (1') measured by GPC was 13,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (1′) was 20% by mass based on the ratio of raw materials charged.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of butyl acetate as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream. Dropping of the mixed liquid A2′ at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A2′, the dropping of the mixed liquid B2′ and the mixed liquid C2′ at 90° C. were started.
• the weight-average molecular weight (Mw) of the resulting silicone chain-containing polymer (2') measured by GPC was 34,000.
• the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (2') was 31.6% by mass based on the ratio of raw materials charged.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of butyl acetate as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream. Dropping of the mixed liquid A3′ at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A3′, dropping of the mixed liquid B3′ and the mixed liquid C3′ at 90° C. were started.
• the molecular weight of the obtained silicone chain-containing polymer (3′) was measured by GPC, and the weight average molecular weight (Mw) was 14,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (3′) was 31.6% by mass based on the ratio of raw materials charged.
• a mixed solution A4' obtained by mixing 180.0 g of polypropylene glycol-polybutylene glycol-monomethacrylate (180.0 g of propylene glycol with an average repeating number of 1, and 6 with an average repeating number of butylene glycol of 6) and 60.43 g of butyl acetate as a solvent, a mixed solution B4' obtained by mixing 2.0 g of t-butyl peroxy-2-ethylhexanoate as an initiator and 50.0 g of butyl acetate as a solvent, 20.0 g of a monomethacrylate compound having a polysiloxane bond represented by the following formula, and acetic acid as a solvent.
• a mixed solution C4' was prepared by mixing 60.0 g of butyl.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 200.0 g of butyl acetate as a solvent, and the temperature was raised to 85° C. while stirring under a nitrogen stream. Dropping of the mixed liquid A4' at 85°C into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A4', the dropping of the mixed liquid B4' and the mixed liquid C4' at 85°C was started.
• the molecular weight of the obtained silicone chain-containing polymer (4') was measured by GPC, and the weight average molecular weight (Mw) was 32,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (4′) was 10.0% by mass based on the ratio of raw materials charged.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 100.0 g of PGMEA as a solvent, and the temperature was raised to 90° C. while stirring under a nitrogen stream.
• Dropping of the mixed liquid A5′ at 90° C. into the flask was started, and 5 minutes after the start of dropping of the mixed liquid A5′, dropwise addition of the mixed liquid B5′ and the mixed liquid C8 at 90° C. were started.
• Dropping of the mixed liquid C5' was completed 120 minutes after the start of dropping, and the dropping of the mixed liquids A5' and B5' was completed 10 minutes after the completion of dropping of the mixed liquid C8 (135 minutes after the start of dropping of the mixed liquid A5').
• the mixture was stirred at 90°C for 5 hours, and then stirred at 110°C for 1 hour.
• the solvent was distilled off to obtain a silicone chain-containing polymer (5').
• the molecular weight of the obtained silicone chain-containing polymer (5') was measured by GPC, and the weight average molecular weight (Mw) was 34,000. Moreover, the content ratio of the polymerizable unsaturated monomer having a silicone chain in the silicone chain-containing polymer (5′) was 20% by mass based on the ratio of raw materials charged.
• Example 1 Coating film formation and smoothness evaluation
• a coating film was formed as follows. 3.0 g of a 40% by mass resin solution of an alkali-soluble resin (Acrydic ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei Chemical Co., Ltd.), 0.0024 g of the silicone chain-containing polymer (1) in terms of solid content, and 6.23 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed. , to prepare a resist composition. 3 ml of the resulting resist composition was dropped onto the central portion of a 10 cm ⁇ 10 cm chrome-plated glass substrate, spin-coated under the conditions of a rotation speed of 1000 rpm and a rotation time of 10 seconds.
• an alkali-soluble resin Alkali-soluble resin
• Aronix M-402 mixture
• Example 2-9 and Comparative Example 1-3 Evaluation was carried out in the same manner as in Example 1 except that the polymers produced in Synthesis Examples 2 to 9 and Synthesis Comparative Examples 1 to 3 were used instead of the silicone chain-containing polymer (1). Table 1 shows the results.
• the coating films of Examples 1 to 4 containing the silicone chain-containing polymer of the present invention as a leveling agent have excellent smoothness and no defects in the coating film.
• Comparative Example 1 in which the weight-average molecular weight of the silicone chain-containing polymer is small, coating film defects (repellency) occur.
• Comparative Example 2 which has a large amount of silicone chains, defects in the coating film also occur.
• Coating film defects also occur in Comparative Example 3, in which the weight average molecular weight of the silicone chain-containing polymer is small and the amount of silicone chains is large.
• Example 10-14 and Comparative Examples 4-5 Pin unevenness evaluation
• coating films were formed as follows. 3.0 g of a 40% by mass resin solution of an alkali-soluble resin (Acrydic ZL-295, manufactured by DIC Corporation), 1.2 g of Aronix M-402 (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei Chemical Co., Ltd.), 0.0024 g of a silicone chain-containing polymer in terms of solid content, and 6.23 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed to form a resist composition.
• an alkali-soluble resin Alkali-soluble resin
• Aronix M-402 mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei Chemical Co., Ltd.
• pin unevenness evaluation The coating film layer of the obtained laminate was visually observed, and pinpoint unevenness of the coating film layer was evaluated according to the following criteria. Table 2 shows the results.
• the term "pin unevenness” refers to film thickness unevenness (drying unevenness) that occurs around the portion where the support pins and the coating base material come into contact with each other. 1: Pin unevenness is hardly observed 2: Pin unevenness is observed
• the coating films of Examples 10 to 14 containing the silicone chain-containing polymer of the present invention as a leveling agent have almost no pinning unevenness.
• the coating film of Comparative Example 4-5 which contains a silicone chain-containing polymer with a small number of siloxane bond repeating units (short silicone chain) as a leveling agent, causes uneven pinning.

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