Classifications

• • 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
  • G03F7/0012—Processes making use of the tackiness of the photolithographic materials, e.g. for mounting; Packaging for photolithographic material; Packages obtained by processing photolithographic materials
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • 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
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/47—Levelling agents
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • 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
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
• • 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
  • 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
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

• the present invention relates to compounds, leveling agents, coating compositions, resist compositions and articles.
• the leveling agent is an additive for improving repelling and unevenness of a coating film obtained by applying a coating composition such as a coating composition and 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 reduce the surface tension of the coating film, and an action of smoothing the obtained coating film can be obtained. A coating film with a smoothed surface can improve the occurrence of cissing and unevenness.
• the leveling agent has various uses, and is also used, for example, in a color resist composition used for producing a color filter for a liquid crystal display.
• a color resist composition is generally applied onto a glass substrate by a coating method such as spin coating or slit coating, and the dried coating film is exposed using a mask and then developed to form a coloring pattern. Including the step of forming. At this time, if the smoothness of the coating film is not good and the film thickness is uneven, or if there is uneven coating, cissing, etc., color unevenness of the pixels may occur.
• the smoothness of the obtained coating film was improved, and red (R), green (G), blue (B) pixels and the pixels formed between these pixels.
• the surface of the black matrix (BM) can exhibit high smoothness, and a color filter with less color unevenness can be obtained.
• a leveling agent for a silicone-based polymer has been proposed (Patent Documents 1 and 2).
• the silicone-based polymers of Patent Documents 1 and 2 are polymers having a plurality of silicone chains in one polymer, and although they can exhibit leveling property, they are all coated with a locally high density of silicone chains. There was a problem that it was not possible to sufficiently suppress the occurrence of defects on the film surface.
• An object to be solved by the present invention is to provide a compound that functions as a leveling agent that imparts high smoothness to a coating film without causing defects on the surface of the coating film.
• the present inventors have obtained excellent leveling performance without causing defects on the surface of the coating film if the compound has a polymer block of a polymerizable monomer at both ends of the silicone chain. We found that it could be obtained and completed the present invention.
• the present invention relates to a compound having a polymer block of a polymerizable monomer at both ends of a silicone chain.
• (meth) acrylate means one or both of acrylate and methacrylate.
• the compound of the present invention is a compound having a polymer block of a polymerizable monomer at both ends of a silicone chain.
• both ends of the silicone chain means both ends of the main chain of the silicone chain (the longest molecular chain among the molecular chains constituting the silicone chain).
• the compound of the present invention has a polymer block of a polymerizable monomer at both ends of the silicone chain, so that the leveling performance is maintained without impairing the compatibility of the coating composition with the base polymer and the solvent. Can be expressed. Since the compatibility is not impaired, it is possible to prevent defects from occurring on the surface of the obtained coating film.
• the number average molecular weight of the silicone chain is, for example, in the range of 100 to 50,000, preferably in the range of 500 to 20,000, more preferably in the range of 1,000 to 15,000, and even more preferably 2. It ranges from 000 to 10,000.
• the number average molecular weight of the silicone chain can be measured by 29 SiNMR analysis.
• the proportion of the silicone chain is, for example, in the range of 1 to 95% by mass, preferably in the range of 5 to 70% by mass, and more preferably in the range of 10 to 50% by mass.
• the ratio of the silicone chain is a value based on the mass of the compound of the present invention (mass of the silicone chain / mass of the compound).
• the ratio of the silicone chain is a value calculated from the raw material charging ratio at the time of production, and can be adjusted by the raw material charging ratio of the silicone compound and the polymerizable monomer used in the manufacturing of the compound of the present invention.
• the silicone chain contained in the compound of the present invention is preferably a silicone chain represented by the following general formula (1).
• R 11 , R 12 , R 13 and R 14 are independently alkyl or phenyl groups having 1 to 18 carbon atoms.
• L 11 and L 12 are each independently a divalent organic group or a single bond.
• n is an integer.
• the alkyl group having 1 to 18 carbon atoms of R 11 , R 12 , R 13 and R 14 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.
• the plurality of R 13s may be the same or different from each other, and the plurality of R 14s may be the same or different from each other.
• n is preferably an integer in the range of 5 to 300, more preferably an integer in the range of 10 to 250, still more preferably an integer in the range of 20 to 200, and most preferably 40 to 150. Is an integer in the range of.
• the divalent organic groups L 11 and L 12 are preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms.
• Examples of the alkylene group having 1 to 50 carbon atoms of L 11 and L 12 include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-heptylene group.
• Examples thereof include n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, isopropylene group, 2-methylpropylene group, 2-methylhexylene group, tetramethylethylene group and the like.
• the alkylene group having 1 to 50 carbon atoms of L 11 and L 12 is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably methylene. Group, ethylene group, n-propylene group or isopropylene group.
• the alkyleneoxy group having 1 to 50 carbon atoms of L 11 and L 12 is, for example, a group in which one or more of the alkylene groups is substituted with —O—.
• the alkyleneoxy groups of L 11 and L 12 having 1 to 50 carbon atoms are preferably alkyleneoxy groups having 1 to 15 carbon atoms, more preferably alkyleneoxy groups having 1 to 8 carbon atoms, and further. It is 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 carbon atom may be further substituted with a hydroxyl group or the like. ..
• the bond possessed by L 11 and L 12 is a bond that bonds directly to the polymer block of the polymerizable monomer or via a linking group.
• the "polymerizable monomer” means a compound having a polymerizable unsaturated group
• the "polymer block” is the above-mentioned polymerizable. It means a segment consisting of a repeating structure derived from a monomer.
• Examples of the polymerizable unsaturated group include (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl ether group, allyl group, styryl group, maleimide group and the like.
• (meth) acryloyl group and (meth) acryloyloxy group are preferable because the raw material is easily available and the polymerization reactivity is good.
• the polymer block of the polymerizable monomer contained in the compound of the present invention is preferably a polymer block of the polymerizable monomer (2) capable of exhibiting compatibility with the base polymer of the coating composition.
• the polymerizable monomer (2) is preferably selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain and a group containing a polyester chain. It is a polymerizable monomer having 1 or more.
• the alkyl group having 1 to 18 carbon atoms contained in 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 and a normal group. Examples thereof include a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group and the like.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (2) is preferably an alkyl group having 1 to 6 carbon atoms.
• Examples of the aromatic group having 6 to 18 carbon atoms contained in the polymerizable monomer (2) include a phenyl group, a naphthyl group, an anthracene-1-yl group, and phenanthrene-1-yl group.
• the group containing the (poly) oxyalkylene chain of the polymerizable monomer (2) is a monovalent group containing a repeating portion of oxyalkylene or a divalent linking group containing a repeating portion of oxyalkylene.
• the polymerizable unsaturated group of the polymerizable monomer (2) is a (meth) acryloyl group
• the polymerizable monomer having a group containing a (poly) oxyalkylene chain is, for example, the following general formula (2-). It is a compound represented by poa1) or (2-poa2).
• Ra 21 is a hydrogen atom or a methyl group independently of each other.
• Ra22 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• p is an integer of 0 or more
• q is an integer of 0 or more
• r is an integer of 0 or more
• p + q + r is an integer of 1 or more.
• X, Y and Z are independently alkylene groups having 1 to 6 carbon atoms.
• the alkylene group having 1 to 6 carbon atoms of X, Y and Z is preferably an alkylene group having 2 to 4 carbon atoms.
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having a polymerizable unsaturated group as a (meth) acryloyl group include methyl (meth) acrylate and 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, stearyl (meth) Alkyl esters of (meth) acrylic acids such as acrylates and isostearyl (meth) acrylates having 1 to 18 carbon atoms; dicyclopentanyloxylethyl (meth) acrylates, isoborny
• 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 polymerizable unsaturated group as a (meth) acryloyl group include, for example. Examples thereof include benzyl (meth) acrylate, phenoxymethyl (meth) acrylate, and 2-phenoxyethyl (meth) acrylate.
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having a polymerizable unsaturated group as a vinyl ether group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, and n.
• -Alkyl vinyl ethers such as 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; cycloalkyl vinyl ether and the like. Be done.
• 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 polymerizable unsaturated group as a (meth) acryloylamino group include N, N-dimethylacrylamide and N, N-. Examples thereof include diethyl acrylamide, N-isopropyl acrylamide, diacetone acrylamide, acroyl morpholine and the like.
• Examples of the polymerizable monomer (2) having an alkyl group having 1 to 18 carbon atoms and having a polymerizable unsaturated group as a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, and hexylmaleimide. Examples thereof include octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.
• Examples of the polymerizable monomer (2) having a group containing a polyoxyalkylene chain and having a polymerizable unsaturated group as a (meth) acryloyl group include polypropylene glycol mono (meth) acrylate and 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 mono (meth) acrylate, poly (propylene glycol / tetramethylene glycol) mono (meth) acrylate, polypropylene glycol / polytetramethylene glycol mono (meth) acrylate ) Acrylate, poly (propylene glycol, 1,2-butylene glycol) mono (meth) acrylate, polypropylene glycol, poly 1,2-butylene glycol mono (meth) acrylate, poly (ethylene glycol, 1,2-butylene glycol) mono (Meta) Acrylate, Polyethylene Glycol / Poly 1,2-butylene Glycol Mono (meth) Acrylate, Poly (Tetraethylene Glycol / 1,2-Burylene Glycol) Mono (Meta) Acrylate, Polytetraethylene Glycol / Poly 1,2- Butylene glycol mono (meth) acrylate
• poly (ethylene glycol / propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
• polyethylene glycol / polypropylene glycol is a block copolymer of ethylene glycol and propylene glycol.
• the polymerizable monomer (2) is preferably a compound represented by the following general formula (2-1), a compound represented by the following general formula (2-2), and a compound represented by the following general formula (2-3).
• the compound is one or more selected from the group consisting of the compounds represented by the following general formula (2-4), more preferably the compounds represented by the following general formula (2-1), and the following general. It is one or more selected from the group consisting of the compound represented by the formula (2-2) and the compound represented by the following general formula (2-3).
• R 21 is a hydrogen atom or a methyl group and is R 22 is an alkyl group having 1 to 18 carbon atoms.
• R 23 is a hydrogen atom or a methyl group and is R 24 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• R25 is a hydrogen atom or a methyl group and is R26 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• R 27 is a hydrogen atom or a methyl group and is R 28 is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, respectively.
• n is an integer in the range 1 to 4
• m is an integer in the range 1 to 200
• p is an integer in the range 1 to 10
• q is an integer in the range 1 to 100
• l is an integer in the range 1 to 100. It is an integer from 0 to 5.
• the compound represented by the formula (2-3) is, for example, a lactone-modified form of the compound represented by the formula (2-2).
• the polymerizable monomer (2) can be produced by a known method. Further, as the polymerizable monomer (2), a commercially available product may be used. For example, as a commercially available product of the polymerizable monomer (2) having a group containing a polyoxyalkylene chain and having a polymerizable unsaturated group as a (meth) acryloyl group, "NK Ester M" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
• the polymerizable monomer constituting the polymer block may be used alone or in combination of two or more.
• the polymer block is a copolymer of two or more kinds of polymerizable monomers
• the polymerization type of the copolymer is not particularly limited, and two or more kinds of polymerizable monomers having different structures from each other are used. It may be a random copolymer or a block copolymer of two or more kinds of polymerizable monomers having different structures from each other.
• the number average molecular weight (Mn) of the compound of the present invention is preferably in the range of 1,000 to 200,000, more preferably in the range of 1,500 to 30,000, and even more preferably in the range of 2,000 to 10. It is in the range of 000.
• the weight average molecular weight (Mw) of the compound of the present invention is preferably in the range of 1,000 to 500,000, more preferably in the range of 2,000 to 100,000, and even more preferably in the range of 4,000 to 40. It is in the range of 000.
• the values of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the compound of the present invention are measured by the method described in Examples.
• the compound of the present invention can be produced by polymerizing a reaction raw material containing a compound (1) having a polymerizable unsaturated group at both ends of a silicone chain and a polymerizable monomer (2).
• reaction raw material means a component constituting the compound of the present invention, and does not include a component not constituting the compound of the present invention such as a catalyst and a solvent used in production, for example.
• a compound having a polymerizable unsaturated group only at one end of the silicone chain is used, but the silicone chain lacking the polymer block during production is used. Only compounds may occur. Since the compound containing only the silicone chain is inferior in compatibility, there is a risk of causing defects on the surface of the coating film. In the present invention, since the compound (1) having a polymerizable unsaturated group at both ends of the silicone chain is used, the possibility that a compound containing only the silicone chain is generated is extremely low, and a component that causes a defect on the coating film surface is substantially contained. Not included in.
• Examples of the polymerizable unsaturated group of the compound (1) include (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl ether group, allyl group, styryl group, maleimide group and the like.
• (meth) acryloyl group and (meth) acryloyloxy group are preferable because the raw material is easily available and the polymerization reactivity is good.
• the compound (1) having a polymerizable unsaturated group at both ends of the silicone chain is preferably a compound represented by the following general formula (1-1).
• R 11 , R 12 , R 13 and R 14 are independently alkyl or phenyl groups having 1 to 18 carbon atoms.
• L 11 and L 12 are each independently a divalent organic group or a single bond.
• n is an integer.
• X 1 and X 2 are independently polymerizable unsaturated groups.
• R 11 , R 12 , R 13 , R 14 , L 11 , L 12 and n is R 11 , R 12 , R 13 , R 14 of the above formula (1).
• L 11 , L 12 and n are the same as the preferred embodiments.
• the polymerizable unsaturated group of X 1 and X 2 is preferably a (meth) acryloyl group, a (meth) acryloyloxy group or a styryl group because of its good polymerizable property. ..
• Specific examples of the compound (1) having a polymerizable unsaturated group at both ends of the silicone chain include the following compounds.
• n is an integer.
• the compound (1) having a polymerizable unsaturated group at both ends of the silicone chain can be produced by a known method (for example, Japanese Patent No. 64056547).
• the same polymerizable monomer (2) as the above-mentioned one can be used as the reaction raw material, and one type may be used alone or two or more types may be used in combination.
• the reaction raw material used for producing the compound of the present invention is not limited to the compound (1) and the polymerizable monomer (2) having polymerizable unsaturated groups at both ends of the silicone chain, and impairs the effect of the present invention.
• a monomer other than the compound (1) having a polymerizable unsaturated group at both ends of the silicone chain and the polymerizable monomer (2) may be used as long as it does not exist.
• the other monomer include hydroxyalkyl (meth) acrylate, paravinylbenzoic acid, N-phenylmaleimide and the like.
• the other monomer as a reaction raw material may be used alone or in combination of two or more.
• the charging ratio of the compound (1) having a polymerizable unsaturated group at both ends of the silicone chain and the polymerizable monomer (2) is not particularly limited, but the weight ratio (compound (1) / polymerizable monomer (2)). )), For example, 1/99 to 99/1, preferably 5/95 to 80/20, and more preferably 10/90 to 60/40.
• polymerization method for example, various polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization and anion polymerization can be used.
• polymerization methods bulk polymerization and solution polymerization are preferable because a polymer having less contamination of minute foreign substances can be obtained.
• solution polymerization a solution prepared by dissolving a mixture of raw materials in a solvent of aromatic hydrocarbons such as toluene and ethylbenzene can be used.
• polymerization by bulk polymerization the polymerization can be started by free radicals generated by heating or ionizing radiation irradiation as is usually performed.
• any initiator that is generally used in radical polymerization can be used.
• an azo compound such as azobisisobutylnitrile
• an organic peroxide such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate or the like is used.
• solution polymerization is common, so that the 10-hour half-life temperature is 80 ° C. or higher and the peroxide, azobis initiator, etc. that are soluble in the organic solvent used are used.
• 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, cyclohexaneperoxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane examples thereof include 1,1-azobis (1-cyclohexanecarbonitrile) and 2- (carbamoylazo) isobutyronitrile. These initiators are usually used in the range of 0.1 to 20% by mass with respect to 100 parts by mass of the polymerization component.
• a molecular weight modifier may be used if necessary.
• the molecular weight modifier any one used in general radical polymerization is used, and examples thereof include mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, and 2-ethylhexyl thioglycolate. These molecular weight modifiers may be added in a concentration range such that the molecular weight is controlled within the above-mentioned range.
• the compound of the present invention can also be produced by performing living polymerization such as living radical polymerization and living anionic polymerization.
• living radical polymerization a dormant species whose active polymerization terminal is protected by an atom or an atomic group reversibly generates radicals and reacts with a monomer to proceed with a growth reaction, and the growth reaction proceeds even if the first monomer is consumed.
• a block polymer can be obtained by reacting with a second monomer added sequentially without losing activity at the ends.
• living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleaving radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), radical polymerization using organic tellurium (TERP), and the like. Can be mentioned.
• ATRP is preferable because of its ease of control.
• 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.
• alkyl ester having 1 to 6 carbon atoms of the 2-halogenated carboxylic acid having 1 to 6 carbon atoms include, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, 2-.
• examples thereof include methyl bromopropionate and ethyl 2-bromoisobutyrate.
• the transition metal compounds that can be used in ATRP are represented by M n + X n .
• the transition metal M n + of the transition metal compound represented by M n + X n includes Cu + , Cu 2+ , Fe 2+ , Fe 3+ , Ru 2+ , Ru 3+ , Cr 2+ , Cr 3+ , Mo 0 , Mo + , Mo.
• X of 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 /.
• R 11 represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 12 is a hydrogen atom or halogen from 1 to 1.
• N of the transition metal compound represented by M n + X n represents a formal charge on the metal and is an integer of 0 to 7.
• the ligand compound that can be coordinated to the transition metal of the transition metal compound includes a coordinate containing one or more nitrogen atom, oxygen atom, phosphorus atom or sulfur atom that can be coordinated to the transition metal via a ⁇ bond. It has a compound having a child, a compound having a ligand containing two or more carbon atoms that can be coordinated with a transition metal via a ⁇ bond, and a ligand having a ligand capable of coordinating with a transition metal via a ⁇ bond or an ⁇ bond. Examples include compounds.
• the transition metal complex is not particularly limited, but preferably, the transition metal complex of groups 7, 8, 9, 10, and 11 is preferable, and more preferably, 0-valent copper, monovalent copper, and divalent ruthenium. Examples include divalent iron or divalent nickel complexes.
• a complex with a ligand such as a polyamine such as (aminoethyl) amine.
• divalent ruthenium complex examples include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichloro p-simenruthenium, and dichloro (norbornadiene) ruthenium.
• Examples thereof include cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium and the like.
• divalent iron complex examples include a bistriphenylphosphine complex and a triazacyclononane complex.
• a solvent used in living radical polymerization
• 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
• Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
• Alcohol solvents such as methanol, ethanol and isopropanol
• Aprotonic polar solvents such as dimethylformamide and dimethyl sulfoxide Can be mentioned.
• the above solvent may be used alone or in combination of two or more.
• the polymerization temperature during the living radical polymerization is preferably in the range of room temperature to 120 ° C.
• the compound of the present invention is produced by living radical polymerization
• a metal due to the transition metal compound used in the polymerization may remain in the obtained compound.
• the metal remaining in the obtained compound may be removed by using activated alumina or the like after the completion of the polymerization.
• the compound of the present invention can be suitably used as a leveling agent for the coating composition, and the coating composition of the present invention contains the compound of the present invention. Since the compound of the present invention can be a fluorine atom-free leveling agent containing no fluorine atom, it is a leveling agent having low environmental load and low environmental load.
• the content of the compound of the present invention contained in the coating composition of the present invention varies depending on the type of base resin, coating method, target film thickness, etc., but is 0. 001 to 10 parts by mass is preferable, 0.01 to 5 parts by mass is more preferable, and 0.02 to 2 parts by mass is further preferable.
• the content of the compound 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 problems such as foaming during coating can be suppressed.
• the application of the coating composition of the present invention is not particularly limited, and it can be used in any application as long as it is required to have leveling properties.
• the coating composition of the present invention can be used, for example, as various coating compositions or photosensitive resin compositions.
• the coating composition of the present invention may be, for example, petroleum resin paint, cellac paint, rosin-based paint, cellulose-based paint, rubber-based paint, lacquer paint, cashew resin paint.
• Paints using natural resins such as oil-based vehicle paints; phenol resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints , Paints using synthetic resins such as fluororesin paints.
• Colorants such as pigments, dyes and carbons; inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide and calcium carbonate; higher fatty acids and poly Organic fine powders such as acrylic resin and polyethylene; various additives such as light resistance improver, weather resistance improver, heat resistance improver, antioxidant, thickener, and sedimentation inhibitor can be appropriately added. ..
• any known and publicly available coating method can be used, for example, a slit coater, a slit & spin coater, a spin coater, a roll coater, electrostatic coating, a bar coater, and the like.
• Methods such as gravure coater, die coater, knife coater, inkjet, dipping coating, spray coating, shower coating, screen printing, gravure printing, offset printing, reverse coating and the like can be mentioned.
• the photosensitive resin composition changes its physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability of the resin by irradiating it with light such as visible light and 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 on a silicon wafer or a glass substrate on which various metals are vapor-deposited so as to have a thickness of about 1 to 2 ⁇ m.
• the coating composition of the present invention has the above-mentioned problems when used as a resist composition because the compound of the present invention can exhibit a high leveling property and form a uniform coating film (cured product). Can be solved.
• the photoresist composition contains an alkali-soluble resin, a radiation-sensitive substance (photosensitive substance), a solvent and the like in addition to the compound 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 developing solution used when patterning a resist.
• the alkali-soluble resin include novolak resins obtained by condensing aromatic hydroxy compound derivatives such as phenol, cresol, xylenol, resorcinol, fluoroglycinol and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde and benzaldehyde; o-.
• Polymers or copolymers of vinylphenol compound derivatives such as vinylphenol, m-vinylphenol, p-vinylphenol, ⁇ -methylvinylphenol; (meth) acrylics such as acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate.
• Acid-based polymer or copolymer polyvinyl alcohol; modification by introducing radioactive ray-sensitive groups such as quinonediazide group, naphthoquinone azide group, aromatic azido group, and aromatic cinnamoyle group via some of the hydroxyl groups of these various resins.
• Resin Urethane resin or the like containing an acidic group such as a carboxylic acid or a sulfonic acid in the molecule can be mentioned. These alkali-soluble resins may be used alone or in combination of two or more.
• the radiation-sensitive substance contained in the photoresist composition is an alkali-soluble resin obtained by irradiating with energy rays such as ultraviolet rays, far ultraviolet rays, excima laser light, X-rays, electron beams, ion rays, molecular beams, and ⁇ -rays. It is a substance that changes the solubility in a developing solution.
• energy rays such as ultraviolet rays, far ultraviolet rays, excima laser light, X-rays, electron beams, ion rays, molecular beams, and ⁇ -rays. It is a substance that changes the solubility in a developing solution.
• the radiation-sensitive substance include quinone-diazide-based compounds, diazo-based compounds, azide-based compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organic metal compounds, organic acid ester compounds, and organic acid amides. Examples thereof include compounds, organic acidimide compounds,
• quinone diazide compound examples include 1,2-benzoquinone azido-4-sulfonic acid ester, 1,2-naphthoquinone diazido-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, and 2, 1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, other 1,2-benzoquinone azide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride , 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, 2,1-naphthoquinonediazide-5-sulfonic acid chloride and other quino
• diazo compound examples include a salt of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, a hexafluorophosphate, a tetrafluoroborate, a perchlorate or a periodate and the condensate.
• diazo resin inorganic salts which are reactive organisms
• diazo resin organic salts which are reaction products of the condensate and sulfonic acids as described in USP 3,300,309.
• azide-based compound examples include azidochalcone acid, diazidobenzalmethylcyclohexanones, azidocinnamylideneacetophenones, aromatic azide compounds, and aromatic diazide compounds.
• halogenated organic compound examples include a halogen-containing oxadiazole-based compound, a halogen-containing triazine-based compound, a halogen-containing acetophenone-based compound, a halogen-containing benzophenone-based compound, a halogen-containing sulfoxide-based compound, a halogen-containing sulfone-based compound, and a halogen-containing compound.
• Thiazol-based compounds include halogen-based compounds.
• halogen-containing oxazole-based compounds include halogen-containing trizole-based compounds, halogen-containing 2-pyrone-based compounds, halogen-containing aliphatic hydrocarbon-based compounds, halogen-containing aromatic hydrocarbon-based compounds, halogen-containing heterocyclic compounds, sulfenyl Examples include halogen-based compounds.
• tris (2,3-dibromopropyl) phosphate tris (2,3-dibromo-3-chloropropyl) phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl , Tribromophenylallyl 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-dibromophenyl) propane
• organic acid ester examples include carboxylic acid ester and sulfonic acid ester.
• organic acid amides examples include carboxylic acid amides and sulfonic acid amides.
• organic acid imide examples include carboxylic acid imide and sulfonic acid imide.
• the radiation-sensitive substance may be used alone 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.
• Examples of the solvent for the photoresist composition include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methylisobutylketone and butyrolactone; methanol, ethanol, n-propyl alcohol and iso.
• -Alcohols such as propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 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; ethyl forerate, propyl forerate, butyl forerate, methyl acetate , Ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionat
• Proteylene glycols such as monoethyl ether acetate and propylene glycol monobutyl ether acetate; dietylel glycol monomethyl ether, dietiel glycol monoethyl ether, dietylell glycol dimethyl ether, dietyl glycol diethyl ether, dietyl glycol methyl ethyl Diethylene glycols such as ether; trichloroethylene, freon solvent, HCFC, HFC Halogenated hydrocarbons such as; fully fluorinated solvents such as perfluorooctane, aromatics such as toluene and xylene; polar solvents such as dimethylacetiamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone Can be mentioned. These solvents may be used alone or in combination of two or more.
• the color resist composition contains an alkali-soluble resin, a polymerizable compound, a colorant and the like in addition to the compound of the present invention.
• the same alkali-soluble resin contained in the above-mentioned photoresist composition can be used.
• the polymerizable compound contained in the color resist composition is a compound having a photopolymerizable functional group capable of polymerizing or cross-linking by irradiation with active energy rays such as ultraviolet rays.
• the polymerizable compound include unsaturated carboxylic acids such as (meth) acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatics. Ester obtained by esterification of polyhydroxy compound and unsaturated carboxylic acid, unsaturated carboxylic acid and polyvalent carboxylic acid, and polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound.
• a polymerizable compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound, a polymerizable compound having an acid group, and the like can be mentioned.
• the polymerizable compound may be used alone or in combination of two or more.
• ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylol propanetri (meth) acrylate, and trimethylol ethanetri ().
• Meta) acrylate pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa.
• acrylic acid esters such as (meth) acrylate and glycerol (meth) acrylate.
• ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid examples include hydroquinone di (meth) acrylate, resorcindi (meth) acrylate, and pyrogalloltri (meth) acrylate.
• the ester obtained by the esterification reaction of the unsaturated carboxylic acid, the polyvalent carboxylic acid and the polyvalent hydroxy compound may be a single substance or a mixture.
• Such esters include, for example, esters obtained from (meth) acrylic acid, phthalic acid and ethylene glycol, esters obtained from (meth) acrylic acid, maleic acid and diethylene glycol, (meth) acrylic acid, terephthalic acid and penta. Examples thereof include esters obtained from erythritol, (meth) acrylic acid, adipic acid, butanediol, and esters obtained from glycerin.
• Examples of the polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; and fats such as cyclohexane diisocyanate and isophorone diisocyanate. Cyclic diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane. Examples thereof include a reaction product with a hydroxy compound having an acryloyl group.
• the polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
• a polyfunctional polymerizable compound having an acid group is preferable. 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, more preferably in the range of 5 to 30, because the developability, curability and the like are good.
• the acid value of the above range is within the above range.
• the polymerizable compound having an acid group examples include a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate as a main component, and the mixture is Aronix TO. It is commercially available as -1382 (manufactured by Toa Synthetic Co., Ltd.).
• polymerizable compounds other than the above examples include (meth) acrylamide such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinylphthalate.
• 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, based on the total solid content of the color resist composition. It is more preferably in the range of 20 to 50% by mass.
• the colorant of 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.
• the pigment can be either an organic pigment or an inorganic pigment.
• the organic pigment pigments having various hues such as red pigment, green pigment, blue pigment, yellow pigment, purple pigment, orange pigment, and brown pigment can be used.
• the chemical structure of the organic pigment include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrone-based, and perylene-based.
• the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.
• the "CI" below means a color index.
• red pigment examples include 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, 112, 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
• C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254, preferably C.I. I. Pigment Red 177, 209, 224 or 254 is more preferred.
• Examples of the green pigment include C.I. I. Pigment greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Among these, C.I. I. Pigment Green 7, 36 or 58 is preferred.
• Examples of the blue pigment include 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, Examples thereof include 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. Among these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6 is preferred. I. Pigment Blue 15: 6 is more preferred.
• yellow pigment examples include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189,
• C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 are preferred.
• I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferred.
• Examples of the purple pigment include 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 can be mentioned. Among these, C.I. I. Pigment Violet 19 or 23 is preferred, C.I. I. Pigment Violet 23 is more preferred.
• Examples of the orange pigment include 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, Examples thereof include 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. Among these, C.I. I. Pigment Orange 38 or 71 is preferred.
• each pixel of the three primary colors of the color filter used in the liquid crystal display device and the organic EL display device is red (R), green (G), and blue (B)
• the red pigment, the green pigment, and the blue pigment are the main components. Therefore, 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, still more preferably 0.3 ⁇ m or less, in order to increase the brightness of the color liquid crystal display device and the organic EL display device. It is preferable to disperse and use the organic pigment so as to have these average particle sizes.
• the average primary particle size of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, further preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm.
• the average particle size of the organic pigment is measured by a dynamic light scattering type particle size distribution meter. For example, Nanotrac particle size distribution measuring devices "UPA-EX150" and “UPA” manufactured by Nikkiso Co., Ltd. -It can be measured with "EX250" or the like.
• the colorant is not particularly limited as long as it is black, but carbon black, lamp black, acetylene black, bone black, thermal black, and channels. Examples include black, furnace black, graphite, iron black, titanium black and the like. Among these, carbon black and titanium black are preferable from the viewpoint of shading rate and image characteristics. Further, a combination of two or more kinds of organic pigments mixed and blackened by color mixing may be used.
• Examples of commercially available carbon black products include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32 manufactured by Mitsubishi Chemical Corporation. , # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexPritEx U ⁇ Printex V ⁇ PrintexG ⁇ Spec
• carbon black coated with a resin is preferable as having the high optical density and high surface resistivity required for the black matrix of the color filter.
• titanium black 10S, 12S, 13R, 13M, 13M-C examples of the commercially available titanium black product
• Examples of the commercially available titanium black product include titanium black 10S, 12S, 13R, 13M, 13M-C manufactured by Mitsubishi Materials Corporation.
• Examples of the colorant used for forming a black matrix (BM) include black pigments in which two or more kinds of organic pigments are mixed and black may be obtained by mixing colors, and three color pigments of red, green and blue are mixed. .. Coloring materials that can be mixed and used to prepare black pigments include Victoria Pure Blue (CI 42595), Auramine O (CI 41000), Cachilon Brilliant Flavin (Basic 13), and Rhodamine 6 GCP (C). I.45160), Rhodamine B (CI45170), Safranin OK70: 100 (CI50240), Eriograusin X (CI42080), No.
• coloring materials that can be mixed and used 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 pigments 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. Examples thereof include brown pigments 23, 25 and 26.
• the average primary particle size of carbon black is preferably in the range of 0.01 to 0.08 ⁇ m, and more preferably in the range of 0.02 to 0.05 ⁇ m because of its good developability.
• carbon black exists in a state called a structure in which primary particles are fused to each other, and may form fine pores on the particle surface by post-treatment. Therefore, in order to represent the particle shape of carbon black, in addition to the average particle size of the primary particles generally obtained by the same method as the organic pigment, the DBP absorption amount (JIS K6221) and the specific surface area by the BET method ( It is preferable to measure JIS K6217) and use it as an index of the structure and the amount of pores.
• the DBP absorption amount JIS K6221
• the specific surface area by the BET method It is preferable to measure JIS K6217
• the absorption amount of carbon black dibutyl phthalate (hereinafter abbreviated as "DBP") is preferably in the range of 40 to 100 cm 3/100 g, and is in the range of 50 to 80 cm 3/100 g because of its good dispersibility and developability. Is more preferable.
• the specific surface area of carbon black by the BET method is preferably in the range of 50 to 120 m 2 / g, and more preferably in the range of 60 to 95 m 2 / g because of its good dispersion stability.
• the dye as a colorant in the color resist composition examples include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like. ..
• azo dye examples include 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. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.
• anthraquinone dye 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 dye include C.I. I. Pad blue 5 and the like can be mentioned, and examples of the quinoneimine dye include C.I. I. Basic Blue 3, C.I. I. Examples thereof include 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. Examples thereof include Disperse Yellow 64, and examples of the nitro dye include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like can be mentioned.
• the colorant of the color resist composition it is preferable to use a pigment in terms of excellent light resistance, weather resistance and fastness of the obtained coating film, but in order to adjust the hue, it is necessary to use a pigment.
• a dye may be used in combination.
• the content of the colorant is preferably 1% by mass or more, more preferably 5 to 80% by mass, and 5 to 70% by mass in the total solid content of the color resist composition. More preferably in the range of%
• the content of the colorant in the color resist composition is the total solid color of the color resist composition. It is preferably in the range of 5 to 60% by mass, and more preferably in the range of 10 to 50% by mass.
• the content of the colorant in the color resist composition is preferably in the range of 20 to 80% by mass in the total solid content of the color resist composition. , 30 to 70% by mass, more preferably.
• the colorant when the colorant is a pigment, it is preferable to use it as a pigment dispersion prepared by dispersing the pigment in an organic solvent using a dispersant.
• the dispersant include surfactants; pigment intermediates or derivatives; dye intermediates or derivatives; and resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins.
• a graft copolymer having a nitrogen atom, an acrylic block copolymer having a nitrogen atom, a urethane resin dispersant and the like are preferable.
• these dispersants have a nitrogen atom, the nitrogen atom has an affinity for the pigment surface, and the portion other than the nitrogen atom enhances the affinity for the medium, thereby improving the dispersion stability.
• These dispersants may be used alone or in combination of two or more.
• organic solvent used in the preparation of the pigment dispersion examples include an acetate-based solvent such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; a propionate-based solvent such as ethoxypropionate; toluene and xylene.
• acetate-based solvent such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate
• a propionate-based solvent such as ethoxypropionate
• toluene and xylene examples of the organic solvent used in the preparation of the pigment dispersion.
• Aromatic solvents such as methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane Solvents; nitrogen compound solvents such as N, N-dimethylformamide, ⁇ -butyrolactam, N-methyl-2-pyrrolidone; lactone solvents such as ⁇ -butyrolactone; carbamate esters and the like. These solvents may be used alone or in combination of two or more.
• Examples of the method for preparing the pigment dispersion liquid include a method of undergoing a kneading and dispersion step of a colorant and a fine dispersion step, and a method of performing only in the fine dispersion step.
• the colorant, a part of the alkali-soluble resin, and if necessary, the dispersant are mixed and kneaded.
• the colorant can be dispersed by dispersing while applying a strong shearing force using a kneader.
• Examples of the machine used for kneading include a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a conider, a homogenizer, a blender, a single-screw or twin-screw extruder, and the like. It is preferable that the colorant has a fine particle size by a salt milling method or the like before the above-mentioned kneading.
• a composition containing a colorant obtained in the kneading and dispersion step is added with a solvent, or a colorant, an alkali-soluble resin, a solvent and, if necessary, the dispersant are mixed.
• a disperser By mixing and dispersing using a disperser together with a medium for dispersing fine particles of glass, zirconia or ceramic, the particles of the colorant can be dispersed to a fine state close to the 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 size of the colorant was measured with a dynamic light scattering type particle size distribution meter.
• Nanotrac particle size distribution measuring devices "UPA-EX150” and “UPA” manufactured by Nikkiso Co., Ltd. -It can be measured with "EX250" or the like.
• the coating composition As described above, as the coating composition, a coating composition, a photoresist composition, and a color resist composition have been exemplified, but the coating composition is not limited thereto.
• the coating composition of the present invention include a liquid crystal display (hereinafter abbreviated as “LCD”), a plasma display (hereinafter abbreviated as “PDP”), and an organic EL display (hereinafter abbreviated as “OLED”).
• LCD liquid crystal display
• PDP plasma display
• OLED organic EL display
• Anti-glare (AG: anti-glare) hard coating material anti-glare
• LR anti-reflection
• QDD quantum dot displays
• Refractory layer coating material high refractive index layer coating material, clear hard coating material, polymerizable liquid crystal coating material; to form each pixel such as RGB of a color filter (hereinafter abbreviated as "CF") such as LCD.
• Color resists, inkjet inks, printing inks or paints used in CF black matrices such as LCDs, black column spacers, black resists for forming black photo spacers, inkjet inks, printing inks or paints; CFs such as LCDs.
• Paint for transparent protective film that protects the CF surface LCD material for liquid crystal display, column spacer, resin composition for photo spacer; resin composition for pixel partition such as LCD, PDP, OLED, QDD, positive type photoresist for electrode formation , Protective film, insulating film, plastic housing, paint for plastic housing, bezel (frame) ink; prism sheet which is a backlight member of LCD, light diffusion film; paint for organic insulating film of liquid crystal TFT array of LCD; LCD Internal polarizing plate surface protective coating material; PDP phosphor; OLED organic EL material, encapsulant (protective film, gas barrier); QDD quantum dot ink, encapsulant, protective film; micro (mini) LED display High refractive index lens, low refractive index encapsulation, LED pixel; positive type photoresist used for semiconductor manufacturing, chemically amplified type photoresist, antireflection film, multilayer material (SOC, SOG), underlayer film, buffer coat, developer , Rinse liquid, pattern collapse prevention agent
• Glass coating material for reading parts of equipment Optical lenses such as cameras, video cameras, glasses, contact lenses or their coating materials; Windshields for watches such as watches, glass coating materials; Windows of various vehicles such as automobiles and railroad vehicles Coating material; Antireflection film coating for solar cell cover glass or film; FRP bathing coating or coating material; PCM for metal building materials or home appliances; Single-layer or multi-layer coating composition for photofabrication processes, etc. And so on.
• the compound of the present invention Since the compound of the present invention has an excellent ability to reduce surface tension, it has not only leveling property but also wettability, permeability, detergency, water repellency, oil repellency, antifouling property, lubricity, and blocking prevention property. Each function of releasability can also be expected. Further, when the compound of the present invention is blended with a paint or a coating agent containing fine particles, the dispersibility of the fine particles is improved, and not only the leveling property but also the function as a dispersant for the fine particles can be expected.
• the compound of the present invention to the pressure-sensitive adhesive composition used for adhesive tapes and the like in addition to the above-mentioned coating composition, not only the leveling property but also the peeling force is reduced, the peeling force fluctuation is suppressed, and the peeling charge is charged. Each function of suppression can also be expected.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-converted values based on gel permeation chromatography (GPC) measurement.
• GPC gel permeation chromatography
• Example 1 Synthesis of a compound having a polymer block of a polymerizable monomer at both ends of a silicone chain
• Polypropylene glycol-polybutylene glycol-monomethacrylate (number average repetition number 1 of polypropylene glycol, number average repetition number 6 of polybutylene glycol) 102.6 g, butyl acetate 152.6 g as solvent, t-butyl peroxy- as initiator Mixture A was prepared by mixing 13.5 g of 2-ethylhexanoate.
• a mixed solution B was prepared by mixing 47.4 g of a dimethacrylate compound having a polysiloxane bond represented by the following formula (A1-1) and 47.4 g of butyl acetate as a solvent.
• the weight average molecular weight (Mw) was 12,100 and the number average molecular weight (Mn) was 2,650. Further, from the raw material charging ratio, the ratio of the silicone chain to the compound (1) was 30% by mass.
• Example 2 Synthesis of a compound having a polymer block of a polymerizable monomer at both ends of a silicone chain
• the initiator t-butylperoxy-2-ethylhexano Synthesis was carried out in the same manner as in Example 1 except that 9.0 g of ate was used to obtain compound (2).
• the weight average molecular weight (Mw) was 10,400 and the number average molecular weight (Mn) was 2,540. Further, from the raw material charging ratio, the ratio of the silicone chain to the compound (2) was 19% by mass.
• Example 3 Synthesis of a compound having a polymer block of a polymerizable monomer at both ends of a silicone chain
• 102.6 g of polypropylene glycol-polybutylene glycol-monomethacrylate is used, 47.4 g of the compound represented by the above formula (A1-1) is used, and t-butylperoxy-2-ethylhexano as an initiator is used.
• Synthesis was carried out in the same manner as in Example 1 except that 22.5 g of ate was used to obtain compound (3).
• the weight average molecular weight (Mw) was 7,000 and the number average molecular weight (Mn) was 2,180. Further, from the raw material charging ratio, the ratio of the silicone chain to the compound (3) was 30% by mass.
• Example 4 Synthesis of a compound having a polymer block of a polymerizable monomer at both ends of a silicone chain
• 102.6 g of polypropylene glycol-polybutylene glycol-monomethacrylate is used, 47.4 g of the compound represented by the above formula (A1-1) is used, and t-butylperoxy-2-ethylhexano as an initiator is used.
• Synthesis was carried out in the same manner as in Example 1 except that 9.0 g of ate was used to obtain compound (4).
• the weight average molecular weight (Mw) was 43,500 and the number average molecular weight (Mn) was 3,270. Further, from the raw material charging ratio, the ratio of the silicone chain to the compound (4) was 30% by mass.
• the weight average molecular weight (Mw) was 12,000 and the number average molecular weight (Mn) was 2,740. .. Further, from the raw material charging ratio, the ratio of the silicone chain to the compound (1') was 30% by mass.
• Comparative Example 2 Synthesis of Polymer with Silicone Chain on Side Chain
• Synthesis was carried out in the same manner as in Comparative Example 1 except that 160.0 g of polypropylene glycol-polybutylene glycol-monomethacrylate was used and 40.0 g of the compound represented by the above formula (A1-2) was used. Obtained (2').
• the weight average molecular weight (Mw) was 11,700 and the number average molecular weight (Mn) was 1,830. .. Further, from the raw material charging ratio, the ratio of the silicone chain to the compound (2') was 19% by mass.
• 3 ml of the obtained resist composition is 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 400 rpm and a rotation time of 20 seconds, and then heated and dried at 100 ° C. for 100 seconds to apply.
• a laminate having a film layer was prepared.
• Coating film defect The coating film layer of the obtained laminate was visually observed, and the coating film defects of the coating film layer were evaluated according to the following criteria. A: Almost no coating film defects are observed. B: Several coating film defects are observed. C: Many coating film defects are observed.

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