WO2006112234A1 - Composition de resine, pellicule durcie et produit stratifie - Google Patents

Composition de resine, pellicule durcie et produit stratifie Download PDF

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Publication number
WO2006112234A1
WO2006112234A1 PCT/JP2006/305869 JP2006305869W WO2006112234A1 WO 2006112234 A1 WO2006112234 A1 WO 2006112234A1 JP 2006305869 W JP2006305869 W JP 2006305869W WO 2006112234 A1 WO2006112234 A1 WO 2006112234A1
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group
meth
curable resin
resin composition
compound
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PCT/JP2006/305869
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English (en)
Japanese (ja)
Inventor
Takaro Yashiro
Mitsunobu Doimoto
Kensuke Miyao
Yasuharu Yamada
Takahiro Kawai
Hideaki Takase
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Jsr Corporation
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Priority to JP2007521151A priority Critical patent/JP5125507B2/ja
Publication of WO2006112234A1 publication Critical patent/WO2006112234A1/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
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a curable resin composition and a cured film comprising the same, and in particular, for example, a cured film having a multilayer structure of two or more layers such as a low refractive index layer and a high refractive index layer is applied as a single coating.
  • the present invention relates to a curable resin composition that can be formed from a film and a cured film comprising the same.
  • an antireflection film including a low refractive index layer that has a cured product having excellent durability in order to remove attached fingerprints, dust, and the like, the surface is often wiped with gauze impregnated with ethanol or the like, and scratch resistance is required.
  • the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate.
  • triacetyl cellulose is used as the base material.
  • an alkali is usually used in order to increase the adhesion when pasted to the polarizing plate. It is necessary to perform kenning with an aqueous solution. Therefore, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in durability.
  • a fluorine-based resin coating containing a hydroxyl group-containing fluorine-containing polymer is known.
  • Patent Document 1 Patent Document 2, Patent Document 3, and the like It is disclosed.
  • a curing agent such as melamine coffin
  • the curing time becomes excessively long and the types of base materials that can be used are limited.
  • the obtained coating film has a problem that it is excellent in weather resistance but poor in scratch resistance and durability.
  • Patent Document 4 discloses that at least one isocyanate is used.
  • An isocyanate group-containing unsaturated compound having an acrylate group and at least one addition-polymerizable unsaturated group and a hydroxyl group-containing fluoropolymer have a ratio of the number of isocyanate groups to the number of hydroxyl groups of 0.01 to 1.0.
  • a coating composition containing an unsaturated group-containing fluorine-containing polymer obtained by reacting at a ratio of
  • Patent Document 1 Japanese Patent Application Laid-Open No. 57-34107
  • Patent Document 2 Japanese Patent Application Laid-Open No. 59-189108
  • Patent Document 3 Japanese Patent Application Laid-Open No. 60-67518
  • Patent Document 4 Japanese Patent Publication No. 6-35559
  • the present invention was made against the background described above, and its purpose is to efficiently produce a low refractive index layer and a high refractive index layer, and a curable resin composition that can be cured by ultraviolet rays. To provide things. Another object of the present invention is to provide a cured film having excellent scratch resistance with high adhesion to a substrate having high transparency and excellent environmental resistance.
  • the present inventors have intensively studied, blending a polymerizable group-containing organic compound having a high refractive index with a polymerizable group-containing fluoropolymer that is cured by irradiation with ultraviolet rays,
  • a composition in which a specific organic solvent is combined is applied to a substrate and the solvent is evaporated, a layer containing a high concentration of fluoropolymer and a high refractive index polymerizable group-containing organic compound are obtained. It has been found that it is separated into two or more layers with a layer present at a high concentration.
  • silica particles when silica particles are blended into this composition, silica particles are present in a high density in a layer containing a high concentration of fluoropolymer, and high refractive index polymerizable group-containing organic compounds are present in a high concentration. It was found that the layer does not exist substantially.
  • the cured films obtained by curing these compositions by irradiating them with ultraviolet rays were confirmed to have low reflection, excellent scratch resistance, chemical resistance, antifouling properties and transparency, and completed the present invention. .
  • the following curable resin composition, a cured film and a laminate thereof are provided.
  • (C) one or more organic solvents selected from the group consisting of ketones and esters, and the group group consisting of the above-mentioned (C) ketones and esters A curable resin composition in which the ratio of one or more organic solvents selected from the above is 30% by mass or more.
  • the fluorine-containing polymer having a polymerizable group (A) is a compound (A-1) having one isocyanate group and one or more ethylenically unsaturated groups, and a fluorine-containing polymer having a hydroxyl group.
  • R 1 represents a fluorine atom, a fluoroalkyl group, or a group represented by OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group, (CH 3) —OR 5
  • R 5 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbo group
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a hydroxyalkyl group
  • a represents a number of 0 or 1
  • the fluoropolymer (A-2) having a hydroxyl group is derived from an azo group-containing polydimethylsiloxane compound with respect to a total of 100 mol parts of the structural units (a) to (c).
  • the following structural unit (d) The curable resin composition according to the above [3], comprising 0.1 to 10 mole parts.
  • R 8 and R 9 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]
  • R 1Q to R 13 represent a hydrogen atom, an alkyl group, or a cyano group
  • R ′′ to R 17 represent a hydrogen atom or an alkyl group
  • b and f are numbers 1 to 6
  • c e Is a number from 0 to 6
  • d is a number from 1 to 200.
  • the fluorine-containing polymer (A-2) having a hydroxyl group has the following structural unit (f) 0 with respect to 100 mol parts of the total of the structural units (a) to (c).
  • R ia represents a group having an emulsifying action.
  • the above-mentioned compound (A-1) having one isocyanato group and one or more ethylenically unsaturated groups is 2- (meth) ataloyloxetyl isocyanate [2] ⁇ V of [6], the curable resin composition according to any one of the above.
  • the organic compound (B) having a polymerizable group is characterized by having one or more of the following structural units (g) to (i) as a repeating unit.
  • the curable resin composition according to any one of [1] to [8] above.
  • X represents a hydrogen atom or a halogen atom (excluding fluorine).
  • the organic compound having a polymerizable group (B) is represented by the following structural formulas (j) to (! N), and any one of the structural units (g) to (i) or 2
  • R 19 represents a methyl group or a hydrogen atom
  • R 2 represents an alkyl group or a hydrogen atom having 3 or less carbon atoms
  • X represents a hydrogen atom or a halogen atom (excluding fluorine).
  • R represents a methyl group or a hydrogen atom, represents an alkyl group having 3 or less carbon atoms or a hydrogen atom.
  • R 24 is a methyl group or a hydrogen atom
  • X is a hydrogen atom or a halogen atom (excluding fluorine) .
  • [0016] [18] A cured film obtained by curing the curable resin composition according to any one of [1] to [17] and having a multilayer structure of two or more layers. [19] One or more layers made of a cured product mainly composed of (A) a fluoropolymer having a polymerizable group, and (B) a refractive index after curing having a polymerizable group of 1
  • the cured film according to the above-mentioned [18] which has a layer structure of two or more layers composed of one or more layers having a cured product strength mainly composed of an organic compound of 55 or more.
  • the curable resin composition of the present invention can form a cured film having a multilayer structure of any two or more layers, such as a low refractive index layer and a high refractive index layer, from one coating film. Therefore, the manufacturing process of the cured film having a multilayer structure can be simplified.
  • the curable resin composition of the present invention does not undergo a curing reaction by heat, it can be cured in a short time and can provide a cured film excellent in productivity.
  • the curable resin composition of the present invention can be used particularly advantageously for the formation of optical materials such as an antireflection film and a selective transmission film filter, and also utilizes the high fluorine content.
  • it can be suitably used as a paint material, a weather resistant film material, a coating material, and the like for a substrate requiring weather resistance.
  • the cured film since the cured film has excellent adhesion to the base material and provides a good antireflection effect with high scratch resistance, it is extremely useful as an antireflection film and can be applied to various display devices. By doing so, the visibility can be improved.
  • FIG. 1 shows a schematic diagram of an antireflection film laminate comprising a cured film formed from the curable resin composition of the present invention.
  • FIG. 2 is a schematic view of an antireflection film laminate including a cured film formed from the curable resin composition of the present invention containing silica particles.
  • FIG. 3 is an electron micrograph showing a typical two-layer separation state of the cured film of the present invention.
  • FIG. 4 is an electron micrograph showing a typical two-layer separation state of the cured film of the present invention containing silica particles.
  • the curable resin composition of the present invention is
  • the component (A) of the present invention is a fluoropolymer having a polymerizable group (hereinafter sometimes referred to as “polymerizable group-containing fluoropolymer”).
  • the polymerizable group is not particularly limited, and examples thereof include an epoxy group, a bur group, and a (meth) atalyloyl group, and among them, a (meth) atallyloyl group is preferable.
  • the polymerizable group-containing fluoropolymer (A) comprises a compound (A-1) having one isocyanate group and one or more ethylenically unsaturated groups, and a fluoropolymer having a hydroxyl group ( A product obtained by reacting with A-2) and obtained by reacting isocyanate group Z hydroxyl group at a ratio of 1.1 to 1.9 is preferable.
  • (A-1) Compound having one isocyanate group and one or more ethylenically unsaturated groups
  • compound (A-1) one isocyanate group and one or more are present in the molecule. If it is a compound which has this polymeric group, it will not restrict
  • a (meth) atallyloyl group is more preferable because the curable resin composition of the present invention can be more easily cured. Examples of such a compound include 2- (meth) atalylooxychetyl isocyanate and 2- (meth) atalylooxypropylisocyanate alone or in combination of two or more.
  • the compound (A-1) can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
  • diisocyanates include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3 xylylene diisocyanate, 1,4 xylylene diisocyanate, 1,5 naphthalene diisocyanate , M phenylene diisocyanate, p-phenol-diisocyanate, 3, 3, 1-dimethyl-4, 4, di-dimethane-dimethane diisocyanate, 4, 4'-diphenylmethane diisocyanate, 3, 3, 1-dimethylphenol-diisocyanate, 4, 4, -biphenyl-diisocyanate, 1, 6 hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), 2, 2
  • Xan is particularly preferred.
  • Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, force prolatatone (meth) acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta (meth) ) Atalylate, pentaerythritol tri (meth) atrelate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid EO modified One kind alone or a combination of two or more kinds such as di (meth) acrylate is included.
  • 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferred.
  • examples of commercially available hydroxyl group-containing polyfunctional (meth) atalylate include, for example, Osaka Organic Chemical Co., Ltd., trade name HEA, Nippon Kayaku Co., Ltd., trade name KAYAR AD DPHA, PET-30, Toagosei Product name Alonics M-215, M-233, M-305, M-400, etc.
  • the amount of the hydroxyl group-containing polyfunctional (meth) acrylate is added to 1 to 1.2 mol with respect to 1 mol of diisocyanate. preferable.
  • the hydroxyl group-containing fluoropolymer (A-2) is preferably composed of the following structural units (a), (b), and (c), and further includes structural units (d) and (f). Is more preferable.
  • the structural unit (a) is represented by the following general formula (1).
  • R 1 represents a fluorine atom, a fluoroalkyl group, or a group represented by OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • the fluoroalkyl group of R 1 and R 2 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoro mouth.
  • examples thereof include fluorinated alkyl groups having 1 to 6 carbon atoms such as xyl group and perfluorocyclohexyl group.
  • the alkyl group of R 2 includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group. Is mentioned.
  • the structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component.
  • a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluoro oral ether or alkoxyalkyl perfluorobule.
  • Perfluoro (alkyl butyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butinolevino reetenole), perfluoro (isobutino vinyl ether), etc.
  • a single perfluoro (alkoxyalkyl butyl ether) such as perfluoro (propoxypropyl butyl ether) or a combination of two or more thereof.
  • hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl butyl ether) are more preferable, and it is more preferable to use these in combination.
  • the content of the structural unit (a) is 20 to 70 when the total of the structural units (a) to (c) of the hydroxyl group-containing fluoropolymer (A-2) is 100 mol%. Mol%. If the content of the structural unit (a) is less than 20 mol%, it is difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present application, while the content exceeds 70 mol%. In addition, the solubility of the hydroxyl group-containing fluoropolymer (A-2) in an organic solvent, transparency, or adhesion to a substrate may be reduced.
  • the content of the structural unit (a) is 25 to 65 mol% with respect to the total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer (A-2). More preferably, it is more preferably 30 to 60 mol%.
  • the structural unit (b) is represented by the following general formula (2).
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group, (CH 3) —OR 5 or
  • a group represented by OCOR 5 (R 5 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbo group]
  • the alkyl group of R 4 or R 5 includes carbon such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, lauryl group, etc. Examples thereof include alkyl groups of 1 to 12, and examples of the alkoxycarbonyl group include a methoxycarbon group and an ethoxycarbonyl group.
  • the structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component.
  • bur monomers include methyl vinyl ethere, ethino levinino le ethere, n propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl vinyl ether, tert- Butyl vinyl etherenole, n-pentinolevinoreethenore, n-hexenolevinoreethenore, n-year-old cutinorebi-noreethenore, n-dodecinolevinorenotere, 2-ethenorehexinolevenoreate, cyclohexyl vinyl ether, etc.
  • the content of the structural unit (b), hydroxyl group-containing fluoropolymer sum of (A- 2) Unit configuration of (a) ⁇ (c) is 100 mol 0/0, 10 it is a 70 mole 0/0.
  • the hydroxyl group-containing fluoropolymer (A-2) becomes an organic solvent.
  • the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer (A-2) may deteriorate. There is.
  • the content of the structural unit (b) is 20 to 60 mol with respect to the total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer (A-2). More preferably, it is 30 to 60 mol%.
  • the structural unit (c) is represented by the following general formula (3).
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a hydroxyalkyl group
  • a represents a number of 0 or 1
  • hydroxyalkyl group of R 7 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, Examples include 5-hydroxypentyl group and 6-hydroxyhexyl group.
  • the structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component.
  • hydroxyl-containing butyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl.
  • Hydroxyl-containing butyl ethers such as vinyl ether, 6-hydroxyhexyl vinyl ether, etc.
  • hydroxyl-containing butyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, allyl alcohol, etc. Can be mentioned.
  • hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and proprolacton.
  • (Meth) acrylate, polypropylene glycol (meth) acrylate, etc. can be used.
  • the content of the structural unit (c) is determined by the structural unit (a) of the hydroxyl group-containing fluoropolymer (A-2).
  • the total of-(c) is 100 mol%, it is preferably 5-70 mol%. If the content rate is less than mol%, the solubility of the hydroxyl group-containing fluoropolymer (A-2) in an organic solvent may decrease. On the other hand, if the content rate exceeds 70 mol%, the hydroxyl group-containing fluorine-containing polymer is reduced. The optical properties such as transparency and low reflectivity of the base polymer (A-2) may deteriorate.
  • the content of the structural unit (c) is 5 to 40 mol with respect to the total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer (A-2). 0/0 more rather preferable is to, still more preferably from 5 to 30 mol%.
  • the hydroxyl group-containing fluoropolymer (A-2) preferably further comprises the following structural unit (d).
  • structural unit (d) will be described.
  • the structural unit (d) is represented by the following general formula (4).
  • R 8 and R 9 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]
  • the alkyl group represented by R 8 or R 9 is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group.
  • a methyl group such as a methyl group, an ethyl group, or a propyl group.
  • trifluoromethyl group such as perfluoroethyl group, perfluoropropyl group, perfluorobutyl group and the like.
  • a naphthyl group, and the like are examples of the alkyl group represented by R 8 or R 9 .
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the general formula (4).
  • azo group-containing polysiloxane compounds include compounds represented by the following general formula (15).
  • R 1Q to R 13 represent a hydrogen atom, an alkyl group, or a cyano group
  • R ′′ to R 17 represent a hydrogen atom or an alkyl group
  • b and f are numbers 1 to 6
  • c e Is a number from 0 to 6
  • d is a number from 1 to 200
  • m is a number from 1 to 20.
  • the structural unit (d) is the structural unit shown below.
  • the structural unit (e) is represented by the following general formula (5).
  • R 1G to R 13 , R ′′ to R 17 , b, c, d, e, and f are the same as those in the general formula (15).
  • alkyl group of R 1G to R 13 include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group, and R
  • Examples of the alkyl group of 14 to R 17 include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.
  • the azo group-containing polysiloxane compound represented by the general formula (15) is particularly preferably a compound represented by the following general formula (16). .
  • the content of the structural unit (d) depends on the structural unit of the hydroxyl group-containing fluoropolymer (A-2) (a ) To (c) is preferably 0.1 to 10 mole parts per 100 mole parts in total. When the content of the structural unit (d) is less than 0.1 mol part, the surface slipperiness of the cured coating film decreases and C ⁇ ⁇ I—
  • the scratch resistance of the coating film may be reduced.
  • the content exceeds 10 parts by mole
  • the group-containing fluorine-containing polymer (A-2) is inferior in transparency, and when used as a coating material, repelling and the like are likely to occur during coating.
  • the content of the structural unit (d) is set to 0. 0 with respect to a total of 100 mole parts of the structural units (a) to (c) of the hydroxyl group-containing fluoropolymer (A-2). It is more preferable to use 1 to 5 parts by mole. 0.1 to 3 parts by mole is even more preferable.
  • the content of the structural unit (e) is determined so that the content of the structural unit (d) contained therein falls within the above range.
  • the hydroxyl group-containing fluoropolymer (A-2) preferably further comprises the above structural unit (f).
  • the structural unit (f) will be described.
  • the structural unit (f) is represented by the following general formula (6).
  • the group having an emulsifying action of R 18 has both a hydrophobic group and a hydrophilic group, and the hydrophilic group is a polyether structure such as polyethylene oxide or polypropylene oxide. The group is preferred.
  • Examples of the group having such an emulsifying action include a group represented by the following general formula (17).
  • the structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component.
  • a reactive emulsifier include compounds represented by the following general formula (18).
  • the content of the structural unit (f) is 0.15 mol with respect to 100 mol parts in total of the structural units (a) to (c) of the hydroxyl group-containing fluoropolymer (A-2). Part.
  • the content of the structural unit (f) is less than 0.1 mol part, the effect of improving the solubility of the hydroxyl group-containing fluoropolymer (A-2) in the solvent is small, but the content exceeds 5 mol parts.
  • the tackiness of the curable resin composition increases excessively, making it difficult to handle, and when used as a coating material, the moisture resistance decreases.
  • the content of the structural unit (f) is set to 0.1 with respect to a total of 100 mole parts of the structural units (a) and (c) of the hydroxyl group-containing fluoropolymer (A-2). More preferred is 3 mole parts. 0.22 More preferred is 3 mole parts.
  • the hydroxyl group-containing fluoropolymer (A-2) has a polystyrene equivalent number average molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • it is 5,000 500,000.
  • the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer (A-2) may decrease, while the number average molecular weight is 500,000. This is because the viscosity of the curable resin composition of the present invention is increased, and thin film coating may be difficult.
  • the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer (A2) is 10,000 300,000. Further preferred.
  • the polymerizable group-containing fluoropolymer (A) used in the present invention includes the compound (A-1) containing one isocyanate group and one or more ethylenically unsaturated groups, as described above, It is preferably obtained by reacting the hydroxyl group-containing fluorine-containing polymer (A-2) with a molar ratio of isocyanate group Z hydroxyl group of 1.1 to 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be lowered.
  • the molar ratio of the isocyanate group Z hydroxyl group is more preferably 1.1 to 1.5, and even more preferably 1.2 to 1.5.
  • the content of the (A) polymerizable group-containing fluoropolymer in the curable resin composition of the present invention is usually 20 to 80% by mass with respect to 100% by mass of the total composition excluding the organic solvent. Is.
  • the reason for this is that when the content is less than 20% by mass, the above two-layer separation is insufficient and the reflectance of the hardened coating film becomes high, or a layer containing a high concentration of fluoropolymer becomes an antireflection film. This is because it is difficult to obtain an appropriate film thickness and a sufficient antireflection effect may not be obtained.
  • the two-layer separation described above becomes insufficient and the reflectance of the cured coating film becomes high, or the layer containing a high refractive index polymerizable compound at a high concentration prevents reflection.
  • the value of the component (A) it is more preferable to set the value of the component (A) in the range of 30 to 60% by mass, more preferably 30 to 70% by mass.
  • the organic compound having a polymerizable group used in the present invention is a polymerizable organic compound (hereinafter referred to as “high refractive index”) having a refractive index measured by an Abbe refractometer of a cured film cured by itself of 1.55 or more.
  • high refractive index a polymerizable organic compound having a refractive index measured by an Abbe refractometer of a cured film cured by itself of 1.55 or more.
  • a polymerizable group-containing organic compound (B) ”.
  • a vinyl group, a (meth) atalyloyl group, a cyclic ether group or the like that can be polymerized by a photo radical initiator or a photo acid generator can be used.
  • the (meth) atalyloyl group is most preferred!
  • benzyl (Meth) Atalylate N— (Meth) acryl morpholide, 1—Hydroxy— 3—Phenoxypropyl (Meth) acrylate, Pacamylyl phenol acrylate, 3— o—Phenol-phenol, —1— (Meth) Ataliloyl (1) 2-hydroxypropane and the like.
  • These commercial products include M-110, 5700 manufactured by Toa Gosei, Biscoat # 160, 192 ⁇ 220, manufactured by Osaka Organic Chemical Industry, PHE manufactured by Daiichi Kogyo, BZ, BZ-A, PO-A manufactured by Kyoeisha, M600, Nippon Kayaku R — 128H, Shin-Nakamura Igaku 401P, etc.
  • the polymerizable organic compound (B) is preferably a compound represented by the following structural formulas (10) to (13).
  • R 19 represents a methyl group or a hydrogen atom, represents an alkyl group or a hydrogen atom having 3 or less carbon atoms, and X represents a hydrogen atom or a halogen atom (excluding fluorine).
  • R represents an alkyl group having 3 or less carbon atoms, or a hydrogen atom.
  • R 4 represents a methyl group or a hydrogen atom
  • X represents a hydrogen atom or a halogen atom (excluding fluorine).
  • A-B PEF A-BPE-4, BPE-200, BPE-500 manufactured by Shin-Nakamura & Co., Ltd.
  • Biscoat 700 Showa Polymer VR60, 70, 90, V776, Sartoma I SR349, 348, 601, Nippon Kaiyaku Carrad R-551, 712, Toagosei M-208, 210, TO-904, TO-905, Kyoeisha BP-2EM, BR-MA, and the like.
  • component (B) Considering the hardness of the cured coating film, it is preferable to use these bifunctional or higher functional organic compounds containing a high refractive index polymerizable group as the component (B).
  • a small amount of a monofunctional high refractive index compound can improve the adhesion to the base substrate, and as a result, can improve the scratch resistance. Therefore, when the total amount of component (B) is 100% by mass, it is preferred that 50% by mass or more of a bifunctional or higher compound is used.
  • the bifunctional or higher bifunctional or higher refractive index polymerizable organic compound is less than 50% by mass in the component (B), sufficient hardness may not be obtained, and scratch resistance may deteriorate.
  • the content of the (B) high refractive index polymerizable group-containing organic compound in the curable resin composition of the present invention is usually 20 to 80% by mass with respect to 100% by mass of the total composition excluding the organic solvent. %. This is because when the content is less than 20% by mass, the above two-layer separation is insufficient and the reflectance of the cured coating film becomes high, or there is a layer in which a high refractive index polymerizable organic compound is present in a high concentration. This is because it is difficult to obtain a film thickness suitable as an antireflection film, and a sufficient antireflection effect may not be obtained, and the scratch resistance may be lowered.
  • the addition amount exceeds 80% by mass, the two-layer separation described above is insufficient and the reflectance of the cured coating film is increased, or the layer containing a high concentration of the low refractive index polymerizable fluoropolymer is reflected. It becomes difficult to obtain an appropriate film thickness for the anti-reflection film, and a sufficient anti-reflection effect cannot be obtained. Also, for these reasons, it is more preferable to set the added amount of the component (B) to 20 to 70% by mass, and it is more preferable to set the value within the range of 20 to 60% by mass.
  • the (C) organic solvent contained in the curable resin composition of the present invention is a highly soluble solvent with respect to the above (A) polymerizable group-containing fluoropolymer, and ketones or esters may be used. it can.
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone, methyl amylken, methyl propyl ketone, methyl acetate, ethyl acetate
  • esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl acetate, and propylene glycol monoethyl acetate.
  • methyl isobutyl ketone, butyl acetate, methyl amyl ketone, and propylene glycol monomethyl acetate are preferred.
  • these solvents can be used alone or as a mixed solvent of two or more.
  • an organic solvent ( C) needs to be contained in an amount of 30% by mass or more in 100% by mass of the total amount of the solvent in the composition of the present invention. If the proportion of the component (C) in the total solvent is less than 30% by mass, the separability of the components (A) and (B) may be insufficient and the reflectance may be increased. Therefore, these organic solvents (C) are preferably contained in an amount of 40% by mass or more in the solvent composition, and more preferably 50% by mass or more.
  • the amount of the organic solvent containing the solvent (C) in the curable resin composition is usually 300 to 5000 parts by weight, preferably 300 to 4000 parts by weight, with the total amount of solid components being 100 parts by weight. More preferably, it is 300-3000 mass parts.
  • (D) a compound having 1 or more polymerizable groups (hereinafter referred to as “polymerizable compound (D1)” or “compound” as long as it does not interfere with layer separation of component (A) and component (B) (D1) ”), and Z or fluorinated with one or more (meth) atalyloyl groups
  • a compound hereinafter, sometimes referred to as “fluorine-containing (meth) ataretoy compound (D2)” or “compound (D2)”
  • the compound (D1) and the compound (D2) may be collectively referred to as “polymerizable monomer (D)”.
  • the polymerizable group is not particularly limited, and examples thereof include a bur group, an epoxy group, and a (meth) atalyloyl group. Among them, a (meth) attaloyl group and a buyl group are preferred (meth) attaroyl. The group is particularly preferred.
  • the polymerizable compound (D1) having one or more polymerizable groups is used for improving the scratch resistance of a cured product obtained by curing a curable resin composition and an antireflection film using the cured product. Used.
  • a polyfunctional (meth) acrylate compound having two or more (meth) atalyloyl groups is preferable.
  • the polymerizable compound (D1) having a bur group is not particularly limited as long as it is a compound having one or more bur groups in the molecule. Examples thereof include N-vinyl-2-pyrrolidone. It is done. Examples of the commercially available polymerizable compound (D1) having such a vinyl group include Alonics M-150 (manufactured by Toagosei Co., Ltd.).
  • the polymerizable compound (D1) having a (meth) atalyloyl group is not particularly limited as long as it is a compound having one or more (meth) acryloyl groups in the molecule.
  • the monomer having one (meth) atrylyl group include acrylamide, (meth) atalyloyl morpholine, 7-amino-1,3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, -Luxetetyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) Acrylamide, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (
  • examples of the polyfunctional monomer having two or more (meth) atalyloyl groups include, for example, ethylene glycol di (meth) acrylate, dicyclopentadi (meth) acrylate, triethylene glycol dialate, Tetraethylene glycol di (meth) acrylate, trisic decandyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, force prolatatatone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”).
  • EO ethylene oxide
  • Modified trimethylolpropane tri (meth) acrylate Lopylene oxide (hereinafter referred to as “Po”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether (Meth) acrylic acid adduct, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta erythritol tetra ( (Meta) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol Sa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritotol
  • the compound (D1) having a polymerizable group preferably contains a compound having two or more (meth) attalyloyl groups in the molecule. Further, a compound having 3 or more (meth) attalyloyl groups in the molecule is particularly preferred.
  • Examples of the compound having a acryloyl group include the above-described tri (meth) ataretoy compounds, tetra (meth) atalertoy compounds, penta (meth) ataretoy compounds, hexa (meta ) Atarilate® compounds and other medium strengths can also be selected, and among these, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate Particularly preferred are rate, dipentaerythritol penta (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.
  • Each of the above compounds may be used alone or in combination of two or more.
  • the fluorine-containing (meth) ataretoy compound (D2) having one or more (meth) attalyloyl groups is used to lower the refractive index of the curable resin composition.
  • the compound (D2) is not particularly limited as long as it is a fluorine-containing (meth) acrylate compound having one or more (meth) atalyloyl groups.
  • a fluorine-containing (meth) acrylate compound having one or more (meth) atalyloyl groups For example, perfluorooctyl cetyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, etc., alone or in combination of two or more Is mentioned.
  • a compound obtained by modifying a fluorine alcohol having two or more hydroxyl groups with (meth) acrylic acid can also be used.
  • the fluoroalcohol having two or more hydroxyl groups specifically refers to ⁇ or 2, 2, 3, 3, 4, 4, 5, 5—one-year-old Kutafunore, one, six-hexane-old, three, , 3, 4, 4, 5, 5, 6, 6-octafluorooctane-1,8-diol.
  • These polyfunctional fluoroalcohols can be obtained by a general esterification method such as an acid chloride method, an acid-catalyzed dehydration condensation method, or a phase transfer catalyst method, to obtain a polyfunctional fluorine monomer having a (meth) atalyloyl group. . Further, a terminal acrylic fluorine oligomer (Cartoma Co., Ltd., CN4000) can also be used. These polyfunctional fluorine (meth) acrylates can be used as the compound (D2), and can reduce the refractive index and improve the strength of the low refractive index layer.
  • the content of the component (D) in the curable resin composition of the present invention is not particularly limited as long as it does not prevent layer separation of the components (i) and (ii). However, it is usually 0 to 30% by mass with respect to 100% by mass of the total composition excluding the organic solvent. Addition amount If it exceeds 30% by mass, the separability of components (A) and (B) will be impaired, the reflectance of the cured coating film will be high, and sufficient antireflection effect may not be obtained.
  • particles containing silica as a main component can be blended.
  • the silica particles are added to increase the hardness of the cured film and improve the scratch resistance.
  • known particles can be used, and if the shape is spherical, the particles are not limited to ordinary colloidal silica but are hollow particles, porous particles, and core-shell type. It may be a particle or the like. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle.
  • the particle size is preferably 1 to 200 nm, more preferably 1 to 100 nm. When the particle size is 200 nm or more, the transparency of the cured coating film may be impaired.
  • the silica particles (E) are preferably colloidal silica having a solid content of 10 to 40% by mass.
  • the dispersion medium is water! /
  • an organic solvent is preferred.
  • the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycolate, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene.
  • Hydrogens Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, ⁇ -butalate ratatones; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
  • silica as a main component
  • colloidal silica manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, MEK-S T-S, ⁇ — ST— L, IPA— ZL, NBA— ST, XBA— ST, DMAC— ST, ST— UP ⁇ ST— OUP ⁇ ST— 20, ST— 40, ST— C, ST— N, ST— 0, ST-50, ST-OL, etc. can be mentioned.
  • the surface of the colloidal silica that has been subjected to a surface treatment such as chemical modification can be used.
  • it contains a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof. Can be reacted.
  • the key compounds include trimethylmethoxysilane, tryptylmethoxysilane, dimethyldimethoxysilane, dibutinoresimethoxymethoxysilane, methyltrimethoxysilane, butinoretrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1, 1, 1-trimethoxy-1,2,2,2 trimethylmonodisilane, hexamethyl-1,3 disiloxane, 1,1,1-trimethoxy 3,3,3 trimethyl-1,3 disiloxane, ⁇ -trimethylsilyl ⁇ -dimethylmethoxysilyl— Examples include polydimethylsiloxane, (X-trimethylsilyl- ⁇ -trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3 disilazane, etc.
  • hydrolyzable silicon compounds having one or more reactive groups in the molecule You can also use 1 in the molecule.
  • Hydrolyzable Kei-containing compound having a reactive group of the above, as having a ⁇ group as the reactive group In example embodiment, urea propyltrimethoxysilane, Nyu-
  • Examples of those having a thiol group such as (xyl) ethyltrimethoxysilane include 3-mercaptopropyltrimethoxysilane.
  • a preferred compound is 3-mercaptopropyltrimethoxysilane.
  • the particles ( ⁇ ⁇ ) containing silica as the main component are those that have been surface-treated with an organic compound having a (meth) atallyloyl group (hereinafter sometimes referred to as "specific organic compound (S)"). It is preferable that Powerful surface treatment enables co-crosslinking with UV curable acrylic monomers, improving scratch resistance.
  • the specific organic compound used in the present invention is a polymerizable compound having a (meth) ataryloyl group in the molecule.
  • This compound is preferably a compound further containing a group represented by the following formula (14) in the molecule, a compound having a silanol group in the molecule, or a compound that generates a silanol group by hydrolysis.
  • X represents NH, 0 (oxygen atom) or S (ion atom), Y represents O or S o)
  • the polymerizable unsaturated group contained in the specific organic compound is an allyloyl group or a methacryloyl group.
  • This polymerizable group is a structural unit that undergoes addition polymerization with an active radical species.
  • the specific organic compound preferably further includes a group represented by the formula (14) in the molecule.
  • These groups can be used alone or in combination of two or more.
  • the specific organic compound is a compound having a silanol group in the molecule (hereinafter referred to as “silanol group-containing compound” t) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “silanol group-generating compound”). Is preferred).
  • silanol group-generating compound include compounds having an alkoxy group, an aryloxy group, a acetoxy group, an amino group, a halogen atom, etc. on the silicon atom. An alkoxy group or an aryloxy group is formed on the silicon atom.
  • a compound containing the compound, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
  • the silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the silica particles by a condensation reaction or a condensation reaction that occurs after hydrolysis.
  • specific organic compound (S) include, for example, a compound represented by the following formula (19).
  • R 25 and R 26 are the same or different hydrogen atom, or an alkyl group or aryl group having 1 to 8 carbon atoms, and r and s are each independently 1, 2 or 3 Indicates a number.
  • R 25 and R 26 examples include methyl, ethyl, propyl, butyl, octyl, phenol, xylyl group and the like.
  • Examples of the group represented by [(R 25 0) R 26 Si—] include, for example, a trimethoxysilyl group, a triethoxy r 3-r
  • Examples thereof include a silyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
  • R 27 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, linear, it may contain a branched or cyclic structure.
  • examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene.
  • preferred examples are methylene, propylene, cyclohexylene, and phenylene.
  • R 28 is a divalent organic group, and a medium force of a divalent organic group having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500 is also selected.
  • chain polyalkylene groups such as hexamethylene, otatamethylene, dodecamethylene, etc .
  • alicyclic or polycyclic divalent organic groups such as cyclohexylene, norvolylene, etc .
  • phenylene, naphthylene, biphenylene, Polyphere And divalent aromatic groups such as amines; and these alkyl group-substituted and aryl-substituted groups.
  • these divalent organic groups may include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, which may contain an atomic group containing an element other than carbon and hydrogen atoms, and further, in the above formula (14). Indicating groups can also be included.
  • R 29 is a (s + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
  • Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species.
  • an active radical species for example, ataryloyl (oxy) group, meta-atallyloyl (oxy) group, bur (oxy) group, probe (oxy) group, butagel (oxy) group, styryl (oxy) group, ethur ( Oxy) group, cinnamoyl (oxy) group, maleate group, allylamido group, methacrylamide group and the like.
  • an allyloyl (oxy) group and a methacryloyl (oxy) group are preferable.
  • b is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.
  • a method described in JP-A-9-100111 can be used. That is, (i) it can be carried out by addition reaction of mercaptoalkoxysilane, polyisocyanate compound, and active hydrogen group-containing polymerizable unsaturated compound. Alternatively, the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can be synthesized directly by addition reaction of a compound having a polymerizable unsaturated group and isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.
  • (i) is preferably used for synthesizing the compound represented by the formula (19). More specifically, for example,
  • mercaptoalkoxysilanes include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysilane, mercapto And propyltributoxysilane.
  • mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable.
  • an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan, or an addition product of an epoxysilane and an ⁇ , ⁇ -dimethylcaptoy compound can also be used.
  • the polyisocyanate compound used for synthesizing a specific organic compound should be selected from the polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons. Can do.
  • polyisocyanate compounds include, for example, 2, 4 tolylene diisocyanate, 2, 6 tolylene diisocyanate, 1, 3 xylylene diisocyanate, 1, 4-kisylylene diisocyanate, 1,5 naphthalene diisocyanate, m-phenylene diisocyanate, ⁇ -ferylene diisocyanate, 3, 3, 1 dimethyl-4, 4, diphenylmethane diisocyanate 4,4'-diphenylmethane diisocyanate, 3,3, -dimethylphenol di-diisocyanate, 4,4'-biphenyl-diisocyanate, 1,6 hexanediisocyanate, isophorone diisocyanate, Methylene bis (4-cyclohexylenoisocyanate), 2, 2, 4 trimethylhexamethylene diisocyanate, bis (2-isocyanate) Chill) fumarate, 6-isopropyl-1,3 di
  • 2,4 tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate), 1,3 bis (isocyanate methyl) cyclohexane and the like are preferable. These can be used alone or in combination of two or more.
  • compounds having at least one active hydrogen atom capable of forming a group and at least one polymerizable unsaturated group are examples.
  • active hydrogen-containing polymerizable unsaturated compounds include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2 hydroxy mono 3 Phenyloxypropyl (meth) acrylate, 1, 4 Butanediol mono (meth) acrylate, 2 Hydroxyalkyl (meth) attaroyl phosphate, 4 Hydroxy cyclohexyl (meth) acrylate, 1, 6 hexanediol mono (meta ) Atarylate, neopentyl glycol mono (meth) acrylate, trimethylol propanedi (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ate relay And the like can be given.
  • a compound obtained by addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid can be used.
  • a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid
  • 2-hydroxyxetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable.
  • the surface treatment method of the particles with the specific organic compound is not particularly limited, but it can also be produced by mixing the specific organic compound and particles, heating and stirring.
  • the reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-generating site of the specific organic compound with the particles.
  • the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.
  • the reaction amount of the particles and the specific organic compound is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably, with the total of the particles and the specific organic compound being 100% by mass. Is 1% by mass or more. If the content is less than 0.01% by mass, the transparency and scratch resistance of the resulting cured product may be insufficient due to insufficient dispersibility of the particles in the composition.
  • the amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment should be such that at least one alkoxy group on the silicon in one molecule is hydrolyzed.
  • the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably two minutes of the number of moles of all alkoxy groups. 1 to less than 3 times.
  • the product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface. In the cured product of the composition containing the composed particles, the effect of developing high hardness and scratch resistance is low.
  • the alkoxysilane compound is separately subjected to a hydrolysis operation, and then mixed with powder particles or a solvent-dispersed sol of particles, followed by heating and stirring.
  • a method of hydrolyzing the alkoxysilane compound in the presence of particles; or a method of surface-treating the particles in the presence of other components such as a polymerization initiator can be selected.
  • a method in which the alkoxysilane compound is hydrolyzed in the presence of particles is preferable.
  • the temperature is preferably 0 ° C or higher and 150 ° C or lower. More preferably, it is 20 ° C or higher and 100 ° C or lower.
  • the processing time is usually in the range of 5 minutes to 24 hours.
  • an organic solvent may be added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound.
  • organic solvent examples include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, Esters such as ethyl lactate and y-petite ratatotone; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N— Examples include amides such as methylpyrrolidone.
  • methanol isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
  • the amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.
  • a solvent-dispersed sol When a solvent-dispersed sol is used as the particles, it can be produced by mixing at least a solvent-dispersed sol and a specific organic compound.
  • an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.
  • acid, salt or base may be added as a catalyst.
  • Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid,
  • Examples of unsaturated organic acids such as itaconic acid include salts such as ammonium salts such as tetramethyl ammonium hydrochloride and tetraptyl ammonium hydrochloride
  • examples of bases include, for example, Ammonia water, jetylamine, triethylamine, dibutylamine, primary amines such as cyclohexylamine, secondary or tertiary aliphatic amines, aromatic amines such as pyridine, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, And quaternary ammonia hydroxides such as
  • the acid are organic acids and unsaturated organic acids
  • the base is tertiary amine or quaternary ammonium hydroxide.
  • the amount of addition of these acids, salts or bases is preferably 0.001 to 1.0 parts by mass, more preferably 0.01 parts by mass and 0.1 parts by mass with respect to 100 parts by mass of the alkoxysilane compound.
  • inorganic compounds such as zeolite, anhydrous silica and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used.
  • orthoesters such as methyl orthoformate and ethyl orthoformate are preferred.
  • the amount of the alkoxysilane compound bound to the particles is usually 110 ° C to 800 ° C in air as a constant value of mass loss% when the dry powder is completely burned in air. It can be obtained by thermal mass spectrometry.
  • the amount of the component (E) in the resin composition is usually preferably less than 30% by mass, more preferably 20% by mass or less, based on the total amount of the composition other than the organic solvent. If the particle amount force is S30% by mass or more, the separability of the components (A) and (B) may be insufficient, and the reflectance of the cured coating film may be increased.
  • the amount of particles means a solid content, and when the particles are used in the form of a solvent dispersion solution, the amount of the solvent does not include the amount of the solvent.
  • a photo radical polymerization initiator (radiation (photo) polymerization initiator) that generates active radical species by radiation (light) irradiation is used.
  • radiation photo
  • the radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization.
  • acetophenone acetophenone benzil ketal, 1-hydroxycyclohexyl.
  • the amount of the radical photopolymerization initiator (F) used as needed in the present invention is usually 100 to 10% by mass of the composition excluding the organic solvent, and is usually compounded in an amount of 0 to 10% by mass, It is preferable to add 0.01 to 10% by mass, and more preferably 0.1 to 10% by mass. If it exceeds 10% by mass, the cured product may not be cured to the inside (lower layer).
  • a photosensitizer a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surface active agent are used as necessary.
  • Agents, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes, slip agents, and the like can be appropriately blended.
  • methanol, ethanol, isopropyl alcohol, t-butyl alcohol, 2-butyl alcohol, propylene glycol monomethyl ether are used within the range not impairing the layer separation in the present invention.
  • organic solvents other than component (C) such as propylene glycol monoethyl ether can be used.
  • composition of the present invention is produced as follows.
  • Polymerizable group-containing fluoropolymer (component (A)), high refractive index polymerizable group-containing organic compound (component (B)), organic solvent (component (C)), and polymerizable monomer ( (D) component), silica particles ((E) particles), photo radical polymerization initiator ((F) component), etc. are placed in a reaction vessel equipped with a stirrer and stirred at 35 ° C. to 45 ° C. for 2 hours. It is set as the curable resin composition of this.
  • the curable resin composition of the present invention is suitable for use as an antireflection film or a coating material.
  • the base material to be used for antireflection or coating include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, Polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like.
  • These base materials may be plate-like, film-like or three-dimensionally formed by a usual coating method such as date coating, spray coating, flow coating, shower coating, ronore coating, spin coating, brush. For example, painting.
  • the thickness of the coating film by these coatings is usually 0.01 to 0.5 / z m after drying and curing, and preferably 0.05 to 0.5.
  • the curable resin composition of the present invention can be cured by radiation (light).
  • the radiation source is not particularly limited as long as the composition can be cured in a short time after coating.
  • a lamp, a resistance heating plate, a laser, or the like is visible.
  • Sun rays, lamps, fluorescent lamps, lasers, etc. as ray sources, mercury lamps, halide lamps, lasers, etc. as ultraviolet ray sources, and electron beam sources, generated from commercially available tungsten filaments Examples include methods that use hot electrons, cold cathode methods that generate high-voltage pulses in metals, and secondary electron methods that use secondary electrons generated by collisions between ionized gaseous molecules and metal electrodes. .
  • beta rays and gamma rays for example, fission materials such as 6G Co
  • a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used.
  • These radiations can be used alone or in combination of two or more simultaneously or over a period of time.
  • the curing reaction of the curable resin composition of the present invention may be performed under anaerobic conditions.
  • an inert gas such as nitrogen, carbon dioxide, or helium can be used. Of these, nitrogen is preferred.
  • the cured film of the present invention is obtained by curing the curable resin composition of the present invention, and has a multilayer structure of two or more layers.
  • the (A) one or more layers in which the polymerizable group-containing fluorine-containing polymer is present at a high concentration and the (B) one or more layers in which the (B) high refractive index polymerizable group-containing organic compound is present at a high concentration. It is preferable to have a layer structure of two or more layers.
  • the cured film of the present invention can be obtained by coating and curing the curable resin composition on various substrates, for example, plastic substrates. Specifically, it is possible to obtain a coated molded body by coating the composition, and preferably drying the volatile component at 15 to 200 ° C. and then performing the curing treatment with the above-mentioned radiation.
  • the preferable irradiation amount of ultraviolet rays is 0.01 to 10 jZcm 2 , and more preferably 0.1 to 2 JZC m 2 .
  • preferable electron beam irradiation conditions are a pressurization voltage of 10 to 300 KV, an electron density of 0.02 to 0.30 mAZcm 2 , and an electron beam irradiation amount of 1 to: LOMrad.
  • the polymerizable group-containing fluorine-containing compound (A) is fluorine.
  • the (A) component is concentrated at a high concentration near the atmosphere interface of the cured coating film.
  • a fat layer is formed.
  • the component (B) is unevenly distributed, and a high refractive index resin layer concentrated to a high concentration is formed.
  • a cured film having a layer structure of two or more layers can be obtained by curing one coating film having a curable resin composition strength.
  • Each of these separately formed layers can be confirmed, for example, by calculating the refractive index of the cured film from the reflectance curve of the obtained cured film.
  • the layer in which the component (A) is present at a high concentration is substantially a layer composed mainly of the component (A), but the component (B) may coexist in the layer.
  • the layer in which the component (B) is present in a high concentration is substantially a layer composed mainly of the component (B), but the component (A) may coexist in the layer.
  • the cured film of the present invention typically has a two-layer structure in which a layer in which the component (A) is present at a high concentration and a layer in which the component (B) is present at a high concentration form a continuous layer.
  • TAC resin used as the base material
  • the base layer usually the base layer, (B) component is present in a high concentration, and (A) component is present in a high concentration in this order. Is formed.
  • a hard coat layer 2 is formed on the substrate 1 as necessary, and a coating film made of the curable resin composition of the present invention is formed on the hard coat layer 2 and cured.
  • the high refractive index layer 3 in which the component (B) is present at a high concentration and the low refractive index layer 4 in which the component (A) is present at a high concentration are formed from one coating film.
  • Figure 3 shows a two-layer electron microscope photograph formed in this way. The right side of FIG. 3 is the air side, and the left side is the side close to the substrate. It can be seen that a layer in which the component (A) is present at a high concentration and a layer in which the component (B) is present at a high concentration form two continuous layers.
  • the (A) polymerizable group-containing fluoropolymer in the curable resin composition of the present invention has an antireflective property whose refractive index is lower than that of a thermosetting resin (for example, a melamine compound). It has favorable optical characteristics as a low refractive index layer of the film.
  • a polymerizable group-containing organic compound having a high refractive index after curing as the constituent material of (B)
  • an antireflection film having better antireflection properties can be obtained.
  • the cured film of the present invention has a high hardness and can form a coating film (film) excellent in scratch resistance and adhesion to adjacent layers such as a substrate and a substrate or a hard coat layer. have.
  • the cured film of the present invention is particularly suitably used for an antireflection film for film-type liquid crystal elements, touch panels, plastic optical parts and the like.
  • the film thickness of the resulting cured film consisting of two or more continuous layers should be set as appropriate according to the purpose and application, but when used as a high refractive index layer and a low refractive index layer of an antireflection film In this case, the thickness of the entire cured film having a force of two or more layers is usually in the range of 0.1 to 1 ⁇ m, and preferably in the range of 0.15 to 0.
  • the thickness of only the low refractive index layer in which the component (A) is present at a high concentration is usually in the range of 0.05 to 0.2 / zm, preferably in the range of 0.05-0.15 / zm. It is.
  • the thickness of only the high refractive index layer in which the component (B) is present in a high concentration is usually in the range of 0.05 to 0.9 / zm, preferably in the range of 0.05 to 0.5 / zm. .
  • the degree of change in reflectance of the cured film obtained can be adjusted by the content and type of components (A) and (B), the content and type of component (D) (polymerizable monomer), and the like. Furthermore, the reflectance of the cured film can also be adjusted by (C) the type and dilution of the organic solvent.
  • the refractive index in the low refractive index portion of the cured film is, for example, 1.30 to: L 50, and the refractive index in the high refractive index portion is 1.55 to: L 70.
  • the component (E) is unevenly distributed in the layer in which the component (A) is present at a high concentration.
  • the (E) component is unevenly distributed at a high density in the (A) low refractive index layer and the (E) component is substantially absent, while the (B) component is present in a high concentration layer.
  • This layer separation can be confirmed by observing the cured coating film with a transmission electron microscope and by calculating the refractive index.
  • the component (E) is unevenly distributed in the low refractive index layer in which the component (A) is present in a high concentration, thereby improving the hardness of the low refractive index layer and improving the scratch resistance.
  • a hard coat layer 2 is formed on the substrate 1 as necessary, and a coating film made of the curable resin composition of the present invention is formed on the hard coat layer 2 and cured.
  • a high refractive index layer 3 in which component (B) is present at a high concentration and a low refractive index layer 4 in which component (A) is present at a high concentration are formed from one coating film.
  • the silica particles 5 as the component (E) are present in the low refractive index layer 4 where the component) is present at a high concentration.
  • Fig. 4 shows an electron micrograph of the two layers thus formed. The left side of Fig. 4 is the air side, and the right side is the side close to the substrate. It can be seen that a layer containing (E) component silica particles and having a high concentration of component (A) and a layer having a high concentration of component (B) forms two continuous layers. Power.
  • the laminate of the present invention is a laminate having a cured film having a layer structure of two or more layers obtained from the curable resin composition of the present invention as a part of the laminate structure. Any two or more adjacent layers other than the base material layer constituting the laminate of the present invention can be produced as a cured film of the curable resin composition of the present invention.
  • the laminate of the present invention is an excellent antireflection film by providing a low refractive index layer on the outermost layer (the layer farthest from the substrate).
  • the laminate of the present invention can be used for optical parts such as a lens and a selective transmission film filter.
  • the specific layer configuration of the antireflection film is not particularly limited. Usually, at least a high-refractive index film and a low-refractive index film are laminated in this order on a base material to provide an antireflection function. In addition to this, a hard coat layer, an antistatic layer and the like can be included in a part of the layer structure of the laminate. Since the cured film obtained by curing the curable resin composition of the present invention can form a high refractive index layer and a low refractive index layer on a substrate in one step, the manufacturing process is simplified. I can do it.
  • the cured film of the present invention usually comprises two layers of a high refractive index layer and a low refractive index layer, and is formed on a base material to form a laminate suitable as an antireflection film. You can.
  • An antireflection film as a typical example of the laminate of the present invention is shown in FIG. [0146]
  • the antireflection film may further include layers other than these. For example, a plurality of combinations of a high refractive index film and a low refractive index film are provided, and the antireflection film is relatively uniform with respect to light in a wide wavelength range.
  • An antistatic layer may also be provided that serves as a so-called wideband antireflection film having excellent reflectance characteristics.
  • the substrate is not particularly limited, but when used as an antireflection film, for example, the above-mentioned plastics (polycarbonate, polymethylmetatalylate, polystyrene, polyesterol, polyolefin, epoxy resin, melamine resin) And triacetyl cellulose (TAC) resin, ABS resin, AS resin, norbornene resin, and the like.
  • plastics polycarbonate, polymethylmetatalylate, polystyrene, polyesterol, polyolefin, epoxy resin, melamine resin
  • TAC triacetyl cellulose
  • Production Example 2 Production of acryloyl group-containing fluoropolymer (A-3)
  • A-3 In a separable flask with a capacity of 1 liter equipped with a magnetic stirrer, glass cooling tube and thermometer, 50.0 g of the hydroxyl group-containing fluoropolymer (A-2) obtained in Production Example 1 was used as a polymerization inhibitor.
  • Olg and methylisobutylketone (hereinafter referred to as “MIBK”) 374 g were charged, and the hydroxyl group-containing fluoropolymer (A-2) was dissolved in MIBK at 20 ° C. Stirring was performed until the solution became clear and uniform.
  • MIBK methylisobutylketone
  • TMM- 3LM- N (consisting of 40 wt% pentaerythritol Atari rate 60 mass 0/0 and pentaerythritol Lumpur tetra strike rate Among them, involved in the reaction It is only pentaerythritol tritalylate having a hydroxyl group.) After dropping 549 parts at 30 ° C over 1 hour, the organic compound containing a polymerizable group is heated and stirred at 60 ° C for 10 hours. Obtained. When the amount of isocyanate remaining in the reaction solution was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed.
  • Production Example 4 Production of silica particles (E-1) having a polymerizable group
  • Composition containing a specific organic compound synthesized in Production Example 3 (S-1) 4.0 parts, methyl ethyl ketone silica sol (MEK-ST-L, manufactured by Nissan Chemical Industries, number average particle size 0.04 ⁇ m, silicic force concentration 30 %) 91.3 parts (solid content: 27.4 parts), 0.2 parts of isopropanol and 0.1 part of ion-exchanged water were stirred at 80 ° C for 3 hours, and then methyl orthoformate 1.4 parts Then, the mixture was further heated and stirred at the same temperature for 1 hour to obtain a colorless transparent particle dispersion (E-1). 2 g of the particle dispersion (E-1) was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 35% by mass.
  • S-1 4.0 parts, methyl ethyl ketone silica sol (MEK-ST-L, manufactured by Nissan Chemical Industries, number average particle size
  • Production Example 5 Production of compound (D-1) having two or more (meth) atalyloyl groups
  • Production Example 8 Production of hydroxyl-containing fluoropolymer (A-6)
  • the pressure when the temperature in the autoclave reaches 60 ° C is 5.3 X 10 5 Pa It was. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 ⁇ 10 5 Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content of 30%. The obtained polymer solution was poured into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 720 g of a fluoropolymer (A-7).
  • Production Example 10 Production of polymerizable group-containing fluoropolymer (A-8)
  • Production Example 11 Production of polymerizable group-containing fluoropolymer (A-9)
  • a separable flask with a capacity of 1 liter equipped with a magnetic stirrer, glass cooling tube and thermometer was charged with 20 g of the hydroxyl group-containing fluoropolymer (A-7) obtained in Production Example 9, MIBK 180 g, and dimethylaline 5 g.
  • the mixture was charged and stirred at room temperature until the solution was uniform.
  • 3.8 g of acrylic acid chloride was added and stirred until the solution became homogeneous, and then stirred for 12 hours while maintaining the temperature at 55 to 65 ° C. Then, it cooled to room temperature and 8g of 10% ammonia water was dripped.
  • the poor solvent was removed with decantation, and 200 g of MIBK was added and stirred until the solution became homogeneous.
  • 2 g of anhydrous magnesium sulfate was added, and the mixture was further stirred for 1 hour.
  • anhydrous magnesium sulfate was filtered off to obtain a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer (A-9).
  • A-9 ethylenically unsaturated group-containing fluoropolymer
  • a curable resin composition was obtained in the same manner as in Examples 1 to 2, except that each component was blended in the proportions shown in Tables 1 to 5.
  • Production Example 2 and Production Example 2 were used except that each dilution solvent listed in Table 3 was used instead of MIBK in Synthesis Example 2 to synthesize the alicyclic fluorinated polymer (A-3).
  • a curable resin composition was obtained using the dilute solvent shown in each example by using the atalyloyl group-containing fluoropolymer (A-3) produced in the same manner.
  • a cured film was prepared using the curable resin composition produced in Examples 1 to 23 and Comparative Examples 1 to 8, and the characteristics of the cured film were evaluated.
  • the method for producing the cured film is as follows: Silica particle sol (MEK-ST, manufactured by Nissan Chemical Industries, number average particle size 0.022 m, silica concentration 30%) 98.6 g, 2-methyl-1 [4 ( Methylthio) phenol] 2 Morpholinop Mouth pan 1-one (IRGACURE907, manufactured by Chinoku 'Specialty' Chemicals) 1. 2g, polyfunctional urethane acrylate oligomer (U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 33.
  • cyclo 7 g of hexanone was mixed and stirred to obtain a composition for a node coat layer containing silica particles.
  • a composition for a node coat layer containing silica particles After coating this silica particle-containing composition for a node coat layer on a triacetyl cellulose film (LOFO, film thickness 80 ⁇ m) using a wire bar coater (# 12), it was heated in an oven at 80 ° C. Dried for 1 minute. Subsequently, a hard coat layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.3 jZcm 2 using a high-pressure mercury lamp in the air. When the film thickness of the hard coat layer was measured with a stylus type film thickness meter, it was 5 ⁇ m.
  • each curable resin composition obtained in Examples 1 to 19 and Comparative Examples 1 to 8 was applied onto the obtained node coat layer. And dried at room temperature for 5 minutes. Then, a cured film layer having a total film thickness of 0.2; zm was formed by irradiating ultraviolet rays under a light irradiation condition of 0.9 jZcm 2 using a high-pressure mercury lamp lamp in a nitrogen atmosphere.
  • the cured film obtained by the above-described method was visually observed under a fluorescent lamp, and appearance defects such as a rainbow pattern due to uneven coating of foreign matter due to foreign matters were evaluated according to the following criteria.
  • Turbidity (Haze value) in the obtained laminate was measured using a Haze meter and evaluated according to the following criteria.
  • Haze value is 0.5% or less.
  • ⁇ Haze value is 1% or less.
  • ⁇ Haze value is 3% or less.
  • Spectral reflectance measurement device large sample chamber
  • the reflectance was measured in the wavelength range of 340 to 700 nm using a self-recording spectrophotometer U-3410 equipped with an integrating sphere attachment device 150-09090 (manufactured by Hitachi, Ltd.) and evaluated.
  • the reflectance of the antireflection laminate (antireflection film) at each wavelength was measured using the reflectance of the deposited aluminum film as a reference (100%), and from the reflectance of light at a wavelength of 550 nm,
  • the antireflection property was evaluated according to the following criteria.
  • the reflectance is 1% or less.
  • ⁇ Reflectance is 2% or less.
  • ⁇ Reflectance is 3% or less.
  • the steel wool resistance test of the cured film was performed by the following method.
  • steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded. Scratching was repeated 10 times under the condition of 500 g, and the presence or absence of scratches on the surface of the cured film was visually evaluated according to the following criteria.
  • the cloth resistance test of the cured film was carried out by the following method.
  • Bencott S-2, manufactured by Asahi Kasei Co., Ltd.
  • a Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.)
  • the surface of the cured film was loaded 100 times under the condition of load lkg.
  • the chemical resistance test of the cured film was performed by the following method. A drop of 3% aqueous sodium hydroxide, 1% hydrochloric acid, ethanol, MEK and glass mypet (manufactured by Kao) was dropped on the resulting antireflection film and left at room temperature for 30 minutes. Thereafter, the chemical solution was wiped off with Bencott (S-2, manufactured by Asahi Kasei Co., Ltd.) and dried at room temperature for 3 minutes. Then, the dropped marks were visually evaluated according to the following criteria.
  • ⁇ One or more kinds of chemicals show peeling or scratches on the cured film.
  • the antifouling test of the cured film was carried out by the following method. A fingerprint was adhered on the obtained antireflection film, and the fingerprint was wiped with Bencot (S-2, manufactured by Asahi Kasei Co., Ltd.). The wiping trace was visually evaluated according to the following criteria.
  • the color space value (b *) from an angle of 10 ° with a C light source was used for evaluation according to the following criteria.
  • ⁇ : b * is less than 5
  • ⁇ : b * is more than -8 and less than 10
  • refractive index after curing means a refractive index measured with an Abbe refractometer of a cured film cured with the component alone.
  • Ataliloyl group-containing fluorine-containing polymer A-3 (Manufactured in Production Example 2)
  • Ataliloyl group-containing fluoropolymer A-5 (manufactured in Production Example 7)
  • Diluting solvent including organic solvent of component (C):
  • PHE Phenoxetyl Atylate
  • Acrylic modified silica particles (E-1) (Manufactured in Production Example 3)
  • the curable resin composition of the present invention can form a cured film having a multilayer structure of two or more layers on a substrate from one coating film.
  • the curable resin composition of the present invention and the cured product thereof may be damaged by, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc.

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Abstract

L’invention concerne une composition de résine durcissable qui comprend les ingrédients (A) à (C) suivants : (A) un fluoropolymère ayant un groupe polymérisable ; (B) un composé organique qui a un groupe polymérisable et qui, après durcissement, présente un index de réfraction de 1,55 ou plus ; et (C) un ou plusieurs solvants organiques sélectionnés parmi le groupe constitué par les cétones et les esters et dans lequel ledit ou lesdits solvants organiques (C) sélectionnés parmi le groupe constitué par les cétones et les esters représentent 30 % ou plus en poids de tous les solvants. L’invention concerne également une pellicule durcie qui a une structure composée de deux couches ou plus et est obtenue par durcissement de ladite composition.
PCT/JP2006/305869 2005-04-13 2006-03-23 Composition de resine, pellicule durcie et produit stratifie WO2006112234A1 (fr)

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JP2006336008A (ja) * 2005-05-02 2006-12-14 Jsr Corp 硬化性樹脂組成物、硬化膜及び反射防止膜積層体
JP2007262127A (ja) * 2006-03-27 2007-10-11 Jsr Corp 硬化性樹脂組成物及び反射防止膜
WO2009078336A1 (fr) * 2007-12-14 2009-06-25 Asahi Kasei E-Materials Corporation Composition de résine photosensible
WO2009145061A1 (fr) * 2008-05-29 2009-12-03 旭硝子株式会社 Composition photodurcissable et procédé de fabrication pour un corps moulé ayant un motif fin sur la surface
WO2010035764A1 (fr) * 2008-09-26 2010-04-01 株式会社巴川製紙所 Stratifié optique et film à revêtement dur
KR100959231B1 (ko) 2007-03-05 2010-05-19 제이에스알 가부시끼가이샤 경화성 조성물, 경화막, 반사 방지막, 및 경화막의 제조방법
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US8071195B2 (en) * 2007-12-12 2011-12-06 Tdk Corporation Multi-layered object comprising hard coat layer and light transmitting layer, and method for producing the same
WO2011161812A1 (fr) * 2010-06-25 2011-12-29 リケンテクノス株式会社 Revêtement et corps stratifié
JP2012518713A (ja) * 2009-02-27 2012-08-16 エルジー・ケム・リミテッド 耐摩耗性および耐汚染性に優れたコーティング組成物およびコーティングフィルム
JP2012168416A (ja) * 2011-02-15 2012-09-06 Fujifilm Corp 反射防止フィルムの製造方法、反射防止フィルム、塗布組成物
JP2012247606A (ja) * 2011-05-27 2012-12-13 Jsr Corp 反射防止用積層体およびその製造方法、ならびに硬化性組成物
JP2012247667A (ja) * 2011-05-30 2012-12-13 Jsr Corp 反射防止用積層体およびその製造方法、ならびに硬化性組成物
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WO2013146778A1 (fr) * 2012-03-27 2013-10-03 三菱化学株式会社 Composition de résine pour peinture de revêtement
JP2014034596A (ja) * 2012-08-07 2014-02-24 Osaka Gas Chem Kk 傾斜膜形成用組成物およびこの組成物により形成される傾斜膜
JP2014105271A (ja) * 2012-11-27 2014-06-09 Kyoeisha Chem Co Ltd 活性エネルギー線硬化型ハードコート用樹脂組成物、ハードコート被覆熱可塑性シート及び光学部材
JP7491454B1 (ja) 2023-09-29 2024-05-28 荒川化学工業株式会社 活性エネルギー線硬化性組成物、硬化物及び積層物

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WO2022086194A1 (fr) * 2020-10-22 2022-04-28 한국화학연구원 Composition de revêtement polymère fluoré présentant une excellente résistance aux agents chimiques et une excellente résistance aux taches

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002311208A (ja) * 2001-04-17 2002-10-23 Jsr Corp 反射防止膜用硬化性組成物及びそれを用いた反射防止膜
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2005089536A (ja) * 2003-09-12 2005-04-07 Jsr Corp 硬化性樹脂組成物及び反射防止膜
JP2005290133A (ja) * 2004-03-31 2005-10-20 Jsr Corp 紫外線硬化型低屈折率材組成物及び反射防止膜
JP2006036835A (ja) * 2004-07-23 2006-02-09 Jsr Corp 硬化性樹脂組成物及び反射防止膜
JP2006097003A (ja) * 2004-08-31 2006-04-13 Jsr Corp 樹脂組成物及び反射防止膜

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2676618B2 (ja) * 1988-06-07 1997-11-17 日本化薬株式会社 樹脂組成物及び光ファイバ用コーティング剤
JP4561977B2 (ja) * 2004-10-20 2010-10-13 株式会社クラレ 光硬化性樹脂組成物及びそれを用いた積層体の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002311208A (ja) * 2001-04-17 2002-10-23 Jsr Corp 反射防止膜用硬化性組成物及びそれを用いた反射防止膜
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2005089536A (ja) * 2003-09-12 2005-04-07 Jsr Corp 硬化性樹脂組成物及び反射防止膜
JP2005290133A (ja) * 2004-03-31 2005-10-20 Jsr Corp 紫外線硬化型低屈折率材組成物及び反射防止膜
JP2006036835A (ja) * 2004-07-23 2006-02-09 Jsr Corp 硬化性樹脂組成物及び反射防止膜
JP2006097003A (ja) * 2004-08-31 2006-04-13 Jsr Corp 樹脂組成物及び反射防止膜

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* Cited by examiner, † Cited by third party
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KR100959231B1 (ko) 2007-03-05 2010-05-19 제이에스알 가부시끼가이샤 경화성 조성물, 경화막, 반사 방지막, 및 경화막의 제조방법
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US8475996B2 (en) 2007-12-14 2013-07-02 Asahi Kasei E-Materials Corporation Photosensitive resin composition
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US8258201B2 (en) 2008-05-29 2012-09-04 Asahi Glass Company, Limited Photocurable composition and process for producing molded product having fine pattern on its surface
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KR101702278B1 (ko) 2008-05-29 2017-02-03 아사히 가라스 가부시키가이샤 광경화성 조성물 및 표면에 미세 패턴을 갖는 성형체의 제조 방법
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JP2012247606A (ja) * 2011-05-27 2012-12-13 Jsr Corp 反射防止用積層体およびその製造方法、ならびに硬化性組成物
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