WO2019107026A1 - Résine fluorée pouvant durcir par un rayonnement à énergie active, agent d'imperméabilisation, composition de résine le contenant et film durci - Google Patents

Résine fluorée pouvant durcir par un rayonnement à énergie active, agent d'imperméabilisation, composition de résine le contenant et film durci Download PDF

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WO2019107026A1
WO2019107026A1 PCT/JP2018/039639 JP2018039639W WO2019107026A1 WO 2019107026 A1 WO2019107026 A1 WO 2019107026A1 JP 2018039639 W JP2018039639 W JP 2018039639W WO 2019107026 A1 WO2019107026 A1 WO 2019107026A1
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group
acid
active energy
energy ray
meth
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PCT/JP2018/039639
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English (en)
Japanese (ja)
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慎 笹本
純平 植野
啓 高野
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Dic株式会社
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Priority to JP2019557072A priority Critical patent/JP6733831B2/ja
Priority to CN201880077226.8A priority patent/CN111417669B/zh
Priority to KR1020207014976A priority patent/KR102520617B1/ko
Publication of WO2019107026A1 publication Critical patent/WO2019107026A1/fr

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    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/142—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • 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

Definitions

  • the present invention relates to a fluorine-containing active energy ray-curable resin that can be suitably used as a surface modifier such as surface smoothness of a cured film or water and oil repellency, or as a liquid repellent agent, and a resin composition containing the same. It relates to the cured film.
  • various fluorine-based surfactants or fluorine-based surface modifiers are various coating materials, from the viewpoint of being excellent in leveling property, wettability, permeability, antiblocking property, sliding property, water and oil repellency, antifouling property, etc. It is widely used as a surface modifier.
  • fluorine-based surfactant an active energy ray-curable composition containing this fluorine-based surfactant or fluorine-based surface modifier (hereinafter collectively referred to simply as “fluorine-based surfactant”).
  • fluorine-based surfactant an active energy ray-curable composition containing this fluorine-based surfactant or fluorine-based surface modifier
  • the resulting cured film exhibits excellent surface properties, while a part of the fluorine-based surfactant is a cured film by heating, humidification, exposure to chemicals such as acid and alkali, and cleaning for dirt removal, etc.
  • the surface is easily detached or volatilized, and as a result, there is a problem that the production line is contaminated or the stain resistance of the coating film surface is reduced.
  • an active energy ray-curable functional group is contained in the structure of the fluorine-based surfactant and is strongly bonded to the surface of the cured film (for example, a patent) Reference 1).
  • the fluorine-containing polymerizable resin provided in Patent Document 1 as one component of the active energy ray-curable resin composition, problems such as detachment from the surface of the above-mentioned cured film are reduced, and the antifouling property of the surface is eliminated. It has become possible to maintain such functions as for a long time.
  • the acrylic copolymer as described in Patent Document 1 has an upper limit to the fluorine atom content that can be contained in one molecule, It was necessary to increase the amount added to the composition.
  • a liquid repellent agent is known as one use of a fluorine-based surfactant.
  • the liquid repellent agent is an ink jet (IJ) using organic layers such as a light emitting layer as dots in the production of an optical element such as an organic EL (Electro-Luminescence) element, a quantum dot display, a TFT (Thin Film Transistor) array, and a thin film solar cell.
  • IJ ink jet
  • the photosensitivity when forming the partition wall by the photolithographic method using the photosensitive resin composition It is an additive to be contained in a resin composition, and is also referred to as an ink repellent agent (see, for example, Patent Document 2).
  • the partition wall needs to exhibit sufficient liquid repellency on the upper surface thereof, and therefore, although a fluorine-based surfactant is blended in the photosensitive resin composition, it is surrounded by the partition wall including the side wall of the partition wall
  • the openings for dot formation need to have ink affinity.
  • a film obtained from a resist composition containing a liquid repellent agent provided in Patent Document 2 is capable of forming such partition walls, the liquid repellency on the upper surface when performing more precise pattern printing In some cases, the hydrophilicity of the opening may become insufficient due to migration of the component derived from the fluorosurfactant to the side of the partition, and further higher performance (more There is a need for a liquid repellent agent that exhibits high liquid repellency and exerts an effect when added in a smaller amount.
  • the problem to be solved by the present invention is that it has a resin structure in which adjustment of the fluorine atom content is easy and has excellent surface segregation when used as one component of an active energy ray curable composition
  • the present inventors have linked structural units having a fluorine-containing alkylene chain and structural units consisting of other divalent hydrocarbon groups in a linear manner.
  • the inventors have found that the above-mentioned problems can be solved by using a fluorine-containing active energy ray-curable resin having a structure in which an active energy ray-curable functional group is contained in the connecting portion, and the present invention has been completed.
  • an alkylene chain in which at least one hydroxyl group at both ends is hydroxy and at least one of hydrogen atoms is substituted with a fluorine atom in one molecule provided that the alkylene chain has an etheric oxygen atom (A), including: And at least one residue of a divalent phenolic hydroxyl group-containing compound (B) other than the above (A) and / or a residue of a divalent carboxylic acid (C), They are structural formula (1) below
  • X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acid group] Having a structural unit bound by a linking group represented by And at least one of the linking groups represented by the structural formula (1) contained in one molecule is a monovalent organic group (x1) having a polymerizable group.
  • the present invention provides an alkylene chain in which at least one carboxy group at both ends is substituted by at least one hydrogen atom in one molecule, provided that said alkylene chain is an ethereal oxygen atom. And (D) or an alkylene chain in which both ends are a hydroxyl group and at least one of the hydrogen atoms is substituted by a fluorine atom, provided that the alkylene chain includes one having an etheric oxygen atom. And a residue of a reaction product of (A) and a dicarboxylic acid anhydride (E) and at least one residue of a divalent hydroxyl group-containing compound (F) other than the above (A), They are structural formula (1) below
  • X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acid group] Having a structural unit bound by a linking group represented by And at least one of the linking groups represented by the structural formula (1) contained in one molecule is a monovalent organic group (x1) having a polymerizable group.
  • the fluorine-containing active energy ray curable resin which can be used suitably can be provided.
  • the fluorine-containing active energy ray-curable resin of the present invention can be used as a liquid repellent agent, and in recent years the pattern in the manufacture of optical elements such as organic EL elements, quantum dot displays, TFT arrays, thin film solar cells etc. It is suitable as a material of the active energy ray curable resin composition used for formation.
  • Example 1 is a GPC chart of the fluorine-containing active energy ray curable resin (1-i) obtained in Example 1.
  • the fluorine-containing active energy ray-curable resin of the present invention has an alkylene chain in which at least one hydroxyl group at both ends is hydroxyl group and at least one hydrogen atom is substituted by a fluorine atom in one molecule (provided that the alkylene chain is (A), including those having an etheric oxygen atom; And at least one residue of a divalent phenolic hydroxyl group-containing compound (B) other than the above (A) and / or a residue of a divalent carboxylic acid (C), They are structural formula (1) below
  • X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acid group] Having a structural unit bound by a linking group represented by Further, at least one of the linking groups represented by the structural formula (1) contained in one molecule is a monovalent organic group (x1) having a polymerizable group.
  • this may be referred to as a fluorine-containing active energy ray curable resin (I-1).
  • the fluorine-containing active energy ray-curable resin of the present invention has an alkylene chain in which at least one carboxyl group at both ends is at least one hydrogen atom is substituted by a fluorine atom in one molecule (however, The alkylene chain includes those having an etheric oxygen atom) (D), or an alkylene chain in which both ends are hydroxyl groups and at least one of hydrogen atoms is substituted by a fluorine atom (provided that the alkylene chain is ethereal)
  • the residue of the reaction product of (A) and dicarboxylic acid anhydride (E) and the residue of at least one other divalent hydroxyl group-containing compound (F) other than the above (A) Have a base, and They are structural formula (1) below
  • X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acid group] Having a structural unit bound by a linking group represented by Further, at least one of the linking groups represented by the structural formula (1) contained in one molecule is a monovalent organic group (x1) having a polymerizable group.
  • this may be referred to as a fluorine-containing active energy ray curable resin (I-2).
  • a fluorine-containing compound such as a fluorine-based surfactant
  • a perfluoroalkyl chain (however, the alkyl chain includes one having an etheric oxygen atom) or a perfluoroalkylene chain (however, the alkylene chain is Many have been provided which are obtained by copolymerizing an acrylic monomer having an etheric oxygen atom, and a monomer copolymerizable therewith.
  • a bifunctional monomer having a (meth) acryloyl group at both ends of a perfluoroalkylene chain (provided that the above-mentioned alkylene chain includes those having an etheric oxygen atom) and other polymerizable monomers Copolymers with the body are also provided.
  • a fluorine-containing active energy ray curable resin is also provided by introducing an active energy ray curable functional group into a portion corresponding to a side chain in a molecular structure.
  • the fluorine-containing compound obtained by applying these acrylic copolymerization methods has a (meth) acryloyl group at both ends of a perfluoroalkylene chain (however, the alkylene chain includes one having an etheric oxygen atom). If one tries to increase the content of fluorine atoms contained in one molecule, gelation will occur because a difunctional monomer having the following is used. Therefore, there is an upper limit to the amount of fluorine atoms that can be introduced into one molecule, and the degree of freedom in design is low. Moreover, in order to exert a certain effect on the water and oil repellency, leveling property, etc.
  • a fluorine-containing active energy ray-curable resin having a new structure is designed using a raw material which is easily obtained industrially.
  • (meth) acryloyl group refers to one or both of methacryloyl group and acryloyl group
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • acrylic acid refers to one or both of methacrylic acid and acrylic acid.
  • a residue in the present invention specifically, an alkylene chain in which both terminals are hydroxyl groups and at least one of hydrogen atoms is substituted by a fluorine atom (however, the alkylene chain has an etheric oxygen atom)
  • the residue of (A), the residue of the divalent phenolic hydroxyl group-containing compound (B), and the residue of the divalent hydroxyl group-containing compound (F) remove hydrogen atoms in hydroxyl groups in the structure.
  • alkylene chain substituted by a fluorine atom (provided that the above-mentioned alkylene chain includes those having an etheric oxygen atom) (A), a divalent phenolic hydroxyl group-containing compound (B), a divalent hydroxyl group-containing compound Compound (F) is not limited to be used.
  • D Residues of (D), an alkylene chain in which both ends are a hydroxyl group and at least one of hydrogen atoms is substituted by a fluorine atom (however, the alkylene chain includes those having an etheric oxygen atom).
  • the alkylene chain in (D) has a fluorine atom. It is a partial structure, in which at least one of the hydrogen atoms in the alkylene chain is substituted by a fluorine atom, and the fluoroalkylene chain is a fluoroalkylene ether chain formed by connecting these via an oxygen atom.
  • the alkylene chain may be linear, branched or a cycloal formed by forming a part of the ring. It may include a lens structure.
  • a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene chain having 1 to 6 carbon atoms linked via an oxygen atom from the viewpoint of ease of handling. It is preferable that it is an alkylene ether chain, and it is preferable that it is a perfluoro alkylene ether chain from the point which adjustment of a fluorine atom content rate is easy. Furthermore, even if it is a structure in which a hydroxyl group is directly bonded to both ends of a perfluoroalkylene ether chain, it may be a structure in which a hydroxyl group is bonded via an alkylene chain having no fluorine atom.
  • the number of carbon atoms directly bonded to a fluorine atom contained in one molecule is preferably in the range of 1 to 100, and in the case of a perfluoroalkylene chain, the number of carbon atoms is 1 to 6 as described above. It is preferably in the range of 6, particularly preferably in the range of 4 to 6.
  • the number of carbon atoms to which a fluorine atom is directly bonded is preferably 1 to 6, and the number of repetitions is preferably in the range of 1 to 50. It is preferable that it is a perfluoroalkylene ether chain having an alkylene chain of 3 as a repeating unit and having a repeating number in the range of 1 to 50.
  • An alkylene chain wherein both ends are a hydroxyl group and at least one of hydrogen atoms is substituted by a fluorine atom (however, the alkylene chain includes those having an etheric oxygen atom).
  • the alkylene chain includes those having an etheric oxygen atom.
  • Rf an alkylene chain in which at least one of hydrogen atoms is substituted by a fluorine atom
  • this residue is “—O It is a structural unit represented by -Rf-O-.
  • an alkylene chain in which both ends are a carboxy group and at least one of hydrogen atoms is substituted by a fluorine atom (provided that the alkylene chain includes those having an etheric oxygen atom)
  • the fluorine-containing active energy ray curable resin (I-1) of the present invention has a structural unit represented by "-O-Rf-O-" and a divalent phenol other than the above (A). And / or a residue of a divalent carboxylic acid (C).
  • the residue of the divalent phenolic hydroxyl group-containing compound (B) is a structural unit represented by "-O- ⁇ -O-" when the aromatic ring moiety is " ⁇ ".
  • this aromatic ring portion is composed of a single benzene ring or a condensed ring such as naphthalene, anthracene, phenanthrene, acenaphthene, fluorene, fluoranthene, pyrene, etc.
  • two or more benzene rings and condensed rings are directly bonded Or a branched or linear alkylene chain (a part or all of the hydrogen atoms may be substituted with a fluorine atom), an oxygen atom, a sulfur atom, or -NR- (wherein R represents a hydrogen atom or an alkyl) Group may be bonded by a divalent linking group such as a group), and may have a monovalent substituent other than a hydroxyl group on the benzene ring and the condensed ring.
  • the residues of the bivalent phenolic hydroxyl group-containing compound (B) present in one molecule may be all identical or different.
  • the substituent may be a monovalent one, and examples thereof include, for example, bromine atom, chlorine atom, iodine atom, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group Group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfone X
  • a structural unit derived from biphenol, bisphenol, binaphthol or naphthalenediol which may have a substituent on the ring is preferable, Particularly preferred is a structural unit derived from biphenol or bisphenol, and most preferred is a structural unit derived from bisphenol A or bisphenol F.
  • the portion of R 1 is not particularly limited, and may be derived from an aliphatic compound or may have an aromatic ring.
  • the residues of the divalent carboxylic acid (C) present in (1) may be identical or may have different residues.
  • succinic acid and maleic acid are excellent in terms of the balance of performance such as industrial raw material availability, heat resistance of the obtained fluorine-containing active energy ray curable resin, and surface segregation property in the manufacturing method described later. It is preferable that it is a structural unit [residue] derived from.
  • an alkylene chain in which both ends are a hydroxyl group and at least one of hydrogen atoms is substituted by a fluorine atom (however, the alkylene chain includes those having an etheric oxygen atom) (A) and dicarboxylic acid anhydride It has a residue of a reactant with the substance (E) and a residue of a divalent hydroxyl group-containing compound (F) other than the above (A).
  • the portion of R 2 in the above is not particularly limited, and may be derived from an aliphatic compound or may have an aromatic ring.
  • R 2 may be derived from phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, etc.
  • the structure of R ′ in one molecule may be the same structure or may be a structure including a plurality of different structures.
  • succinic anhydride and maleic anhydride are superior in terms of performance balance such as industrial raw material availability, heat resistance of the resulting fluorine-containing active energy ray curable resin and surface segregation property in the production method described later. It is preferable that it is a structural unit derived from an acid.
  • Examples of the residue of the divalent hydroxyl group-containing compound (F) other than the above (A) include the residues of the aforementioned divalent phenolic hydroxyl group-containing compound (B) and the residues of aliphatic diols, and the skeleton When “R 3 ” is designated, it is a structural unit represented by “—O—R 3 —O—”.
  • R 3 moiety in the above is the same as ⁇ mentioned as the residue of the above-mentioned bivalent phenolic hydroxyl group-containing compound (B), or a cyclocycle such as an alkylene chain, oxyalkylene chain, cyclopentane, cyclohexane or the like
  • R 3 having a plurality in one molecule may have the same structure or may contain a plurality of different structures.
  • it from the viewpoint of excellent balance of performance such as industrial raw material availability, heat resistance of the resulting fluorine-containing active energy ray curable resin and surface segregation property in the production method described later, it has 1 to 6 carbon atoms. It is preferable that it is an alkylene chain.
  • the fluorine-containing active energy ray-curable resin of the present invention has a linear structure as described above, and the structural unit having an oxygen atom forming an ether bond at the end described in detail above has the following structural formula (1 )
  • X is a hydrogen atom, a monovalent organic group (x1) having a polymerizable group, or a monovalent organic group (x2) having an acid group] Having a structural unit bound by a linking group represented by Further, at least one of the linking groups represented by the structural formula (1) contained in one molecule is a monovalent organic group (x1) having a polymerizable group.
  • Examples of the polymerizable group contained in the organic group (x1) include a vinyl group or a (meth) acryloyl group, and from the viewpoint of polymerizability when used as an active energy ray curable resin composition described later, (meth) It is preferable that it is an organic group containing an acryloyl group.
  • X as a monovalent organic group (x1) having a polymerizable group, for example, an isocyanate group, a carboxy group or a secondary hydroxyl group in which X is a hydrogen atom
  • a method of reacting a compound having a carboxylic acid halide group and a vinyl group or a (meth) acryloyl group for example, an isocyanate group, a carboxy group or a secondary hydroxyl group in which X is a hydrogen atom
  • a method of reacting a compound having a carboxylic acid halide group and a vinyl group or a (meth) acryloyl group for example, an isocyanate group, a carboxy group or a secondary hydroxyl group in which X is a hydrogen atom
  • a method of reacting a compound having a carboxylic acid halide group and a vinyl group or a (meth) acryloyl group for example, an isocyanate group, a carboxy
  • Y is a divalent linking group
  • R is a hydrogen atom or a methyl group
  • the linking group contains a structure represented by
  • Examples of the (meth) acrylate having an isocyanate group include the compounds shown below, a monomer having one isocyanate group and one (meth) acryloyl group, one isocyanate group and two (meth) Monomer having acryloyl group, monomer having one isocyanate group and three (meth) acryloyl groups, monomer having one isocyanate group and four (meth) acryloyl groups, one isocyanate group and five The monomer etc. which have one (meth) acryloyl group are mentioned.
  • R ′ is an alkylene chain having 2 to 4 carbon atoms
  • R is a hydrogen atom or a methyl group
  • n is an integer of 1 to 5.
  • Examples of specific products of these (meth) acrylates having an isocyanate group include 2-acryloyloxyethyl isocyanate (trade name: "Kalens AOI” manufactured by Showa Denko KK, etc.), 2-methacryloyloxyethyl isocyanate (trade name) C .: “Kalens MOI” manufactured by Showa Denko KK and the like, 1,1-bis (acryloyloxymethyl) ethyl isocyanate (trade name: "Karens BEI” manufactured by Showa Denko Co., Ltd., etc.).
  • the diisocyanate compound used in the reaction is butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl Aliphatic diisocyanates such as xylylene diisocyanate;
  • Cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, etc .;
  • 1,5-Naphthylene diisocyanate 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate
  • aromatic diisocyanates such as 1,4-phenylene diisocyanate and tolylene diisocyanate.
  • At least one of X in the general formula (1) is a monovalent organic group (x1) having a polymerizable group as described above, but in a plurality of linking groups present in one molecule, Further, it is preferable to use a curable composition described later, in particular, as a resist composition, which further includes a monovalent organic group (x2) having an acid group.
  • the acid group is not particularly limited and includes, for example, a carboxy group, a sulfo group, and a phosphoric acid group, and in particular, it is a linking group having a carboxy group from the viewpoint of good alkali solubility and availability of raw materials. It is preferable to
  • the method for introducing the acid group is not particularly limited, and examples thereof include a method in which a compound having an acid anhydride group is reacted with a secondary hydroxyl group in which X is a hydrogen atom.
  • the introduction of an acid group is more excellent in alkali developability, and is useful for forming a high-definition pattern.
  • the introduction amount of the acid group is appropriately set according to the use and the performance level thereof, but the acid value is preferably in the range of 5 to 120 mg KOH / g, and 7 to 100 mg KOH It is more preferably in the range of 1 / g, and most preferably in the range of 10 to 80 mg KOH / g.
  • the fluorine-containing active energy ray curable resin of the present invention has a chain structural unit as described above, but the terminal end thereof is derived from the compound used as a raw material and is not particularly limited.
  • the terminal is a hydrogen atom, a glycidyl group, or a carboxy group when it is synthesized by the production method described later.
  • These terminal structures are naturally determined by the feed ratio of the raw materials and the reaction sequence, and even if a plurality of compounds contained in the resin consist only of one having the same terminal structure, they have different terminal structures. Even a mixture of compounds can be preferably used.
  • a fluorine-containing active energy ray curable resin of this invention what is represented by a following formula can be mentioned, for example.
  • m and n each represent the number of repetitions and are integers of 1 or more.
  • PFPE shows a perfluoro alkylene ether chain.
  • the fluorine atom content of the fluorine-containing active energy ray curable resin of the present invention can be easily set according to the application and desired water and oil repellency, liquid repellency, leveling property, etc. It is preferably in the range of 1 to 45% by mass, particularly preferably in the range of 3 to 40% by mass, from the viewpoint of compatibility with other resins, compounds, solvents, etc. in the case of using a linear curable resin composition. Is preferred.
  • this fluorine atom content rate is calculated from the raw material type at the time of resin design, and the ratio, it can also be measured by combustion ion chromatography. In the present invention, the latter range is preferable in the actual measurement value of the latter.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the fluorine-containing active energy ray curable resin of the present invention have good compatibility with other compounding components when used as a curable resin composition.
  • the number average molecular weight (Mn) is preferably in the range of 500 to 100,000, and preferably 1,000 to 50,000, because high leveling property, water and oil repellency, and liquid repellency can be easily realized. The range is more preferred.
  • the weight average molecular weight (Mw) is preferably in the range of 5,000 to 200,000, and more preferably in the range of 10,000 to 100,000.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
  • GPC gel permeation chromatography
  • Measuring device "HLC-8220 GPC” manufactured by Tosoh Corporation, Column: Guard column “HHR-H” (6.0 mm ID ⁇ 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” manufactured by Tosoh Corporation (7.8 mm ID x 30 cm) + “TSK-GEL GMHHR-N” manufactured by Tosoh Corporation (7.8 mm ID x 30 cm) + “TSK-GEL GMHHR-N” manufactured by Tosoh Corporation (7.8 mm ID x 30 cm) + “TSK-GEL GMHHR-N” manufactured by Tosoh Corporation (7.8 mm ID x 30 cm) Detector: ELSD (Ortech "ELSD 2000”) Data processing: Tosoh Corp.
  • the fluorine-containing active energy ray curable resin of the present invention is excellent in curability when used as a curable resin composition to be described later, and is excellent in water and oil repellency and liquid repellency over a long period on the surface of the cured film. More preferably, the active energy ray-curable functional group concentration is in the range of 0.5 to 3.0 mmol / g.
  • the method for producing the fluorine-containing active energy ray-curable resin of the present invention is not particularly limited, but it is produced by the following method from the viewpoint of excellent industrial availability of raw materials and production efficiency in production. Is preferred.
  • Production method 1 a compound (a1) having an alkylene chain in which at least one of hydrogen atoms is substituted by a fluorine atom (wherein the alkylene chain includes those having an etheric oxygen atom) and an epoxy group, and a bivalent Secondary hydroxyl group in the reaction product obtained by reacting the above-mentioned phenolic hydroxyl group-containing compound (a2) and / or divalent carboxylic acid (a3) as an essential raw material, an active energy ray-curable functional group and isocyanate A method of reacting a compound (a4) having a group and
  • Production method 2 a compound (a5) having an alkylene chain in which at least one hydrogen atom is substituted by a fluorine atom (wherein the alkylene chain includes those having an etheric oxygen atom) and a carboxy group or a hydroxyl group, Method of reacting a compound (a4) having an active energy ray-curable functional group and an isocyanate group with a secondary hydroxyl group in a reaction product obtained by reacting a divalent epoxy compound (a6) as an essential raw material .
  • the alkylene chain in the compound (a1) having an alkylene chain in which at least one of the hydrogen atoms is substituted by a fluorine atom (provided that the above-mentioned alkylene chain includes those having an etheric oxygen atom) and an epoxy group is
  • it is a perfluoroalkylene ether chain having a repeating structure in which a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene chain having 1 to 6 carbon atoms is linked by an oxygen atom. Is preferred.
  • Examples of the compound (a1) include those represented by the following structural formulas.
  • the terminal epoxy group in the compound (a1) is excellent in reactivity, it is linear by the ring-opening reaction of the epoxy group with the divalent phenolic hydroxyl group-containing compound (a2) or the divalent carboxylic acid (a3) While a compound is obtained, the secondary hydroxyl group derived from an epoxy group can be produced in the linking group part.
  • a fluorine-containing active energy ray curable resin is easily obtained by reacting the compound (a4) having an active energy ray curable functional group and an isocyanate group as described above with respect to the above secondary hydroxyl group. Can.
  • a divalent epoxy compound (a6) other than the compound (a1) may be used in combination to adjust to a desired molecular weight, or to adjust heat resistance, fluorine atom content and the like.
  • the terminal structure of the resin thus obtained that is, the terminal of the fluorine-containing active energy ray-curable resin can be any of a hydrogen atom, a glycidyl group and a carboxy group according to the raw material ratio to be used.
  • the use ratio of the compound (a1) and the divalent phenolic hydroxyl group-containing compound (a2) or the divalent carboxylic acid (a3), or the use ratio of the divalent epoxy compound (a6) used in combination is particularly
  • the total number of moles of epoxy groups in the compound (a1) and epoxy groups of the divalent epoxy compound (a6) used in combination as required is not limited, but phenolic hydroxyl group or carboxy group It is preferable to use the total number of moles of groups in the range of 0.9 to 1.1. Since this reaction is a usual ring opening reaction of epoxy group, it is easily stirred at 150 to 180 ° C. using a catalyst such as quaternary onium salts, imidazoles and TPP in a solvent-free or organic solvent. A reactant can be obtained.
  • the organic solvent that can be used here is not particularly limited, and examples thereof include, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary Alcohol compounds such as butanol and tertiary butanol, Glycol ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, etc.
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • methanol ethanol
  • ethanol 1-propyl alcohol
  • isopropyl alcohol 1-butanol
  • secondary Alcohol compounds such as butanol and tertiary butanol
  • Glycol ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, etc.
  • ether compounds such as 1,4-dioxane, 1,3-dioxane, diethoxyethane, acetonitrile
  • aprotic polar solvents such as dimethylsulfoxide and dimethylformamide.
  • organic solvents may be used alone, or two or more may be used in combination as appropriate to adjust the polarity.
  • divalent phenolic hydroxyl group-containing compound (a2) examples include resorcin, catechol, hydroquinone, biphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol Z, binaphthol. And dihydroxy naphthalene, and compounds having the above-mentioned monovalent substituent on the aromatic ring thereof.
  • R 1 is each independently a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an aryl group or an aralkyl group, and p is an integer of 1 to 4) , L is 0 or 1, q is 1 or 2.
  • biphenol, bisphenol, binaphthol, or naphthalenediol may be used from the viewpoint of the excellent balance of performance such as industrial raw material availability, heat resistance of the fluorine-containing active energy ray curable resin obtained, surface segregation property, etc.
  • bisphenol A and bisphenol F are preferably used.
  • the divalent carboxylic acid (a3) may be either aliphatic or aromatic and, for example, malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pimelic acid, Aliphatic divalent carboxylic acids such as suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid and maleic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acids, and The compound etc. which have the said monovalent substituent on these aromatic rings are mentioned. These may be used alone or in combination of two or more. Among these, succinic acid and maleic acid are preferably used from the viewpoints of industrial raw materials availability, heat resistance of the obtained fluorine-containing active energy ray-curable resin, and performance balance such as surface segregation.
  • the compound (a4) having an active energy ray-curable functional group and an isocyanate group it is preferable to use a compound having an isocyanate group and a (meth) acryloyl group from the viewpoint of good reactivity, And the like. It is preferable to use 2-ethyl isocyanato acrylate and 2-ethyl isocyanato methacrylate. Moreover, these may be individual or may use 2 or more types together.
  • this reaction is a reaction of a usual isocyanate group and a hydroxyl group, for example, amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phophins such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate and octyl Organotin compounds such as tin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octylate and the like; products having a secondary hydroxyl group obtained above using a urethanization catalyst such as an organic metal compound such as zinc octylate Alternatively, the compound (a4) may be added dropwise while heating to 50 to 120.degree. C. or the like.
  • amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine
  • phophins
  • the use ratio of the compound (a4) having an active energy ray-curable functional group and an isocyanate group can be appropriately set according to the target functional group concentration, and for example, an isocyanate group relative to a secondary hydroxyl group It is preferable to use the mole number of in the range of 0.3 to 1.0.
  • the divalent epoxy compound (a6) which may be used in combination for the adjustment of molecular weight etc. is not particularly limited.
  • bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl type Examples thereof include epoxy resins, tetramethylbiphenyl type epoxy resins, dihydroxynaphthalene type epoxy resins, and dicyclopentadiene-phenol addition reaction type epoxy resins.
  • the compound etc. which epoxidized the alkylene oxide adduct of bisphenol may be sufficient.
  • an acidic radical is introduce
  • This acid group can be easily obtained, for example, by reacting an acid anhydride group-containing compound (a7) with a secondary hydroxyl group which has not reacted with an isocyanate group.
  • the acid anhydride group-containing compound (a7) is not particularly limited, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Acids, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and the like can be mentioned, and these may be used alone or in combination of two or more. From the viewpoint of easy reaction, it is preferable to use succinic anhydride and maleic anhydride.
  • Production method 2 a compound (a5) having an alkylene chain in which at least one of hydrogen atoms is substituted by a fluorine atom (wherein the alkylene chain includes those having an etheric oxygen atom) and a carboxy group or a hydroxyl group
  • a compound (a4) having an active energy ray-curable functional group and an isocyanate group is reacted with a secondary hydroxyl group in a reaction product obtained by reacting a divalent epoxy compound (a6) as an essential raw material
  • the active energy ray-curable functional group is introduced, but the divalent epoxy compound used at this time, and the compound (a4) having an active energy ray-curable functional group and an isocyanate group, are produced by the production method 1
  • the same compounds as those used can be mentioned, and preferred ones are also the same.
  • the alkylene chain in the compound (a5) having an alkylene chain in which at least one of the hydrogen atoms is substituted by a fluorine atom (provided that the alkylene chain includes those having an etheric oxygen atom) and a carboxy group or a hydroxyl group is And the above-mentioned, that is, a perfluoroalkylene ether chain having a repeating structure in which a perfluoroalkylene chain having 1 to 6 carbon atoms or a perfluoroalkylene chain having 1 to 6 carbon atoms is connected by an oxygen atom Is preferred.
  • Examples of the compound (a5) include those represented by the following structural formulas.
  • PFPE is the same as described above.
  • As a method of introducing a carboxy group at the end it is possible to easily obtain by reacting a compound having a hydroxyl group at the end with a dicarboxylic acid anhydride.
  • the reaction of the carboxy group or hydroxyl group in the compound (a5) with the divalent epoxy compound (a6) is a general ring opening reaction of an epoxy group, and the reaction causes the compound (A) to have a secondary hydroxyl group-containing linking group A reactant having a structure in which a5) and the compound (a6) are linked is obtained.
  • An active energy ray-curable functional group and an acid group can be introduced to the secondary hydroxyl group by the same raw materials and reaction as in Production method 1.
  • the above-mentioned divalent carboxylic acid (a3) other than the compound (a5) or the above-mentioned divalent phenol You may use together an active hydroxyl group containing compound (a2).
  • the terminal structure of the resin thus obtained that is, the terminal of the fluorine-containing active energy ray-curable resin can be any of a hydrogen atom, a glycidyl group and a carboxy group according to the raw material ratio to be used.
  • This reaction is a usual ring opening reaction of epoxy group, it is easily stirred at 150 to 180 ° C. using a catalyst such as quaternary onium salts, imidazoles and TPP in a solvent-free or organic solvent. A reactant can be obtained.
  • the organic solvent that can be used here is not particularly limited, and examples thereof include, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary Alcohol compounds such as butanol and tertiary butanol, Glycol ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, etc.
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • methanol ethanol
  • ethanol 1-propyl alcohol
  • isopropyl alcohol 1-butanol
  • secondary Alcohol compounds such as butanol and tertiary butanol
  • Glycol ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, etc.
  • ether compounds such as 1,4-dioxane, 1,3-dioxane, diethoxyethane, acetonitrile
  • aprotic polar solvents such as dimethylsulfoxide and dimethylformamide.
  • organic solvents may be used alone, or two or more may be used in combination as appropriate to adjust the polarity.
  • the subsequent reaction is the same as in Production method 1. Since each of the above reactions proceed stoichiometrically, each compound used as a raw material hardly remains in the system in an unreacted state, so a low molecular weight compound in the resin obtained Is difficult to be included. Therefore, when the obtained resin is used in the same manner as a conventional fluorine-based surfactant, it is possible to effectively suppress volatilization during curing, detachment from the surface of the cured film, and the like.
  • the fluorine-containing active energy ray-curable resin of the present invention can be used as a main ingredient of an active energy ray-curable composition itself, but has extremely excellent surface modification performance, so the active energy ray-curable resin Stain resistance such as water repellency, oil repellency, liquid repellency (ink repellency), etc. excellent for cured film by using as a fluorine-based surfactant (fluorine-based surface modifier) to be added to the base composition Leveling can be provided.
  • the active energy ray curable composition of the present invention contains the fluorine-containing active energy ray curable resin of the present invention, and as its main component, active energy other than the above-mentioned fluorine-containing active energy ray curable resin It contains a radiation curable resin (II) or an active energy ray curable monomer (III).
  • the active energy ray curable resin (II) and the active energy ray curable monomer (III) may be used alone or in combination.
  • fluorine-containing active energy ray curable resin of the present invention is a surface-modified in the active energy ray-curable composition. Act as an agent.
  • active energy ray-curable resin (II) examples include urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, acrylic acrylate resin, maleimide group-containing resin, cardo type resin and the like.
  • the urethane (meth) acrylate resin is, for example, a resin having a urethane bond obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound and a (meth) acryloyl group. Etc.
  • Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate Hydrogenated tolylene diisocyanate, hydrogenated xylized Diisocyanates, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate and
  • aromatic polyisocyanate compound examples include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate and naphthalene diisocyanate.
  • Examples of the hydroxy group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Dihydric alcohols such as 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate hydroxypivalate Mono (meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di Mono or di (meth) acrylates of trihydric alcohols such as meta) acrylates, bis (2
  • reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound with the hydroxy group-containing (meth) acrylate compound can be performed, for example, in the presence of a urethanization catalyst according to a conventional method.
  • urethanization catalyst examples include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phophins such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate and octyl Organotin compounds such as tin diacetate, dibutyltin diacetate and tin octylate; and organometallic compounds such as zinc octylate.
  • amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine
  • phophins such as triphenylphosphine and triethylphosphine
  • dibutyltin dilaurate octyltin trilaurate and octyl
  • Organotin compounds such as tin diacetate,
  • urethane (meth) acrylate resins those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound are particularly excellent in the transparency of the cured film and have a sensitivity to active energy rays. It is preferable from the point which is favorable and excellent in curability.
  • the unsaturated polyester resin is, for example, a curable obtained by polycondensation of an ⁇ , ⁇ -unsaturated dibasic acid or an acid anhydride thereof, a dibasic acid other than the dibasic acid or an acid anhydride thereof, and glycols. Resin etc. are mentioned.
  • the ⁇ , ⁇ -unsaturated dibasic acid or an acid anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters of these.
  • dibasic acids other than the ⁇ , ⁇ -unsaturated dibasic acids or their acid anhydrides and their acid anhydrides include, for example, aromatic saturated dibasic acids, aliphatic dibasic acids, and alicyclic saturated dibasic acids And their acid anhydrides and the like.
  • aromatic saturated dibasic acid or its acid anhydride for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endo methylene tetrahydrophthalic anhydride, halogenated phthalic anhydride and These esters etc. are mentioned.
  • Aliphatic dibasic acids, alicyclic saturated dibasic acids and acid anhydrides thereof include, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and These esters etc. are mentioned.
  • glycols ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol
  • examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, etc.
  • oxides such as ethylene oxide and propylene oxide can be used in the same manner.
  • epoxy (meth) acrylate resin for example, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, etc. And the like.
  • the acrylic acrylate resin is an acrylic resin containing an acryloyl group. Specifically, a compound obtained by adding acrylic acid to an acrylic resin obtained by copolymerizing glycidyl methacrylate, an acrylic resin obtained by copolymerizing 2-acryloyloxyethyl isocyanate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate And compounds obtained by adding 2-acryloyloxyethyl isocyanate to an acrylic resin obtained by copolymerizing a hydroxyl group-containing monomer.
  • the maleimide group-containing resin for example, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethyl maleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol And tetrafunctional maleimide ester compounds obtained by esterifying maleimide caproic acid and tetraethylene oxide adduct of pentaerythritol, and polyfunctional maleimide ester compounds obtained by esterifying maleimide acetic acid and polyhydric alcohol compounds.
  • active energy ray-curable resins can be used alone or in combination of two or more.
  • the cardo resin is generally a generic term for a resin having a structure in which a cyclic group is directly bonded to a polymer chain, and for example, a resin having the following structure can be exemplified.
  • R represents a hydrogen atom or an alkyl group.
  • R ′ represents a hydrogen atom or a methyl group.
  • N is an integer of 0 to 20.
  • the compound which has one or more ethylenically unsaturated bonds can be illustrated, for example.
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid esters having a hydroxyl group such as glycerol mono (meth) acrylate ;
  • Aromatic vinyl compounds such as styrene and derivatives thereof; Vinyl compounds such as N-vinyl pyrrolidone; N-substituted maleimides such as N-cyclohexyl maleimide, N-phenyl maleimide, N-benzyl maleimide and the like;
  • a lactone such as ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone
  • Examples include polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly 2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers.
  • active energy ray-curable monomers having two ethylenic unsaturated bonds include, for example, 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopen Glycol di (meth) acrylate, 3-methyl-pentaned
  • an active energy ray curable monomer having three ethylenically unsaturated bonds for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri ( Meta) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone modified pentaerythritol tri (meth) Acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, reaction product of caprolactone modified pentaerythritol tri (meth) acrylate and acid anhydride Reactants, and the like of the caprolactone-modified dipentaeryth
  • an active energy ray curable monomer having four ethylenically unsaturated bonds for example, pentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, etc. Can be mentioned.
  • an active energy ray curable monomer having five or more ethylenically unsaturated bonds for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, Tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritol hepta (meth ) Acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate,
  • trimethylolpropane tri (meth) acrylate trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, in particular, from the viewpoint of excellent hardness of the cured coating film.
  • the trifunctional or higher polyfunctional (meth) acrylate such as meta) acrylate is preferable.
  • active energy ray curable monomers (III) can be used alone or in combination of two or more.
  • the amount used is the leveling property of the resulting cured film, and the repellency It is easy to make the water and oil repellency and the stain resistance sufficient, and the hardness and the transparency after curing of the composition are also well balanced.
  • the amount is preferably in the range of 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the linear curable resin (II) and the active energy ray curable monomer (III) More preferably, it is in the range of
  • the fluorine-containing active energy ray curable resin (I) of the present invention alone or the above-described active energy ray curable composition can be made a cured film by applying an active energy ray after being applied to a substrate.
  • the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays.
  • ultraviolet rays are irradiated as active energy rays to form a cured film, it is preferable to add a photopolymerization initiator to improve the curability. Further, if necessary, a photosensitizer can be further added to improve the curability.
  • curing is performed quickly without using a photopolymerization initiator or a photosensitizer, and in particular, a photopolymerization initiator or Although it is not necessary to add a photosensitizer, there is no problem even if it is added.
  • ionizing radiation such as electron beam, alpha ray, beta ray, and gamma ray
  • the photopolymerization initiator examples include an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator.
  • the intramolecular cleavage type photopolymerization initiator for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy -2-Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl Acetophenone compounds such as propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone; benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether; -Tri
  • hydrogen abstraction type photopolymerization initiators examples include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylic Benzophenone compounds such as benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone and the like; 2-isopropylthioxanthone, 2,4-dimethyl Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; aminobenzophenone compounds such as Michael-ketone, 4,4'-diethylaminobenzophenone; 10-butyl- - chloro acridone, 2-ethyl an
  • photopolymerization initiators from the viewpoint of excellent compatibility with the active energy ray curable resin (II) and the active energy ray curable monomer (III) in the active energy ray curable composition, 1 -Hydroxycyclohexyl phenyl ketone and benzophenone are preferred, in particular 1-hydroxy cyclohexyl phenyl ketone.
  • photopolymerization initiators can be used alone or in combination of two or more.
  • amines such as aliphatic amines and aromatic amines
  • ureas such as o-tolyl thiourea, sodium diethyl dithiophosphate, s-benzyl isothiuronium-p-toluene sulfonate and the like
  • sulfur compounds of the photosensitizer for example, amines such as aliphatic amines and aromatic amines, ureas such as o-tolyl thiourea, sodium diethyl dithiophosphate, s-benzyl isothiuronium-p-toluene sulfonate and the like
  • sulfur compounds of the photosensitizer for example, amines such as aliphatic amines and aromatic amines, ureas such as o-tolyl thiourea, sodium diethyl dithiophosphate, s-benzyl isothiuronium-p-toluene sulfonate
  • the amount of the photopolymerization initiator and the photosensitizer used is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the non-volatile component in the active energy ray curable composition. Part is more preferable, and 0.3 to 7 parts by mass is further preferable.
  • the active energy ray-curable composition of the present invention may be adjusted in viscosity or refractive index, or adjusted in color tone of a coating film, or the like within the range that does not impair the effects of the present invention.
  • Polymerization initiator polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weather resistance Agents, heat stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss modifiers, mold release agents, compatibilizers, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, silicones, carbonized A hydrogen surfactant or the like can be used in combination.
  • the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and in particular, in order to perform thin film coating, the film thickness may be adjusted. It becomes easy.
  • organic solvents that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol and t-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents may be used alone or in combination of two or more.
  • Examples of the active energy ray for curing the active energy ray-curable composition of the present invention include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays and gamma rays as described above, but specific energy sources
  • ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays and gamma rays as described above, but specific energy sources
  • a curing apparatus for example, a germicidal lamp, a fluorescent lamp for ultraviolet light, a carbon arc, a xenon lamp, a high pressure mercury lamp for copying, a medium or high pressure mercury lamp, an ultra high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light Ultraviolet rays, or electron beams by scanning type, curtain type electron beam accelerators, etc. may be mentioned.
  • ultraviolet light it is particularly preferable to use ultraviolet light, and in order to avoid inhibition of curing by oxygen or the like, it is preferable to irradiate ultraviolet light under an inert gas atmosphere such as nitrogen gas. Further, if necessary, heat may be used as an energy source, and after curing with ultraviolet light, heat treatment may be performed.
  • the coating method of the active energy ray-curable composition of the present invention varies depending on the application, for example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheel coater, spin coater Coating methods using dipping, screen printing, spraying, an applicator, a bar coater or the like, or molding methods using various molds, etc. may be mentioned.
  • the cured film of the present invention has excellent antifouling property, scratch resistance and the like, so that by applying and curing it on the surface of the article, antifouling property, scratch resistance and the like can be imparted to the surface of the article. .
  • the cured film of the present invention can maintain the antifouling property of the surface of the cured film even after the dirt adhering to the surface of the cured film is wiped off.
  • the fluorine-containing active energy ray-curable resin (I) of the present invention as a surface modifier to a coating material, it is possible to impart leveling to the coating material, so that the active energy of the present invention
  • the linear curable composition has high leveling properties.
  • An article capable of imparting antifouling properties by using the fluorine-containing active energy ray curable resin (I) or the active energy ray curable composition of the present invention is a film for polarizing plate of a liquid crystal display (LCD) such as a TAC film; Various display screens such as plasma display (PDP) and organic EL display; touch panel; case or screen of electronic terminal such as mobile phone; transparent protective film for color filter for liquid crystal display (hereinafter referred to as "CF"); liquid crystal TFT Organic insulating film for array; Optical recording medium such as CD, DVD, Blu-ray disc; Transfer film for insert mold (IMD, IMF); Rubber roller for OA equipment such as copier, printer etc .; OA equipment such as copier, scanner etc Glass surface of reading unit; Optical lens such as camera, video camera, glasses Windshields of watches such as watches, glass surfaces; windows of various vehicles such as automobiles and railways; cover glasses or films for solar cells; various construction materials such as decorative panels; window glass of houses;
  • antifouling properties can be imparted to the article surface.
  • an active energy ray such as ultraviolet light
  • the fluorine-containing active energy ray-curable resin (I) of the present invention is added to improve the leveling property, and as a coating material capable of imparting antifouling property and chemical resistance to a coating film, an LCD such as a TAC film.
  • IMD transfer film for mold
  • IMF Coating material for rubber roller for OA equipment such as copying machine, printer etc.
  • Coating material for glass of reading part of OA equipment such as copying machine, scanner etc .
  • Camera video camera
  • Coating materials for optical lenses such as glasses
  • windshields for watches such as watches
  • coating materials for glasses coating materials for windows of various vehicles such as automobiles and railway cars
  • coatings for cover glasses for solar cells or films for films
  • Printing inks or paints for various building materials such as decorative panels
  • Coating materials for window glass in houses Coating materials for woodworking such as furniture; Coating materials for artificial and synthetic leathers; Coating materials or molding materials for various plastic molded articles such as housings for home appliances And FRP bath paint or coating material.
  • a backlight of LCD examples thereof include a prism sheet or a diffusion sheet which is a member.
  • the fluorine-containing active energy ray curable resin (I) of the present invention to a coating material for a prism sheet or a diffusion sheet, the leveling property of the coating material is improved and the coating film is scratch-resistant. (Scratch resistance) and stain resistance can be imparted.
  • the cured film of the fluorine-containing active energy ray curable resin (I) of the present invention has a low refractive index, it is low in the antireflective layer which prevents the reflection of fluorescent lamps etc. on the surface of various displays such as LCD. It can also be used as a coating material for a refractive index layer.
  • the fluorine-containing active energy ray curable resin (I) of the present invention to the coating material for the antireflective layer, particularly the coating material for the low refractive index layer in the antireflective layer, the low refractive index of the coating film The antifouling property can also be imparted to the coating film surface while maintaining the
  • the active energy ray-curable composition of the present invention when used as an antiglare coating material in a coating material application for a protective film of a polarizing plate for LCD, silica fine particles, acrylic resin fine particles, polystyrene resin among the respective compositions described above Excellent in antiglare property by blending inorganic or organic fine particles such as fine particles in a proportion of 0.1 to 0.5 times the total mass of the curing component in the active energy ray curable composition of the present invention It is preferable because it becomes a thing.
  • fluorine-containing active energy ray curable resin (I) or active energy ray curable composition of this invention for the antiglare coating material for protective films of the polarizing plate for LCDs, it is uneven before hardening a coating material. After being brought into contact with a mold having a surface shape, it is also applicable to a transfer method in which an active energy ray is irradiated from the opposite side of the mold for curing to emboss the surface of the coated layer to impart antiglare properties.
  • the curable composition containing the fluorine-containing active energy ray curable resin (I) of the present invention is suitably used as a resist composition.
  • a resist composition a photoresist composition, a color resist composition, etc. are mentioned, for example.
  • the photoresist composition comprises, for example, the fluorine-containing active energy ray curable resin (I) of the present invention and a photoresist agent, and the photoresist agent includes, for example, an alkali soluble resin, a radiation sensitive substance (photosensitive substance ), Including solvents.
  • the alkali solubility refers to the property of being soluble in an aqueous solution (developer) of an alkali compound.
  • a resin film with a film thickness of 1 ⁇ m is formed on a substrate by a resin solution with a resin concentration of 20 mass% (solvent: propylene glycol monomethyl ether acetate), and 1 minute in a KOH aqueous solution with a concentration of 0.05 mass%. It can be exemplified that the film can be dissolved by a film thickness of 0.01 ⁇ m or more when it is immersed.
  • the alkali-soluble resin is not particularly limited as long as it is soluble in an alkaline developer, but a resin having at least one acid group selected from the group of carboxy group, phenolic hydroxyl group and sulfonic acid group or a salt thereof preferable.
  • alkali-soluble resin For example, alkali-soluble resin (photocurable group non-containing alkali-soluble resin) which does not have photocuring property, alkali-soluble resin (photocurable group-containing alkali-soluble resin) which has photocuring property Resin etc. can be illustrated.
  • Examples of the photocurable group-free alkali-soluble resin include the following resins.
  • Alkali-soluble resin (1) obtained by polymerizing a (meth) acrylic polymerizable monomer having an acidic group as an essential component.
  • ⁇ A polymer having no acidic group obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component, and a reactive group having reactivity to the reactive group
  • Alkali-Soluble Resin (2) Obtained by the Reaction of a Compound Having an Acrylate Group with an Acid Group
  • Examples of the photocurable group-containing alkali-soluble resin include the following resins. ⁇ An unsaturated monocarboxylic acid is added to a copolymer of an epoxy group-containing (meth) acrylate and another polymerizable monomer to at least a part of the epoxy group of the copolymer, and further unsaturated An alkali-soluble resin (3) obtained by subjecting an acid anhydride of a polycarboxylic acid to an addition reaction with at least a part of a hydroxyl group generated by an addition reaction of a monocarboxylic acid.
  • the above (1) to (5) will be described in detail below.
  • an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxy group as an essential component and a (meth) acrylic resin having a sulfonic acid group examples thereof include alkali-soluble resins obtained by polymerizing a polymerizable monomer as an essential component. Among them, an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxy group as an essential component is preferable.
  • Examples of the (meth) acrylic polymerizable monomer having a carboxy group include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, and 2- (meth) acryloyloxyethyl.
  • These (meth) acrylic polymerizable monomers having a carboxy group may be used alone or in combination of two or more.
  • (meth) acrylic polymerizable monomers having a carboxy group (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable.
  • Examples of the (meth) acrylic polymerizable monomer having a sulfonic acid group include 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, and 2-hydroxy-3- (meth) acrylate.
  • alkali-soluble resin (1) When preparing the alkali-soluble resin (1), other polymerizable monomers may be used in combination as long as the effects of the present invention are not impaired.
  • another monomer for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) Acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as glycerol mono (meth) acryl
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid esters having a hydroxyl group such as glycerol mono (meth) acrylate ;
  • Aromatic vinyl compounds such as styrene and derivatives thereof; Vinyl compounds such as N-vinyl pyrrolidone; N-substituted maleimides such as N-cyclohexyl maleimide, N-phenyl maleimide, N-benzyl maleimide and the like;
  • Examples include polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly 2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers.
  • the other polymerizable monomers may be used alone or in combination of two or more.
  • styrene methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxy Propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexyl maleimide, N-benzyl maleimide, and N-phenyl maleimide are preferable from the viewpoint of good transparency and less loss of heat resistance.
  • alkali-soluble resin (1) examples include, for example, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate and cyclohexyl (meth) acrylate And a hydroxyl group-containing polymerizable monomer such as cyclohexyl maleimide and a hydroxyl group-containing polymerizable monomer such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate
  • Copolymers of (meth) acrylic acid and (meth) acrylic esters such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc .;
  • Copolymers of (meth) acrylic acid and styrene ; copolymers of (meth) acrylic acid, styrene and ⁇ -methylstyrene, copolymers of (meth) acrylic acid and cyclohexylmaleimide, and the like.
  • alkali-soluble resins (1) alkali-soluble resins using benzyl (meth) acrylate are preferable.
  • the acid value of the alkali-soluble resin (1) is preferably in the range of 10 to 300, more preferably in the range of 20 to 350, and still more preferably in the range of 30 to 300.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the alkali-soluble resin (1) is preferably in the range of 2,000 to 100,000, and more preferably in the range of 3,000 to 70,000. The range of 4,000 to 50,000 is more preferable.
  • the alkali-soluble resin (1-1) to which is added can also be used as a photocurable group-containing alkali-soluble resin.
  • epoxy group-containing unsaturated compound examples include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl- ⁇ -ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl) -4-glycidyl) benzyl acrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether and the like.
  • an alicyclic epoxy group-containing unsaturated compound is preferable because it can improve the heat resistance and the dispersibility when using a pigment as a colorant.
  • an alicyclic epoxy group which the said alicyclic epoxy group containing unsaturated compound has, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5.2. 1.0] dec-2-yl] group and the like.
  • an ethylenically unsaturated group a (meth) acryloyl group is preferable.
  • the alicyclic epoxy group-containing unsaturated compound may be used alone or in combination of two or more.
  • a well-known method can be used.
  • carboxy group-containing alkali-soluble resin and epoxy group-containing unsaturated compound tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethyl Quaternary ammonium salt such as ammonium chloride; epoxy group on the carboxy group of the resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours in the presence of a catalyst such as pyridine or triphenylphosphine Containing unsaturated compounds can be added.
  • a catalyst such as pyridine or triphenylphosphine Containing unsaturated compounds
  • the acid value of the alkali-soluble resin (1-1) is preferably in the range of 10 to 300, more preferably in the range of 20 to 250, and still more preferably in the range of 30 to 200.
  • the polystyrene equivalent weight average molecular weight of the alkali-soluble resin (1-1) measured by GPC is preferably 2,000 to 100,000, more preferably 4,000 to 50,000, and 5, The range of 000 to 30,000 is more preferable.
  • ether dimer examples include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n- Propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2′- [Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate Di (stearyl) -2,2 —
  • dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[ Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
  • These ether dimers can be used alone or in combination of two or more.
  • the solvent used in the solution polymerization method may be one used in a conventional radical polymerization reaction.
  • ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether
  • Aromatic hydrocarbons such as toluene, xylene, ethylbenzene; Chloroform; dimethyl sulfoxide etc. Can be mentioned.
  • These solvents may be used alone or in combination of two or
  • a polymerization initiator When polymerizing the polymerizable monomer, if necessary, a polymerization initiator may be used.
  • the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl peroxy-2 Organic peroxides such as -ethylhexanoate, t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), Azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate) and the like can be mentioned.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the amount of these polymerization initiators to be used may be appropriately set according to the combination of monomers to be used, reaction conditions, the molecular weight of the target alkali-soluble resin, etc., and is not particularly limited. A range of 0.1 to 15% by mass is preferable, and a range of 0.2 to 10% by mass is preferable based on all polymerizable monomer components, since an alkali-soluble resin having an average molecular weight of several thousand to several tens of thousands can be obtained. More preferable.
  • chain transfer agent for molecular weight adjustment.
  • chain transfer agents include mercaptan-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate; ⁇ -methylstyrene dimer and the like, but the chain transfer effect is high and remains in the reaction system Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can reduce polymerizable monomers and are easily available.
  • the amount used in the case of using a chain transfer agent may be appropriately set according to the combination of monomers to be used, reaction conditions, molecular weight of the target monomer, etc., and is not particularly limited, but gelation Since it is possible to obtain an alkali-soluble resin having a weight average molecular weight of several thousand to several tens of thousands, the range of 0.1 to 15 mass% is preferable with respect to all monomers, and the range of 0.5 to 10 mass% is more preferable. preferable.
  • the alkali-soluble resin (2) used in the present invention is a polymer having no acidic group obtained by polymerizing a (meth) acrylic polymerizable monomer having a reactive group as an essential component, and the reactivity It is obtained by reacting a compound having a group having reactivity with a group and an acid group.
  • Examples of the alkali-soluble resin (2) include the following alkali-soluble resins.
  • An acid such as succinic acid anhydride, tetrahydrophthalic acid anhydride, or maleic acid anhydride is obtained after a polymer is obtained using a polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate as an essential component.
  • Alkali-soluble resin obtained by adding an anhydride.
  • a polymer having an epoxy group-containing polymerizable monomer such as glycidyl (meth) acrylate as an essential component it has an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol Alkali-soluble resin obtained by adding a compound.
  • the weight average molecular weight of the alkali-soluble resin (2) is 1,000 to 200,000, as measured by GPC, as the weight average molecular weight measured by GPC is that a coating film is formed well and a coating film excellent in heat resistance is obtained. Is preferable, the range of 2,000 to 10,000 is more preferable, and the range of 2,000 to 50,000 is more preferable. Moreover, you may obtain alkali-soluble resin (2) using the polymerizable monomer used for preparation of said alkali-soluble resin (1) together as needed.
  • the alkali-soluble resin (3) used in the present invention is a copolymer of an epoxy group-containing (meth) acrylate and another polymerizable monomer, in which at least a part of the epoxy group of the copolymer is not It is obtained by addition of a saturated monocarboxylic acid, and addition reaction of an acid anhydride of polycarboxylic acid with at least a part of the hydroxyl group generated by the addition reaction of unsaturated monocarboxylic acid.
  • epoxy group-containing (meth) acrylates examples include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • Acrylate glycidyl ether etc. are mentioned. Among them, glycidyl (meth) acrylate is preferable.
  • These epoxy group-containing (meth) acrylates can be used alone or in combination of two or more.
  • polymerizable monomer which does not have an alicyclic structure as other polymerizable monomers other than the said epoxy group containing (meth) acrylate.
  • polymerizable monomers for example, vinyl aromatics such as styrene, ⁇ -, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;
  • Dienes such as butadiene, 2,3-dimethyl butadiene, isoprene and chloroprene;
  • (Meth) acrylic acid amide (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid-N (Meth) acrylic acid amides such as N-di-i-propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide, (meth) acrylic nitrile, acrolein, vinyl chloride, vinylidene chloride, fluorine Vinyl compounds such as vinyl chloride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate;
  • Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate; N-phenyl maleimide, N-cyclohexyl maleimide, N-lauryl maleimide, N- (4-hydroxyphenyl) maleimide, etc.
  • Monomaleimides; N- (meth) acryloyl phthalimide and the like can be mentioned.
  • At least one of styrene, benzyl (meth) acrylate and monomaleimides is preferably used because the heat resistance and mechanical strength of the cured product can be improved.
  • the use ratio of styrene, benzyl (meth) acrylate and monomaleimides is preferably 1 to 70 mol%, more preferably 3 to 50 mol%, based on the total amount of other polymerizable monomers.
  • the copolymerization reaction of the said epoxy group containing (meth) acrylate and said other polymerizable monomer can use well-known polymerization methods, such as the solution-polymerization method using a radical polymerization initiator.
  • the solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
  • the alkali-soluble resin (3) is, for example, an unsaturated monocarboxylic acid (polymerizable component) in the epoxy group portion of a copolymer of the above-mentioned epoxy group-containing (meth) acrylate and another polymerizable monomer; It can be obtained by reacting with an acid anhydride (alkali soluble component) of polycarboxylic acid.
  • Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, haloalkyl group at the ⁇ -position, alkoxyl group, halogen atom, nitro group or cyano.
  • Monocarboxylic acids such as (meth) acrylic acid substituted by group etc., etc. are mentioned. Among these, (meth) acrylic acid is preferable.
  • These unsaturated monocarboxylic acids can be used alone or in combination of two or more. By using this unsaturated monocarboxylic acid, the alkali-soluble resin (3) can be given polymerizability.
  • the unsaturated monocarboxylic acid is preferably added to 10 to 100 mol%, more preferably 30 to 100 mol%, and more preferably 50 to 100 mol% of the epoxy group of the copolymer. It is further preferable to add.
  • Examples of the acid anhydride of the polycarboxylic acid include acid anhydrides of dicarboxylic acids such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. And anhydrides of carboxylic acids having three or more carboxy groups such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride and the like. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable.
  • the acid anhydrides of these polycarboxylic acids can be used alone or in combination of two or more. By using the acid anhydride of this polycarboxylic acid, alkali solubility can be imparted to the alkali-soluble resin (3).
  • the acid anhydride of the polycarboxylic acid is usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monocarboxylic acid to the epoxy group of the copolymer, and preferably 20 to 90 It is more preferable to add to mol%, and it is further preferable to add to 30 to 80 mol%.
  • the polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the alkali-soluble resin (3) is preferably in the range of 3,000 to 100,000, and in the range of 5,000 to 50,000. Is more preferred.
  • the dispersion degree (Mw / Mn) of the alkali-soluble resin (3) is preferably in the range of 2.0 to 5.0.
  • the epoxy (meth) acrylate resin (4) is prepared, for example, by adding an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having an carboxy group to the ⁇ , ⁇ -unsaturated monocarboxylic acid or ester moiety to the epoxy resin, and It is obtained by reacting polybasic acid anhydride.
  • epoxy resin examples include bisphenol A epoxy resin (commercially available as “epicoat 828”, “epicoat 1001", “epicoat 1002”, “epicoat 1004", etc. manufactured by Mitsubishi Chemical Corporation), bisphenol A epoxy Epoxy resin obtained by the reaction of the alcoholic hydroxyl group of the resin and epichlorohydrin (commercially available, "NER-1302” (epoxy equivalent 323, softening point 76 ° C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (commercially available As “Epikote 807”, “EP-4001”, “EP-4002”, “EP-4004”, etc.
  • TEPIC trisphenol methane type epo Resin
  • EPPN-501 commercially available as “EPPN-501”, “EPN-502”, “EPPN-503” manufactured by Nippon Kayaku Co., Ltd.
  • fluorene epoxy resin commercially available as Caldo manufactured by Nippon Steel Chemical Co., Ltd.
  • Epoxy resin "ESF-300” alicyclic epoxy resin
  • Cyeroxide 2021P "Ceroxide EHPE” manufactured by Daicel Chemical Industries, Ltd.
  • dicyclopentadiene obtained by glycidylating a phenol resin by reaction of dicyclopentadiene and phenol Type epoxy resin
  • XD-1000 manufactured by Nippon Kayaku Co., Ltd.
  • EXA-7200 manufactured by DIC Co., Ltd.
  • NC-3000 NC-7300 manufactured by Nippon Kayaku Co., Ltd.
  • An epoxy resin having a fluorene skeleton can be used.
  • the epoxy resin is a copolymer epoxy resin.
  • the copolymerizable epoxy resin for example, monomers having an epoxy group such as glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like, methyl (meth) acrylate, ethyl (meth) acrylate, butyl ( Meta) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, ⁇ -methylstyrene, glycerin mono (meth)
  • Examples of the (meth) acrylate having a polyoxyalkylene chain include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate and tetraethylene glycol mono (meth) acrylate; And alkoxypolyethylene glycol (meth) acrylates such as methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate and methoxytetraethylene glycol mono (meth) acrylate.
  • polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate and tetraethylene glycol mono (meth) acrylate
  • alkoxypolyethylene glycol (meth) acrylates such as methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate and
  • the molecular weight of the copolymerized epoxy resin is preferably in the range of 1,000 to 200,000.
  • the amount of the epoxy group-containing monomer used as a raw material for the copolymerized epoxy resin is preferably in the range of 10 to 70% by mass, and more preferably in the range of 20 to 50% by mass with respect to the monomer having no epoxy group. preferable.
  • copolymer type epoxy resin for example, "CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, "CP-50S”, “CP-50M”, “CP-20MA” etc. are mentioned.
  • the molecular weight of the epoxy resin is 200 to 200, as a weight average molecular weight in terms of polystyrene measured by GPC, because the coating film formation is good and gelation at the time of addition reaction of ⁇ , ⁇ -unsaturated monocarboxylic acid can be prevented.
  • the range of 000 is preferable, and the range of 300 to 100,000 is more preferable.
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid are preferable, and acrylic acid is good in reactivity. More preferred.
  • ⁇ -unsaturated monocarboxylic acid ester having a carboxy group in the ester part 2-succinoyloxyethyl acrylate, 2-maleinoyloxyethyl acrylate, 2-phthaloyloxyethyl acrylate, Acrylic acid 2-hexahydrophthaloyl oxyethyl, methacrylic acid 2-succinoyloxy ethyl, methacrylic acid 2-maleinoyloxy ethyl, methacrylic acid 2-phthaloyl oxyethyl, methacrylic acid 2-hexahydrophthaloyl Iroxyethyl, crotonic acid-2-succinoyloxyethyl and the like are mentioned, and acrylic acid-2-maleinoyloxyethyl and acrylic acid-2-phthaloyloxyethyl are preferable, acrylic acid-2-maleinoyloxyethyl is preferable. More preferable.
  • the addition reaction of the ⁇ , ⁇ -unsaturated monocarboxylic acid or its ester with the epoxy resin can be carried out using a known method, for example, a method of reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst It can be mentioned.
  • an esterification catalyst tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used.
  • the amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid or ester thereof to be used is preferably in the range of 0.5 to 1.2 equivalents, preferably 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the starting epoxy resin. Is more preferable.
  • polybasic acid anhydrides to be further added to epoxy resins to which ⁇ , ⁇ -unsaturated carboxylic acids or esters thereof have been added include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid dianhydride, methyl hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Biphenyl tetracarboxylic acid dianhydride etc.
  • maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride and biphenyltetracarboxylic dianhydride are preferable. More preferred are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride.
  • These polybasic acid anhydrides can be used alone or in combination of two or more.
  • a known method can also be used for the addition reaction of polybasic acid anhydride, and the reaction can be carried out continuously under the same conditions as the addition reaction of ⁇ , ⁇ -unsaturated carboxylic acid or its ester.
  • the amount of the polybasic acid anhydride used is preferably such that the acid value of the epoxy (meth) acrylate resin to be formed is in the range of 10 to 150, because the alkali developability and coating film formation can be improved. More preferred is an amount in the range of 20-140.
  • an epoxy (meth) acrylate resin having a carboxy group a naphthalene-containing resin described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331, The fluorene-containing resin described in JP-A-2001-354735; and the resins described in JP-A-2005-126674, JP-A-2005-55814, JP-A-2004-295084, etc. can also be exemplified. Further, as a commercially available product, "ACA-200M” manufactured by Daicel Chemical Industries, Ltd. can be exemplified.
  • the cardo resin type resin (5) has a carboxy group and a polymerizable unsaturated group.
  • cardo type resin is a polymer material having various properties such as high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, high gas permeability, etc., and each pixel of a color filter or black It is used as a binder resin when forming a matrix, and in particular, it can be preferably used as a binder resin when forming a black matrix.
  • the cardo type resin is a general term for resins having a structure in which a cyclic group is directly bonded to a polymer main chain, and the presence of bulky substituents in the main chain allows (1) rotational binding of the polymer main chain. (2) Conformational regulation of main chain and side chain, (3) inhibition of intermolecular packing, (4) increase of aromaticity by introduction of aromatic substituent of side chain, etc. In addition to high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, etc., it is considered to exhibit higher gas permeability.
  • resin shown by the following general formula can be mentioned preferably, for example.
  • X is a group represented by the following chemical formula
  • Y is a residue obtained by removing a carboxylic acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride
  • Z is a tetracarboxylic acid dianhydride It is a residue obtained by removing two carboxylic acid anhydride groups from the compound.
  • n is an integer of 0 to 20.
  • Y-derived dicarboxylic acid anhydride (dicarboxylic acid anhydride before removing carboxylic acid anhydride group) include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, methyl endo methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.
  • tetracarboxylic acid dianhydride (the tetracarboxylic acid dianhydride before removing the two carboxylic acid anhydride groups) for inducing the above Z
  • tetracarboxylic acid dianhydride for inducing the above Z
  • examples thereof include anhydrides, tetracarboxylic acid dianhydrides such as biphenyltetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by weight gel permeation chromatography (GPC) of the cardo resin is preferably 1,000 to 1,000,000, more preferably 3,000 to 50,000, and 5 And most preferably from 1,000,000 to 15,000.
  • the alkali-soluble resin one of the above-mentioned alkali-soluble resins (1) to (5) may be used alone, or two or more may be used in combination. Further, by using an alkali-soluble resin in combination with a pigment dispersant to be described later, a high concentration color pixel having excellent adhesion with the substrate is formed without leaving undissolved matter in the non-pixel portion on the substrate. It is preferable because it can be done. Specifically, it is preferable to use a part of the alkali-soluble resin together with a pigment dispersant described later in the dispersion treatment step. In this case, the alkali-soluble resin is preferably used in an amount of 5 to 200% by mass, and more preferably 10 to 100% by mass, based on the pigment.
  • alkali-soluble resins other than the above-mentioned alkali-soluble resins (1) to (5) may be used.
  • a resin for example, an alkali-soluble resin obtained by using a polymerizable monomer having a phenolic hydroxyl group as an acidic group as an essential component, or a polymerizable monomer having a sulfonic acid group as an acidic group is an essential component
  • alkali-soluble resins obtained by using examples of the polymerizable monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like.
  • one or more hydrogen atoms other than phenolic hydroxyl group and vinyl group bonded to the aromatic ring of these monomers are substituted by alkyl group, alkoxyl group, halogen atom, nitro group, cyano group, amide group Compounds etc. are also mentioned.
  • a polymerizable monomer having a sulfonic acid group as an acidic group for example, vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, Examples thereof include (meth) acrylic acid 2-sulfoethyl or salts thereof.
  • the content ratio of the alkali-soluble resin in the composition is 0.1% of the total solid content because the appearance of the cured film and the adhesion to the substrate become good.
  • the range of ⁇ 80% by mass is preferable, and the range of 1 ⁇ 60% by mass is more preferable.
  • the radiation-sensitive substance (photosensitive substance) used in the resist composition is mixed with the above-mentioned alkali-soluble resin, and is ultraviolet light, far ultraviolet light, excimer laser light, X-ray, electron beam, ion beam, ion beam, molecular beam, gamma ray, Any substance can be used as long as it is a substance that changes the solubility of the alkali-soluble resin in the developing solution by irradiating the light.
  • the radiation sensitive substance examples include quinone diazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organic metal compounds, organic acid ester compounds, organic acids Examples thereof include amide compounds, organic acid imide compounds, and poly (olefin sulfone) compounds described in JP-A-59-152.
  • quinone diazide compounds examples include 1,2-benzoquinone azido-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, and 2, 1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, other 1,2-benzoquinoneazido-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride And sulfonic acid chlorides of quinone diazide derivatives such as 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, and 2,1-naphthoquinonedia
  • diazo compound examples include salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the above-mentioned condensates.
  • inorganic salt of diazo resin which is a reactive product organic salt of diazo resin which is a reaction product of the above-mentioned condensate and sulfonic acid as described in US Pat. No. 3,300,309, and the like can be mentioned.
  • azide compound and the diazide compound examples include azide chalconic acid, diazide benzal methyl cyclohexanones and azido cinnamylidene acetophenones as described in JP-A-58-203438, Journal of Japan Chemical Society No. 12, an aromatic azide compound or an aromatic diazide compound as described in p. 1708-1714 (1983).
  • a halogenated organic compound for example, a halogenated compound of an organic compound can be used, and as a specific example, a halogen containing oxadiazole compound, a halogen containing triazine compound, a halogen containing acetophenone compound, a halogen Containing benzophenone compound, halogen containing sulfoxide compound, halogen containing sulfone compound, halogen containing thiazole compound, halogen containing oxazole compound, halogen containing trizole compound, halogen containing 2-pyrone compound, halogen containing aliphatic hydrocarbon compound Compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, various compounds such as sulphenyl halide compounds, and further, for example, tris (2,3-dibromopropyl) phosphate, Scan (2,3-dibromo-3-ch
  • organic acid ester examples include carboxylic acid ester and sulfonic acid ester.
  • organic acid amide examples include carboxylic acid amide, sulfonic acid amide and the like.
  • organic acid imide examples include carboxylic acid imide, sulfonic acid imide and the like.
  • the mixing ratio of the radiation sensitive substance is preferably in the range of 10 to 200 parts by mass, and more preferably in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone and butyrolactone; methanol, ethanol, n-propyl alcohol, iso -Alcohols such as propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, decanol, etc.
  • Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane, etc.
  • Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc.
  • Cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc.
  • alkali-soluble resin used for a color resist composition alkali-soluble resin etc. which are used for the said photoresist composition can be used, for example.
  • the polymerizable compound can be used without particular limitation as long as it is a compound having a photopolymerizable functional group that can be polymerized or crosslinked by irradiation with active energy rays such as ultraviolet rays.
  • a polymerizable compound for example, 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, aroma Obtained by the esterification reaction of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid ester, an unsaturated carboxylic acid and a polyvalent carboxylic acid, and a polyhydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound Examples thereof include a polymerizable compound having a urethane skeleton in which an ester, a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound are reacted.
  • ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolethane tri (for example, Meta) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa
  • examples include (meth) acrylates such as (meth) acrylates and glycerol (meth) acrylates.
  • itaconic acid esters in which the (meth) acrylic acid part of these acrylates is replaced with itaconic acid crotonic acid esters in which crotonic acid is replaced, or maleic acid esters in which maleic acid is replaced.
  • ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid examples include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate and the like.
  • 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 include, for example, esters obtained from (meth) acrylic acid, phthalic acid and ethylene glycol, (meth) acrylic acids, esters obtained from maleic acid and diethylene glycol, (meth) acrylic acid, terephthalic acid and penta And esters obtained from erythritol, (meth) acrylic acid, adipic acid, butanediol, and esters obtained from glycerin.
  • Examples of the polymerizable compound having a urethane skeleton in which the polyisocyanate compound and the (meth) acryloyl group-containing hydroxy compound are reacted include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; fats such as cyclohexane diisocyanate and isophorone diisocyanate Cyclic diisocyanates; 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
  • aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate
  • fats such as cyclohexane diisocyanate and isophorone diisocyanate Cy
  • Examples of the polymerizable compound other than the above include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.
  • polymeric compound which has an acidic radical is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • Polyfunctional monomers having an acid group are preferred.
  • pentaerythritol or dipentaerythritol as the aliphatic polyhydroxy compound. These monomers may be used alone or in combination of two or more.
  • the polyfunctional polymerizable compound having an acid group for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentamer which are commercially available from Toagosei Co., Ltd. as “Alonics TO-1382”.
  • a mixture containing a succinate ester of erythritol pentaacrylate as a main component is mentioned.
  • This polyfunctional polymerizable compound can also be used in combination with other polyfunctional polymerizable compounds.
  • the acid value of the polyfunctional polymerizable compound having an acid group is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30, because the developability, curability, and the like are improved.
  • all polyfunctional polymerizable compounds are mixed. It is preferred that the acid value of the mixture be in the above range.
  • the content of the polymerizable compound is preferably in the range of 5 to 80% by mass, and more preferably in the range of 10 to 70% by mass, based on the total solid content. More preferably, it is in the range of 50% by mass.
  • the ratio of the polymerizable compound to the colorant described later is preferably 5 to 200% by mass, more preferably 10 to 100% by mass, and further preferably 20 to 80% by mass. Is more preferred.
  • any pigment or dye can be used without particular limitation as long as it can be colored.
  • the pigment may be either an organic pigment or an inorganic pigment.
  • organic pigment pigments of respective colors such as red pigment, green pigment, blue pigment, yellow pigment, violet pigment, orange pigment, brown pigment and the like can be used.
  • an azo type, a phthalocyanine type, a quinacridone type, a benzimidazolone type, an isoindolinone type, a dioxazine type, an indanthrene type, a perylene type etc. are mentioned, for example.
  • the following "CI" 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: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 1 9, 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, and C.I. I. Pigment red 177, 209, 224 or 254 is more preferable.
  • Examples of the green pigment include 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. 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, 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 are preferred, and C.I. I. Pigment blue 15: 6 is more preferable.
  • 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, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183,
  • C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 are preferable, and C.I. I. Pigment yellow 83, 138, 139, 150 or 180 are more preferable.
  • 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, 25, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
  • C.I. I. Pigment violet 19 or 23 is preferable, and C.I. I. Pigment Violet 23 is more preferable.
  • orange pigment examples 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, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like.
  • C.I. I. Pigment orange 38 or 71 is preferred.
  • the pixels of the three primary colors of the color filter used in the liquid crystal display device and the organic EL display device are red (R), green (G) and blue (B), so the red pigment, green pigment and blue pigment are main components
  • red pigment, green pigment and blue pigment are main components
  • organic pigments of colors such as yellow, purple and orange may be used as the hue adjustment.
  • examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and the like.
  • the average particle diameter of the organic pigment is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.3 ⁇ m or less in order to increase the luminance of the color liquid crystal display device and the organic EL display device. It is preferable to use an organic pigment in a dispersion process so as to obtain the average particle diameter of these.
  • 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 by a dynamic light scattering type particle size distribution analyzer. For example, Nanotrac (Nanotrac) particle size distribution measuring apparatus “UPA-EX150”, “UPA manufactured by Nikkiso Co., Ltd.”, “UPA -EX 250 "and so on.
  • the colorant used when forming the color resist composition to form a black matrix (BM) is not particularly limited as long as it is black, but carbon black, lamp black, acetylene black, bone black , Thermal black, channel black, furnace black, graphite, iron black, titanium black and the like.
  • two or more types of organic pigments may be mixed, and a combination may be made black by color mixing.
  • carbon black and titanium black are preferable from the viewpoint of light blocking ratio and image characteristics.
  • carbon black coated with a resin is, for example, disclosed in JP-A-9-26571, JP-A-9-71733, JP-A-9-95625, JP-A-9-238863 or JP-A-11-60989. It can be obtained by treating known carbon black by the method described in Japanese Patent
  • a method for producing the titanium black a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere described in JP-A-49-5432, described in JP-A-57-205322
  • Examples thereof include a method of reducing titanium oxide at high temperature in the presence of ammonia, a method of adhering a vanadium compound to titanium dioxide or titanium hydroxide described in JP-A-61-201610, and reducing at high temperature in the presence of ammonia.
  • Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C and the like manufactured by Mitsubishi Materials Corporation.
  • Examples of a combination of two or more organic pigments mixed and made black by mixing include black pigments in which red, green and blue three-color pigments are mixed.
  • Color materials which can be mixed and used to prepare a black pigment include Victoria Pure Blue (C.I. 42 595), Auramine O (C. I. 41000), Cathylon Brilliant Flavin (Basic 13), Rhodamine 6 GCP (C Rhodamine B (C.I. 45170), Safranin OK 70: 100 (C.I. 50240), Eliograusin X (C.I. 42080), No. 1. 120 / Lionol Yellow (C.I. 21090), Lionol Yellow GRO (C.I. 21090), Shimla Fast Yellow 8 GF (C.I.
  • coloring materials that can be mixed and used to prepare a black pigment
  • the average primary particle size 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 good developability.
  • dibutyl phthalate of the carbon black to be used (hereinafter,. Abbreviated as "DBP") absorption amount, 40 ⁇ 100 cm 3 / is preferably in the range of 100 g, 50 since it is good dispersibility, developing property ⁇ 80 cm 3 The range of / 100 g is more preferable.
  • BET specific surface area of carbon black used is more preferably in the range of 50 ⁇ 120m 2 / g is preferably in the range of the dispersion 60 from the stability that good ⁇ 95m 2 / g.
  • carbon black is different in particle shape from organic pigments and the like, exists in a state called a structure in which primary particles are fused, and may sometimes form fine pores on the particle surface by post-treatment. Therefore, in order to express the particle shape of carbon black, in addition to the average particle diameter of primary particles determined by the same method as the organic pigment, the DBP absorption amount (JIS K 6221) and the specific surface area by BET method ( It is preferable to measure JIS K 6217) and use it as an index of the structure and the amount of pores.
  • the DBP absorption amount JIS K 6221
  • BET method It is preferable to measure JIS K 6217
  • Dyes can also be used as colorants.
  • a dye for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, xanthene dyes, triarylmethane dyes
  • Other dyes such as coumarin dyes, trimethine dyes, anthraquinone dyes and the like can also be used.
  • the other dyes include oil-soluble dyes, acid dyes, dyes such as amine salts of acid dyes and sulfonamide derivatives of acid dyes, etc. Specifically, for example, Color Index (The Society of Dyers) and Colorists published as dyes, and various dyes described in Dyeing Notes (Color Dyeing Company).
  • Examples of the other dyes include C.I. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow will be omitted and only the number will be described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 And C. I. Solvent red 45, 49, 125, 130; C.I. I. Solvent orange 2, 7, 11, 15, 26, 56; I. Solvent dyes,
  • a pigment in that the light resistance, weather resistance and fastness of the finally obtained cured film are excellent, but in order to adjust the hue, if necessary
  • the pigment may be used in combination with a dye.
  • the ratio by weight of the pigment to the dye is preferably 1:99 to 99: 1, more preferably 99: 1 to 40:60, and still more preferably 95: 5 to 60:40.
  • the content ratio of the coloring agent in the color resist composition is preferably 1% by mass or more, more preferably 5 to 80% by mass, and still more preferably 5 to 70% by mass in the total solid content. More preferably, it is in the range.
  • the content ratio of the colorant in the color resist composition is the total solid
  • the content 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 ratio of the colorant in the color resist composition is preferably in the range of 20 to 80% by mass in the total solid content. More preferably, it is in the range of 30 to 70% by mass.
  • the organic pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like having an acidic group or a basic group introduced, graft treatment to a pigment surface with a polymer compound or the like, sulfuric acid atomization method, if necessary.
  • the fine particles may be subjected to atomization treatment by an organic solvent or the like, washing treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like.
  • the particle size is preferably uniform, and the organic pigment having a uniform particle size can be obtained, for example, by containing a pigment dispersant and performing dispersion treatment.
  • the amount thereof used is preferably 1 part by mass or less, and more preferably 0.05 parts by mass or more and 0.5 parts by mass or less, per 1 part by mass of the pigment.
  • the amount of the pigment dispersant used is in this range, a pigment dispersion liquid in a uniform dispersion state (dispersed in an organic solvent) tends to be obtained, which is preferable.
  • the pigment dispersant examples include surfactants; pigment intermediates or derivatives; dye intermediates or derivatives; resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, acrylic resins, etc. .
  • resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, acrylic resins, etc.
  • graft copolymers having a nitrogen atom, acrylic block copolymers having a nitrogen atom, a urethane resin dispersant and the like are preferable. Since these dispersants have a nitrogen atom, the nitrogen atom has an affinity for the pigment surface, and the part other than the nitrogen atom improves the affinity for the medium, whereby the dispersion stability is improved.
  • These dispersants may be used alone or in combination of two or more.
  • Acetic-acid ester solvents such as a propylene glycol monomethyl ether acetate and a propylene glycol monoethyl ether acetate
  • Propionate solvents such as an ethoxy propionate
  • Aromatic solvents such as xylene and methoxybenzene
  • Ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether
  • Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • Aliphatic carbonization such as hexane Hydrogen based solvents
  • Nitrogen compound based solvents such as N, N-dimethylformamide, ⁇ -butyrolactam, N-methyl-2-pyrrolidone, etc .
  • Examples of the method of preparing the pigment dispersion include a method of subjecting a colorant to a kneading and dispersing step and a fine dispersing step, and a method of performing only the fine dispersing step.
  • the coloring agent, a part of the alkali-soluble resin, and, if necessary, the dispersing agent are mixed and kneaded.
  • the machine used for kneading includes two-roll, three-roll, ball mill, tron mill, disper, kneader, co-kneader, homogenizer, blender, single- or twin-screw extruder, etc.
  • the colorant can be dispersed by dispersing while applying a force.
  • the fine dispersion step a composition obtained by adding a solvent to the composition containing the colorant obtained in the kneading and dispersion step, or a colorant, an alkali-soluble resin, a solvent and, if necessary, the dispersant is mixed.
  • the particles of the colorant can be dispersed to a minute state close to that of the primary particles by mixing and dispersing the particles with a dispersion medium of fine particles of glass, zirconia or ceramic using a dispersing machine.
  • the average particle diameter of the primary particles of the colorant is preferably 10 to 100 nm, and more preferably 10 to 60 nm.
  • the average particle size of the coloring agent is measured by a dynamic light scattering type particle size distribution analyzer.
  • Nanotrac Nanotrac particle size distribution measuring apparatus "UPA-EX150” manufactured by Nikkiso Co., Ltd., " It can be measured by UPA-EX 250 "or the like.
  • the resist composition may contain a photopolymerization initiator.
  • a biimidazole compound an alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, and an oxime compound are preferable, for example.
  • a cationic photopolymerization initiator for example, one composed of an onium cation and an anion derived from a Lewis acid
  • oxime compounds are preferable in terms of sensitivity.
  • biimidazole compounds examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A Nos.
  • 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5, 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole can be mentioned.
  • alkylphenone compound examples include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl)- 2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl ketone Oligomers of -1- (4-isopropenylphenyl) propan-1-one, etc.
  • triazine compounds examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-). Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy) Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethyl
  • acyl phosphine oxide initiator examples include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide and the like.
  • a commercial product such as Irgacure 819 (manufactured by Ciba Japan) may be used.
  • Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one.
  • N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine N-acetoxy-1- [9-ethyl -6- ⁇ 2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl ⁇ -9H-carbazol-3-yl] ethane-1-imine and the like.
  • a polymerization initiator having a group capable of causing chain transfer a photopolymerization initiator described in JP-A-2002-544205 may be used.
  • a polymerization initiator which has the group which can raise said chain transfer the compound of a following formula, etc. are mentioned, for example.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′- Benzophenone compounds such as methyl diphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl And quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. It is preferable to use these in combination with the below-mentioned polymerization
  • the resist composition may further contain a polymerization initiator.
  • the polymerization initiator is a compound or a sensitizer used in combination with the photopolymerization initiator to accelerate the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator.
  • an amine compound, a thiazoline compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound etc. are mentioned, for example.
  • the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -Dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly called Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis Examples thereof include (ethylmethylamino) benzophenone and
  • alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10 And -dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.
  • thioxanthone compound examples include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone and the like.
  • carboxylic acid compound examples include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl Acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.
  • the resist composition may further contain a polyfunctional thiol compound.
  • This polyfunctional thiol compound is a compound having two or more sulfanyl groups in the molecule. Among them, a compound having two or more sulfanyl groups adjacent to an aliphatic hydrocarbon group is preferable because a pattern can be formed with high sensitivity.
  • the solvent contained in the resist composition is not particularly limited, and solvents commonly used in the relevant field can be used.
  • solvents commonly used in the relevant field can be used.
  • ester solvents solvents containing -COO-
  • ether solvents other than ester solvents solvents containing -O-
  • ether ester solvents solvents containing -COO- and -O-
  • ketones other than ester solvents It can be selected from solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.
  • ester solvent examples include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate And butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, ⁇ -butyrolactone and the like.
  • ether solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.
  • ether ester solvent examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionate Acid methyl, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol monopropyl ether a
  • ketone solvent examples include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and cyclopentanone.
  • examples include cyclohexanone and isophorone.
  • alcohol solvent examples include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
  • aromatic hydrocarbon solvent examples include benzene, toluene, xylene, mesitylene and the like.
  • amide solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
  • an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm is preferable from the viewpoint of coating property and drying property.
  • propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.
  • the content of the solvent is preferably 60 to 95% by mass, more preferably 70 to 90% by mass, based on the resist composition.
  • the solid content of the resist composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.
  • surfactant other than fluorine-containing active energy ray curable resin (I) in the range which does not impair the effect of this invention.
  • the surfactant include silicone surfactants, fluorine surfactants, silicone surfactants having a fluorine atom, surfactants having a fluorine atom and an ethylenically unsaturated bond, and the like.
  • the resist composition may, if necessary, contain various additives such as a filler, an adhesion promoter, an antioxidant, a UV absorber, an aggregation inhibitor, an organic amine compound, a curing agent and the like.
  • microparticles such as glass and an alumina, are mentioned, for example.
  • adhesion promoter examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.
  • antioxidants examples include 4,4′-thio-bis (6-tert-butyl-3-methylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl- 4-hydroxyphenyl) propionate], 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl- -Methylphenol, 2,6-di-tert-butyl-4-ethyl
  • UV absorbers examples include benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole; 2-hydroxy-4-octyloxybenzophenone and the like Benzophenone series; benzoate series such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3,5-triazine And triazines such as -2-yl) -5-hexyloxyphenol.
  • benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole
  • benzoate series such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate
  • anticoagulation agent examples include sodium polyacrylate and the like.
  • the organic amine compound By the addition of the organic amine compound, a residue can not be generated on the substrate of the unexposed area during development, and a pixel with excellent adhesion to the substrate can be provided.
  • the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine and n-octyl Monoalkyl amines such as amines, n-nonyl amines, n-decyl amines, n-undecyl amines, n-dodecyl amines;
  • Monocycloalkyl amines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n -Dialkylamines such as propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine and di-n-hexylamine;
  • Monoalkyl monocycloalkyl amines such as methylcyclohexylamine and ethylcyclohexylamine; Dicycloalkylamines such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldialkylamine -N-propylamine, ethyl di-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n- Trialkylamines such as pentylamine, tri-n-hexylamine;
  • Dialkyl monocycloalkyl amines such as dimethylcyclohexylamine and diethylcyclohexylamine; monoalkyl dicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine; 2-aminoethanol, 3-amino-1-propanol, Monoalkanolamines such as 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, etc .; mono such as 4-amino-1-cyclohexanol Cycloalkanolamines; diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexene Dialkanolamines
  • Dicycloalkanolamines such as di (4-cyclohexanol) amine; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri n-butanolamine, triisobutanolamine, tri-n-pentanolamine, Trialkanolamines such as tri-n-hexanolamine; Tricycloalkanolamines such as tri (4-cyclohexanol) amine; 3-amino-1,2-propanediol, 2-amino-1,3-propanediol , 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino 1,3-propanediol, 2-diethyl ester Amino alkane dio
  • Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, etc .; amino-containing cyclos such as 1-aminocyclopentanonemethanol, 4-aminocyclopentanonemethanol Alkanone methanols; amino group-containing cyclopentanone such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol, etc.
  • Alkanemethanols ⁇ -alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5- Mino valeric acid, 6-aminocaproic acid, 1-amino cyclopropane carboxylic acid, 1-amino-cyclohexanecarboxylic acid, 4-amino carboxylic acids such as amino cyclohexanecarboxylic acid;
  • Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p Aminobenzyl alcohols such as -aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p-aminophenol,
  • crosslink an alkali-soluble resin by being heated are mentioned, for example.
  • polymerize alone and can produce a cured film is also mentioned.
  • an epoxy compound, an oxetane compound etc. are mentioned, for example.
  • epoxy compound examples include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resin, and fat.
  • Epoxy resins such as cyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils, brominated derivatives of these epoxy resins, fats other than epoxy resins and their brominated derivatives Group, alicyclic or aromatic epoxy compounds, epoxy compounds of (co) polymer of butadiene, epoxy compounds of (co) polymer of isoprene, (co) polymer of glycidyl (meth) acrylate, triglycidyl isocyanurate Etc.
  • oxetane compounds include carbonate bisoxetane, xylylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexanedicarboxylate bisoxetane.
  • an epoxy compound, an oxetane compound or the like When an epoxy compound, an oxetane compound or the like is contained as a curing agent, the epoxy group of the epoxy compound or a compound capable of ring-opening polymerization of the oxetane skeleton of the oxetane compound may be included.
  • the compound include polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, acid generators and the like.
  • polyvalent carboxylic acids examples include phthalic acid, 3,4-dimethyl phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and the like.
  • Aromatic polyvalent carboxylic acids such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acid; succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, Aliphatic polyhydric carboxylic acids such as itaconic acid;
  • polyvalent carboxylic acid anhydrides examples include aromatic polyvalent acids such as phthalic acid anhydride, pyromellitic acid anhydride, trimellitic acid anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, etc.
  • Polyvalent carboxylic acid anhydrides hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentane tricarboxylic acid anhydride, 1,2,4-cyclohexane tricarboxylic acid anhydride, Cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, hymic acid anhydride, Alicyclic polycarboxylic acid anhydrides, such as water familiar acid, ethylene glycol bis trimellitate acid, an ester group-containing carboxylic acid anhydrides such as glycerin tris trimellitate anhydride.
  • curing agent examples include Adeka Hardener EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.) and Rikasid HH and MH-700 (all manufactured by Shin Nippon Rika Co., Ltd.) under the trade names.
  • Adeka Hardener EH-700 manufactured by Asahi Denka Kogyo Co., Ltd.
  • Rikasid HH and MH-700 all manufactured by Shin Nippon Rika Co., Ltd.
  • the above curing agents may be used alone or in combination of two or more.
  • the resist composition may also contain an organic acid having a molecular weight of 1,000 or less.
  • organic acids include the organic acids disclosed in JP-A-5-343631. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid, Methacrylic acid is mentioned, Preferably malonic acid, oxalic acid, fumaric acid and phthalic acid are mentioned.
  • the content of the fluorine-containing active energy ray-curable resin (I) in the resist composition varies depending on the type of the resist composition, the coating method, the target film thickness, etc.
  • the content is preferably 0.0001 to 10 parts by mass, more preferably 0.00001 to 5 parts by mass, and still more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the solid content in the resist composition.
  • the coating method of the resist composition varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, screen printing, spray An applicator, a bar coater, a coating method using electrostatic coating or the like, or a molding method using various molds can be mentioned.
  • the resist composition described above is such that physical properties such as solubility, viscosity, transparency, refractive index, conductivity and ion permeability of the resin are changed by irradiation with light such as visible light and ultraviolet light.
  • resist compositions photoresist compositions, color resist compositions for color filters, etc.
  • a resist composition is applied by spin coating or slit coating on a silicon wafer or a glass substrate on which various metals are vapor-deposited so as to have a thickness of about 0.01 to 5 ⁇ m. Is common.
  • variation of a coating film thickness may become a fall of quality of a semiconductor or a liquid crystal element, or a defect
  • fluorine-containing active energy ray curable resin (I) of this invention as an additive of this composition. Since a uniform coating film can be formed by the high leveling property, productivity improvement of a semiconductor and a liquid crystal element, high functionalization, etc. are attained.
  • the fluorine-containing active energy ray curable resin (I) of the present invention can be suitably used as a liquid repellent.
  • a liquid repellent it is preferable to use for the negative resist composition (photosensitive resin composition) which has the above-mentioned alkali-soluble resin as a main component, and the present invention is used for the whole solid content in the composition.
  • the fluorine-containing active energy ray curable resin (I) is preferably used in an amount of 0.01 to 5.0% by mass.
  • a negative resist composition comprising the above-mentioned fluorine-containing active energy ray curable resin (I) as a liquid repellent agent is coated on the surface of a substrate, exposed and developed, whereby a cured film having a pattern can be obtained.
  • This pattern is also referred to as a partition wall, and the fluorine-containing active energy ray curable resin (I) of the present invention is segregated and cured on the upper part thereof to exhibit ink repellency and to be used in the IJ method.
  • the ink can be uniformly applied in the area surrounded by the partition, and the ink is prevented from being injected into the area beyond the partition and not desired, and the ink has a desired pattern Can print well.
  • the optical element printed by the IJ method using the partition wall can be suitably used as an organic EL blocking, a color filter of a liquid crystal element, an organic TFT array element or the like.
  • Example 1 Production of Fluorine-Containing Active Energy Ray-Curable Resin (Ii)
  • the compound (1) a perx having hydroxyl groups at both ends represented by the following formula Fluoropolyether compound (hereinafter referred to as "the compound (1).
  • Hydroxy group equivalent is 740 g / eq. Repeating number a is 5 and b is 7) 50 parts, epichlorohydrin 62.5 parts Stirring was then started under a nitrogen stream, and 8.3 parts of a 49% aqueous solution of sodium hydroxide was added dropwise over 2 hours while maintaining the temperature in the flask at 50 ° C. After heating to 60 ° C. and stirring for 3 hours, the temperature was returned to room temperature.
  • reaction solution returned to room temperature was washed with ion exchange water.
  • the washing was carried out by repeating twice the operation of adding 50 parts of ion-exchanged water to the reaction solution and stirring, leaving the mixture to stand and separating the aqueous layer by liquid separation.
  • unreacted epichlorohydrin is distilled off by distillation under reduced pressure, filtered and taken out, and a poly (perfluoroalkylene ether) chain represented by the following formula (a1-1)
  • compound (a1-1) 52.2 parts of a compound having an epoxy group at both ends thereof.
  • This compound (a1-1) is a transparent liquid and has an epoxy equivalent of 1,112 g / eq.
  • the average value of the number n of repeating units in the following compound (a1-1) was 0.4.
  • the reaction was carried out by warming and further stirring for 2 hours, and as a result, the disappearance of the absorption peak near 2360 cm -1 derived from the isocyanate group was confirmed by IR spectrum measurement.
  • PGMEA was added to obtain a PGMEA solution containing 10% of a fluorine-containing active energy ray curable resin (1-i).
  • Example 2 Production of fluorine-containing active energy ray-curable resin (2-i)
  • a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, represented by the same formula as the compound (1) 50 parts of a compound (3) having a hydroxyl group equivalent of 754 g / eq, where a is 5 and b is 7, and 6.5 parts of maleic anhydride are charged.
  • Stirring was then started under a nitrogen stream, and the temperature in the flask was raised to 160 ° C. and stirred for 1 hour. Thereafter, 0.01 part of dibutyltin dilaurate as an esterification catalyst was added, and the temperature in the flask was raised to 170 ° C.
  • compound (a5-1) a compound having a poly (perfluoroalkylene ether) chain represented by the following formula (a5-1) and a carboxy group at both ends thereof (hereinafter referred to as “compound (a5-1)”) I obtained 56.5 parts.
  • the compound (a5-1) was a transparent liquid and had an acid value of 64.0 mg KOH / g.
  • the reaction was carried out by warming and further stirring for 2 hours, and as a result, the disappearance of the absorption peak near 2360 cm -1 derived from the isocyanate group was confirmed by IR spectrum measurement.
  • PGMEA was added to obtain a PGMEA solution containing 10% of a fluorine-containing active energy ray curable resin (1-ii).
  • Example 4 Production of fluorine-containing active energy ray curable resin (1-iii) In a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, 51.4 parts of a compound (a1-1) and 1, 1 Charge 15.2 parts of 6-naphthalenediglycidyl ether, 12.2 parts of 1,6-naphthalenediol, and 1000 ppm of tetrabutylphosphonium hydroxide (TBPH), and heat at 150 ° C. for 40 hours to obtain a compound of Mw 27,000 (6 Got).
  • TBPH tetrabutylphosphonium hydroxide
  • the reaction was carried out by warming and further stirring for 2 hours, and as a result, the disappearance of the absorption peak near 2360 cm -1 derived from the isocyanate group was confirmed by IR spectrum measurement.
  • PGMEA was added to obtain a PGMEA solution containing 10% of a fluorine-containing active energy ray curable resin (1-iii).
  • Comparative synthesis example 1 20 parts of the compound (a1-1-1), 20 parts of diisopropyl ether as a solvent, 0.02 parts of p-methoxyphenol as a polymerization inhibitor, and a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device
  • a neutralizing agent 3.1 parts by mass of triethylamine was charged, stirring was started under an air stream, and 2.7 parts by mass of acrylic acid chloride was dropped over 1 hour while maintaining the inside of the flask at 10 ° C. After completion of the dropwise addition, the mixture is stirred at 10 ° C. for 1 hour, heated and stirred at 30 ° C. for 1 hour, heated to 50 ° C.
  • a is 5 on average and b is 8 on average.
  • the oxyperfluoromethylene units and the oxyperfluoroethylene units are random bonds.
  • the reaction was started, and 44.8 parts of 2-acryloyloxyethyl acrylate was added dropwise over 1 hour while maintaining 60.degree. After completion of the dropwise addition, the reaction mixture was stirred at 60 ° C. for 1 hour and then heated to 80 ° C. and stirred for 10 hours. As a result, absorption spectrum near 2360 cm -1 due to isocyanate group was lost by IR spectrum measurement. confirmed. Subsequently, 37.4 parts of methyl ethyl ketone was added as a solvent to obtain 224.6 parts of a methyl ethyl ketone solution containing 50% of a polymerizable fluorine-based compound.
  • the dried coating film was cured by being irradiated with ultraviolet light (UV) using an ultraviolet curing device (in an air atmosphere, a high pressure mercury lamp, an ultraviolet irradiation amount of 0.5 kJ / m 2). Further, heat treatment was carried out at 230 ° C. for 20 minutes to prepare coating films as Examples 6 to 10 and Comparative Example 1.
  • a coating film of Comparative Example 2 was produced in the same manner as Comparative Example 1 except that the fluorine-based surfactant was not used.

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Abstract

L'invention concerne une résine fluorée qui peut durcir par un rayonnement à énergie active, qui présente une structure de résine qui permet un ajustement aisé de la teneur en atomes de fluor, et qui présente d'excellentes propriétés de ségrégation en surface, tout en présentant des propriétés suffisantes d'étalement, hydrofuges et oléofuges, d'imperméabilisation et autres, même si la quantité utilisée en est petite ; un agent d'imperméabilisation ; une composition de résine qui contient cette résine fluorée pouvant durcir par un rayonnement à énergie active ; un film durci. Plus précisément, l'invention porte sur une résine fluorée qui peut durcir par un rayonnement à énergie active, qui comprend, dans chaque molécule, un résidu d'une chaîne alkylène (A), dont les groupes hydroxyle se trouvent aux deux extrémités, et dont au moins un atome d'hydrogène est substitué par un atome de fluor, et un résidu d'un composé divalent contenant un groupe hydroxyle phénolique (B) autre que le composant (A) et/ou un résidu d'un acide dicarboxylique (C), et qui possède un motif structural dans lequel les constituants décrits ci-dessus sont liés au moyen d'un groupe de liaison représenté par la formule (1) (dans laquelle X représente un atome d'hydrogène, un groupe organique (x1) ayant un groupe polymérisable ou un groupe organique (x2) ayant un groupe acide. Cette résine fluorée pouvant durcir par un rayonnement à énergie active est également configurée de sorte qu'au moins un groupe de liaison contenu dans chaque molécule, ledit groupe de liaison étant représenté par la formule décrite (1) ci-dessus, est un groupe organique monovalent (x1) ayant un groupe polymérisable.
PCT/JP2018/039639 2017-11-29 2018-10-25 Résine fluorée pouvant durcir par un rayonnement à énergie active, agent d'imperméabilisation, composition de résine le contenant et film durci WO2019107026A1 (fr)

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CN201880077226.8A CN111417669B (zh) 2017-11-29 2018-10-25 含氟活性能量射线固化性树脂、拒液剂、包含其的树脂组合物及固化膜
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