WO2006070710A1 - Antireflective film - Google Patents

Antireflective film Download PDF

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Publication number
WO2006070710A1
WO2006070710A1 PCT/JP2005/023708 JP2005023708W WO2006070710A1 WO 2006070710 A1 WO2006070710 A1 WO 2006070710A1 JP 2005023708 W JP2005023708 W JP 2005023708W WO 2006070710 A1 WO2006070710 A1 WO 2006070710A1
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group
formula
carbon atoms
compound represented
key compound
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PCT/JP2005/023708
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French (fr)
Japanese (ja)
Inventor
Ryoji Tatara
Hitoshi Kato
Kensuke Miyao
Yasuharu Yamada
Takaro Yashiro
Takahiko Kurosawa
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Jsr Corporation
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Publication of WO2006070710A1 publication Critical patent/WO2006070710A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays

Definitions

  • the present invention relates to an antireflection film. More specifically, the present invention relates to an antireflection film excellent in antistatic properties, scratch resistance and stain resistance.
  • an antireflection film including a low refractive index layer made of a cured product having excellent contamination properties.
  • These display panels are required to have scratch resistance that is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like. There is also a need for anti-contamination that can easily wipe off attached fingerprints and dust.
  • the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate.
  • the base material for example, triacetyl cellulose is used, but in the antireflection film using such a base material, in order to increase the adhesion when bonded to the polarizing plate, Usually, it is necessary to saponify with an alkaline 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 fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known (for example, Patent Documents:! To 3).
  • an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition-polymerizable unsaturated group, and a hydroxyl group-containing fluorine-containing polymer.
  • a composition for coatings containing an unsaturated group-containing fluorinated vinyl polymer obtained by reacting a polymer with an isocyanate group at a ratio of the number of isocyanate groups to the number of hydroxyl groups of 0.01 to 1.0 is proposed. (For example, Patent Document 4).
  • Patent Document 4 when preparing a fluorine-containing vinyl polymer containing an unsaturated group,
  • an isocyanate group-containing unsaturated compound in an amount sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluoropolymer was not used, and unreacted hydroxyl groups were actively left in the polymer. .
  • a coating composition containing such a polymer can be cured at a low temperature in a short time, but is further cured using a curing agent such as a melamine resin in order to react the remaining hydroxyl group.
  • a curing agent such as a melamine resin
  • Patent Document 1 Japanese Patent Laid-Open No. 57-34107
  • Patent Document 2 JP 59-189108 A
  • Patent Document 3 JP-A-60-67518
  • Patent Document 4 JP-A-61-296073
  • the present invention has been made in view of the above-described problems, and an object of the present invention is to provide an antireflection film excellent in antistatic property, scratch resistance, and contamination resistance.
  • the following antireflection film is provided.
  • R 1 is an alkyl group having 1 to 8 carbon atoms
  • a carboxyl group an alkyl group having 2 to 4 carbon atoms.
  • h is an integer of 0 to 1.
  • R 2 is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms, or A methacryloxyalkyl group having 5 to 8 carbon atoms
  • j represents an integer of 1 to 3.
  • X in formula (1) and X in formula (2) may be the same or different.
  • a low refractive index layer comprising a cured product of a curable resin composition containing
  • (B2) a key compound represented by the following formula (1), a key compound represented by the formula (2) and a hydrolyzate and / or a hydrolyzed condensate of the key compound represented by the formula (3)
  • R 1 is an alkyl group having 1 to 8 carbon atoms
  • a siloxycarbonyl group or an alkylamino group having 1 to 4 carbon atoms, h is an integer of 0 to 1.
  • R 2 is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms, or Charcoal A methacryloxyalkyl group having a prime number of 5 to 8, j represents an integer of 1 to 3; R 3 represents a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and k represents an integer of 1 to 3.
  • X in 3 can be the same or different.
  • a low refractive index layer comprising a cured product of a curable resin composition containing
  • the hydrolyzate And / or the hydrolysis condensate comprises a reactant of 67 to 99 mol% of the key compound represented by formula (1) and 33 to 1 mol% of the key compound represented by formula (2).
  • the porous silica particles (B2) are a total of the key compound represented by the formula (1), the key compound represented by the formula (2), and the key compound represented by the formula (3). Is 100 mol%, the hydrolyzate and Z or hydrolysis condensate are 60 to 98 mol% of the key compound represented by the formula (1) and the key compound represented by the formula (2). 3.
  • the hydroxyl group-containing fluoropolymer has a total of 100 structural units (a), (b) and (c) below: And the structural unit (a) 20 to 70 mol%, the structural unit (b) 10 to 70 mol% and the structural unit (c) 5 to 70 mol% with respect to mol%, and
  • R 4 represents a fluorine atom, a fluoroalkyl group or a group represented by —OIT (R 5 represents an alkyl group or a fluoroalkyl group)]
  • OCOR 8 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group
  • R 9 represents a hydrogen atom or a methyl group
  • R 1Q represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • R 11 and R 12 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
  • FIG. 1 is a cross-sectional view of an antireflection film according to an embodiment of the present invention.
  • the conductive layer in the antireflection film of the present invention functions as an antistatic layer.
  • the conductive layer formed by gas phase polymerization can be produced by, for example, the method described in JP-A-2003-82105, and can be specifically formed from a conductive polymer.
  • an oxidant is applied to the base layer with a thickness of several ⁇ units, and the monomer (monomer) is brought into contact with the oxidant coating film in a gaseous state, whereby the polymerization proceeds and the conductive polymer film is formed as a base.
  • a polymer such as polyurethane, polyvinyl chloride, polyvinyl alcohol, methylcellulose, chitosan together with an organic solvent.
  • the monomer is vapor-phase polymerized on the base layer coated with the oxidizing agent to conduct the A conductive layer made of a polymer is formed, and the reaction temperature at this time is preferably 0 to 140 ° C.
  • the polymerization method will be described in more detail, but the present invention is not limited thereto.
  • oxidizing agent 0.5 to 10% by mass of an oxidizing agent is applied to the surface of the base layer in units of several zm.
  • oxidizing agents include CuCl, iron toluenesulfonate ( ⁇ ),
  • the solvent conditions at this time vary depending on the type of base layer used.
  • the organic solvent used can be used. These can be used alone or in combination of two or more. For example, an organic solvent composed of methyl alcohol, 2_butyl alcohol and ethyl acetate sorb 7: 2: 1, 6: 2: 2, 6: Mix at a ratio of 3: 1, 5: 3: 2, etc.
  • the base layer to which the oxidizing agent is applied is dried with a hot air dryer at 80 ° C. or lower in consideration of decomposition of the oxidizing agent.
  • the base layer coated with the oxidizing agent is selected from the group consisting of pyrrole, thiophene, furan, selenophene, 3,4-ethylenedioxythiophene, and derivatives thereof.
  • the monomer is vaporized and brought into contact, and a polymerization reaction is performed on the surface of the base layer.
  • examples of the method for vaporizing the monomer include a method in which the monomer is distilled at 0 to 140 ° C. in a sealed chamber, a method by CVD (Chemical Vapor Deposition), and the like.
  • CVD Chemical Vapor Deposition
  • a washing step is performed to remove unreacted monomers and oxidizing agents.
  • alcohol such as methanol is usually used, and in some cases, it can be washed with water.
  • the series of steps as described above can be performed stepwise or continuously, and from the polymerization of the monomers to the formation of the conductive film, they can be performed in a series of working steps.
  • the obtained conductive polymer film has good adhesion to the base layer and has sufficient resistance to alcohol solvents.
  • the thickness of the conductive layer is preferably:! -2000 nm. If the film thickness is less than 1 nm, pinholes or the like are generated, and it is difficult to form a film immediately. Further, the surface resistance is increased and the antistatic property may be deteriorated.
  • a particularly preferred film thickness is 5 to 300 nm from the viewpoint of the balance of transparency, color tone, and surface resistance.
  • the surface resistance of the conductive layer is usually 10 2 ⁇ / port to 10 12 ⁇ / port.
  • the curable resin composition used in the present invention may contain the following components (A) to (F). Among these components, (A) and (B) are essential components, and (C) to (F) are optional components that can be appropriately contained.
  • It comprises a key compound represented by the following formula (1), a key compound represented by the formula (2) and a hydrolyzate and / or a hydrolytic condensate of the key compound represented by the formula (3), Porous silica particles having an average particle size of 5 to 50 nm
  • R 2 , X, h, j, and k are as described above.
  • the ethylenically unsaturated group-containing fluorine-containing polymer is obtained by combining a compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer. It is obtained by reacting at a ratio of 1.1 to 1.9.
  • a compound containing one isocyanate group and at least one ethylenically unsaturated group a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule If it is, it will not be restrict
  • the compound which has a (meth) taroloyl group is more preferable.
  • examples of such compounds include 2- (meth) ataryloxychetyl isocyanate, 2- (meth) ataryloxypropyl isocyanate, 1,1-bis [(meth) ataryloxymethyl ] Ethyl isocyanate is a single type or a combination of two or more types.
  • Such a compound can be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
  • diisocyanates examples include 2,4_tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylisocyanate), 1,3_bis (isocyanate) Methyl) cyclohexane is preferred.
  • Examples of the hydroxyl group-containing (meth) acrylate are 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate.
  • 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 KAYARAD DPHA, PET
  • the hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
  • R 4 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR 5 (R 5 represents an alkyl group or a fluoroalkyl group)]
  • R 6 is a hydrogen atom or a methyl group
  • R 7 is an alkyl group, — (CH 2) —OR 8 or
  • R 8 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group
  • the fluoroalkyl group of R 4 and R 5 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group. And a fluoroalkyl group having 1 to 6 carbon atoms such as a perfluorocyclohexyl group.
  • the alkyl group for R 5 include alkyl groups having 1 to 6 carbon atoms such as methinole group, ethyl group, propyl group, butyl group, hexyl group, and cyclohexyl group.
  • 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 perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers.
  • Perfluoro (alkyl vinyl ethers) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl butyl ether), etc .; Perfluoro (alkoxy alkeno butyl ether) s such as propoxypropyl bietherenole) may be used singly or in combination of two or more.
  • hexafluoropropylene and perfluoro (alkyl vinyl etherol) 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 mono% with respect to a total of 100 mol% of the structural units (a), (b) and (c). This is because if the content is less than 20 mole 0/0, which is the optical characteristics of the fluorine-containing material when the present invention is intended, it may be a case where the expression of the low refractive index becomes difficult, whereas If the content exceeds 70 mol%, the solubility of the hydroxyl group-containing fluorine-containing polymer in an organic solvent, transparency, or adhesion to a substrate may decrease. Because there is.
  • examples of the alkyl group represented by R 7 or R 8 include alkyl groups having 1 to 12 carbon atoms such as a methinole group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group.
  • examples of the alkoxycarbonyl group for R ′ include a methoxycarbonyl group and an ethoxycananol group.
  • the structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component.
  • bur monomers include methyl buule tenole, ethino levinino ree tenole, n- propino levino lee tenole, isopropino levino renol ether, n-butyl butyl ether, isobutyl butyl ether.
  • the content of the structural unit (b) is 10 to 70 mol% with respect to a total of 100 mol% of the structural units (a), (b) and (c). This is because if the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, Transparency and low reflection of fluorine-containing polymer This is because the optical characteristics such as efficiency may deteriorate.
  • R 1Q hydroxyalkyl groups include 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 5-hydroxypentyl. Group, 6-hydroxyhexyl group and the like.
  • the structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component.
  • hydroxyl-containing bur monomers include 2-hydroxyethylenovininoleetenore, 3-hydroxypropinorevininoleetenore, 2-hydroxypropinorevininoleetenore, 4-hydroxybutinolebi Hydroxyl-containing vinyl ethers such as ninoleatenole, 3-hydroxybutynolebinino ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl aryl ether, 4-hydroxybutyl aryl ether And hydroxyl group-containing aryl ethers such as glycerol monoallyl ether, aryl alcohol and the like.
  • the hydroxyl group-containing vinyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, force prolatathone ( (Meth) acrylate, polypropylene glycol (meth) atrelate, etc. can be used.
  • the content of the structural unit (c) is preferably 5 to 70 mol% with respect to the total of 100 mol% of the structural units (a), (b) and (c). ,.
  • the reason for this is that when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced.
  • the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).
  • R 11 and R 12 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 of R 11 or R 12 is an alkyl group having 1 to 3 carbon atoms such as a methinole group, an ethyl group, or a propinole group, and the halogenated alkyl group is a trifluoromethyl group.
  • the aryl groups are phenyl groups, benzyl groups, naphthyl groups, etc. Can be mentioned.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (7).
  • An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (8).
  • R 13 to R 16 represent the same or different hydrogen atoms, alkyl groups or cyan groups, and R 17 to R 2 ° may be the same or different.
  • the structural unit (d) is represented by the following structural unit (e): As part, it is contained in a hydroxyl group-containing fluoropolymer.
  • R 13 to R 16 , R 17 to R 2 °, p, q, s, t and y are the same as in the above formula (8).
  • Examples of the alkyl group of R 17 to R 2 ° include alkyl groups having! 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 above formula (8) is particularly preferably a compound represented by the following formula (10).
  • the content of the structural unit (d) may be 0.1 to 10 mole parts with respect to a total of 100 mole parts of the structural units (a), (b) and (c). preferable.
  • the reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing is lowered, and the scratch resistance of the coated film may be lowered.
  • the amount exceeds 10 mol parts the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating.
  • the content of the structural unit (d) is set to 0.:! To 5 monolayers with respect to a total of 100 monolayers of the structural units (a), (b) and (c). More preferably, the force S is 0.:! To 3 monolayers.
  • the content of structural unit (e) is included in it It is desirable to determine the content of the structural unit (d) to be within the above range.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (f).
  • R 21 represents a group having an emulsifying action
  • the group having an emulsifying action of R 21 has both a hydrophobic group and a hydrophilic group, and the hydrophilic group has a polyether structure such as polyethylene oxide and polypropylene oxide. A certain group is preferred.
  • Examples of such a group having an emulsifying action include a group represented by the following formula (12).
  • n is a number from 1 to 20
  • m is a number from 0 to 4
  • u is a number from 3 to 50
  • the structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component.
  • a reactive emulsifier examples include compounds represented by the following formula (13).
  • the content of the structural unit (f) is preferably 0.:! To 5 mol parts with respect to a total of 100 mol parts of the structural units (a), (b) and (c). .
  • the reason is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved.
  • the content is 5 mol part or less, the curable resin composition is used. This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
  • the content of the structural unit (f) is changed from 0.:! To 3 monolayers B for a total of 100 monolayers of the structural units (a), (b) and (c). More preferably, it is more preferably 0.2 to 3 monolayers.
  • the hydroxyl group-containing fluoropolymer preferably has a polystyrene equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography using tetrahydrofuran as a solvent.
  • the reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered.
  • the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.
  • the hydroxyl-containing fluoropolymer has a polystyrene equivalent number average molecular weight of 10,000 to 300,000, more preferably S, more preferably 10,000 to 100,000. .
  • the ethylenically unsaturated group-containing fluorine-containing polymer comprises the above-mentioned compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. It is obtained by reacting at a molar ratio of 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. On the other hand, if the molar ratio exceeds 1.9, the coating film of the curable resin composition may be used. This is because the scratch resistance after immersion in an alkaline solution may be reduced.
  • the molar ratio of the isocyanate group Z hydroxyl group is preferably 1.1 to 1.5, and more preferably 1.2 to 1.5.
  • the amount of the additive (A) added in the curable resin composition is not particularly limited, but is usually 1 to 95% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 1% by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. This is because if the addition amount exceeds 95% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
  • the amount of added force of the component (A) is 2 to 90% by mass, and it is more preferable that the value is within the range of 3 to 85% by mass.
  • the curable resin composition used in the present invention is blended with porous silica particles (B) for the purpose of improving the scratch resistance of the cured film of the curable resin composition, particularly the scratch resistance against steel wool.
  • porous silica particles (B) As the porous silica particles (B), the first porous silica particles (B1) or the second porous silica particles (B2) are used.
  • the first porous silica particles (B1) are obtained by hydrolysis and / or hydrolysis condensation of a key compound represented by the following formula (1) and a key compound represented by the following formula (2). That is, it is obtained by subjecting the key compound represented by the formula (1) to carohydrolysis and / or hydrolysis condensation, and hydrolyzing and / or hydrolytic condensation of the key compound represented by the formula (2). It is done.
  • the key compound represented by the formula (1) and the key compound represented by the formula (2) may be mixed and simultaneously hydrolyzed and / or hydrolyzed or condensed.
  • the represented key compound may be hydrolyzed and / or hydrolyzed and condensed, and then the key compound represented by the formula (2) may be added for further hydrolysis and / or hydrolytic condensation.
  • the second porous silica particle (B2) is composed of a key compound represented by the following formula (1), a key compound represented by the following formula (2), and a key compound represented by the following formula (3). Obtained by hydrolysis of Z and Z or hydrolytic condensation.
  • hydrolysis and Z or hydrolytic condensation of the key compound represented by the formula (1), and hydrolysis and Z or hydrolytic condensation of the key compound represented by the formula (2) It is obtained by hydrolysis and Z or hydrolysis condensation of the key compound represented by (3).
  • the key compound represented by the formula (1), the key compound represented by the formula (2) and the key compound represented by the formula (3) are mixed and simultaneously hydrolyzed and Z or hydrolyzed and condensed. Or expressed by formula (1) Hydrolyzing and / or hydrolytically condensing the key compound, then adding the key compound represented by formula (2) and the key compound represented by formula (3) to further hydrolyze and / or Hydrolysis condensation may be performed.
  • R 1 is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group. .
  • each X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, a carboxyl group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, or An alkylamino group having 1 to 4 carbon atoms, preferably an alkoxy group or a halogeno group, more preferably an alkoxy group.
  • X may be the same or different.
  • h is an integer of 0 to:!, Preferably 0.
  • Examples of the compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrachlorosilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, etyltrichlorosilane, Examples include titrimethoxysilane and ethyltriethoxysilane.
  • R 2 is an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably a Bier group, An aryl group, an attaryloxychetyl group, an attaryloxypropyl group, an attaryloxybutyl group, a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxybutyl group.
  • j is an integer of 1 to 3, preferably 1 to 2.
  • Examples of the compound represented by the formula (2) include butyltrimethoxysilane, butyltrioxysilane, butyltrichlorosilane, attaryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.
  • the porous silica particles can contain an ethylenically unsaturated group.
  • Curable composition by containing ethylenically unsaturated groups The scratch resistance of the antireflection film of the present invention having a cured film obtained by curing the product is improved.
  • R 3 is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, preferably a fluorine-substituted alkyl group having 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms.
  • k is an integer of 1 to 3, preferably 1 to 2.
  • Examples of the compound represented by the formula (3) are 3, 3, 3_trifluoropropyltrimethoxysilane, 2_perfluorohexylmethyltrimethoxysilane, 2_perfluorohexoxyperfluorooctyl. Ethyltriethoxysilane, 3,3-di (trifluoromethyl) _3_fluoropropyltriethoxysilane, and the like.
  • the porous silica particles can contain a fluorine-containing alkyl group.
  • the stain resistance of the cured film obtained by curing the curable composition can be improved.
  • Two or more types of the key compound represented by the formula (1), the key compound represented by the formula (2), and the key compound represented by the formula (3) may be used.
  • the formula ( Kei fluorinated compounds represented by 1) / Kei-containing compound represented by the formula (2) is preferably 67-99 / :! to 33 (mol 0/0), more preferably 70 to 98 / Hydrolyzed and / or hydrolyzed and condensed at a ratio of 2 to 30 (mol%).
  • the total of the key compound represented by formula (1), the key compound represented by formula (2), and the key compound represented by (3) is 100.
  • the key compound represented by the formula (1) / the key compound represented by the formula (2) Z the key compound represented by the formula (3) is preferably 60 to 98. / :! ⁇ 30Z:! ⁇ 20 ( Monore 0/0), more preferably 65 ⁇ 96Z2 ⁇ 20Z2 ⁇ : 15 is hydrolyzed and Z or hydrolytic condensation at a ratio of (Monore%).
  • the first and second porous silica particles (Bl) and (B2) used in the present invention have an average particle size force of ⁇ 50 nm, preferably 5 to 45 nm, more preferably 5 to 40 nm. flat
  • the average particle diameter is a number average particle diameter, and is measured by a transmission electron microscope observation image.
  • the "multi-porous" the specific surface area is 50 to: be 1000 m 2 / g, preferably 50 to 800 m 2 / g, it means that more preferably 100 ⁇ 800m 2 / g .
  • the specific surface area is measured by the BET method.
  • the average particle size is within the above range, scattering of the obtained coating film in the visible light region can be suppressed.
  • the density is lowered, and the refractive index of the film containing such porous silica particles is lowered.
  • porous silica particles (B) are obtained by the production method described below.
  • the first or second porous silica particles (Bl) and (B2) are at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and half ethers of diols.
  • the formula (2) It can be produced by hydrolyzing and / or hydrolytically condensing the key compound represented by the formula (1) and the key compound represented by the formula (3).
  • an amine compound for example, an amine compound is used.
  • Specific examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethylanolamine, dimethylmonoethanolamine.
  • ammonia, ethanolamine, tetramethylamine hydroxide or the like is used.
  • the acid amide, diol or diol half ether is preferably compatible with water and an alcohol.
  • acid amides include N, N-dimethylformamide, N, N-dimethylacetamide,
  • N-methylpyrrolidone or the like is used, and N, N-dimethylformamide, N, N-dimethylacetamide is preferably used.
  • the diol for example, ethylene glycol, propylene glycol, 1,2-butanediol and the like are used, and preferably ethylene glycol and propylene glycol are used.
  • ethylene glycol monomethyl ether or propylene glycol monomethyl ether is used as the half ether of the diol.
  • porous silica particles used in the present invention can be made porous by the coexistence of acid amide, diol or diol half ether during synthesis.
  • the total concentration of the key compound of formula (1) and the key compound of formula (2) or the total concentration of the key compounds of formulas (1) to (3) in the reaction solution is a complete hydrolysis condensate. Usually in terms of conversion: 0.5 to 10% by mass, preferably:! To 8% by mass.
  • “in terms of fully hydrolyzed condensate” is a theoretical value calculated on the assumption that the key compound has been completely hydrolyzed and condensed, and includes the key compound of formula (1) and the key of formula (2). This corresponds to the mass in the case where X of the elemental compound or X of the compound of the formulas (1) to (3) is substituted with an oxygen atom of 1/2 mol of X.
  • the key compound of formula (1) and the key compound of formula (2), or the key compound of formula (1), the key compound of formula (2) and the key compound of formula (3) are mixed simultaneously. In the presence of at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and half ethers of diols.
  • the key compound represented by formula (1) is hydrolyzed and / or hydrolyzed and condensed, and then the key compound represented by formula (2) or the key represented by formula (2), respectively.
  • An elemental compound and a key compound represented by the formula (3) may be added, followed by hydrolysis and Z or hydrolytic condensation.
  • the reaction temperature of hydrolysis and / or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of the alcohol and acid amide to be used.
  • the reaction time is represented by the formula (1), the formula (2), the formula (3) and the formula (3).
  • the optimum value depends on the type of elemental compound, reaction rate, type and amount of base, etc., and is not limited.
  • the porous silica particles are made organic.
  • a dispersion liquid dispersed in a solvent can be obtained.
  • the dispersion medium is preferably water or an organic solvent.
  • the organic solvent include methanols, isopropylenoreconoles, ethylene glycolanols, butanols, ethyleneglycolone monopropyl ethers, and the like; ketones such as methyl ethyl ketone and methyl isobutyl ketone; toluene, xylene and the like Aromatic hydrocarbons; Amides such as dimethylformamide, dimethylacetamide, N_methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, ⁇ - butarate ratatones ; Ethers such as tetrahydrofuran, 1, 4_dioxane, etc.
  • Organic solvents can be mentioned, and among these, alcohols and ketones are preferable. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
  • the amount of the porous silica particles ( ⁇ ) in the resin composition is usually 5 to 99% by mass, preferably 10 to 98% by mass, based on the total amount of the composition other than the organic solvent. More preferred is 97% by mass. If it is less than 5% by mass, the hardness of the cured film may be insufficient, and if it exceeds 99% by mass, sufficient film strength may not be obtained.
  • the amount of particles means solid content, and when the particles are used in the form of a solvent dispersion, the amount of the solvent does not include the amount of solvent.
  • the curable resin composition contains a polyfunctional (meth) acrylate compound containing at least two or more (meth) attaroyl groups and ⁇ or at least one (meth) acryloyl group as required. It is also possible to add a fluorine-containing (meth) atareto toy compound.
  • a polyfunctional (meth) atareto toy compound containing at least two (meth) atalyloyl groups The compound is not particularly limited as long as it is a compound containing at least two (meth) atallyloyl groups in the molecule.
  • Examples include neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, penta erythritol nortri (meth) acrylate, trimethylol ethane tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate relay , Dipentaerythritol hexa (meth) acrylate, force prolatatone modified dipentaerythritol hex (meth) acrylate, ditrimethylolpropane tetra (meth)
  • U-15HAJ (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
  • neopentyl glycol di (meth) acrylate dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and force prolatatatone.
  • Modified dipentaerythritol hexa (meth) acrylate is particularly preferred.
  • This compound is not particularly limited as long as it is a fluorine-containing (meth) atreyl H compound containing at least one (meth) attalyloyl group.
  • fluorine-containing (meth) atreyl H compound containing at least one (meth) attalyloyl group.
  • examples thereof include perfluorooctyl cetyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
  • the amount of the additive (C) added is not particularly limited, but is usually 0 to 90 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. The reason for this is that when the addition amount exceeds 90 parts by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained.
  • the amount of added force of the component (C) is 80 parts by mass or less, and it is more preferable that the amount of added force is 60 parts by mass or less.
  • D Compound that generates active species by irradiation of active energy rays or heat
  • a compound that generates active species by irradiation of active energy rays or heat can also be added.
  • a compound that generates active species upon irradiation with active energy rays or heat is used to cure the curable resin composition.
  • photopolymerization initiators examples include photoradical generators that generate radicals as active species.
  • the active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species.
  • active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, strands, j3 rays, and ⁇ rays.
  • ultraviolet rays it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, increasing the curing speed, and relatively low cost of the irradiation apparatus and relatively small size.
  • photoradical generators include, for example, acetophenone, acetophenone benzil ketal, anthraquinone, 1- (4-isopropylphenyl) 1-2-hydroxy-1-2-methylpropanepanone, carbazole, xanthone, 4 Benzophenone, 4, 4'-amino minobenzophenone, 1,1-dimethoxydeoxybenzoin, 3, 3'-dimethyl-4-methoxybenzophenone, thixanthone, 2,2-dimethoxy 2-phenenoreacetophenone, 1- (4-Dodecylphenyl) 2-hydroxy-1-2-methylpropane-1-one, 2-methyl-1-1-1 [4 (methylthio) phenyl] 2-morpholinopropane 1-one, triphenylamine, 2, 4, 6 _Trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2- Droxyl 2_methyl _ 1 _
  • photopolymerization initiators 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxyoxy-2-methyl-1 1-phenylpropane-1-one, 1-hydroxycyclohexyl Norenyl diketone, 2, 4, 6 _Trimethylbenzoyldiphenylphosphine oxide, 2 —Methylolone 1 _ [4_ (methylthio) phenyl] _ 2_morpholinopropane 1-one, 2- (dimethylamino) — 1 _ [4_ (morpholinyl) phenyl] _ 2 -phenylmethyl) -1 -butanone is preferred, more preferably 1-hydroxycyclohexylphenylketone, 2-methyl mono 1 _ [4_ (methylthio) phenyl ] _ 2 _ morpholinopropane 1-one, 2 _ (dimethylamino) 1 _ [4_ (morpholinyl) phenyl] _
  • the addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. The reason for this is that when the addition amount is less than 0.01 parts by mass, the curing reaction becomes insufficient and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, if the addition amount of the photopolymerization initiator exceeds 20 parts by mass, the refractive index of the cured film may increase and the antireflection effect may decrease.
  • the addition amount of the photopolymerization initiator is 0.05 to 15 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. More preferably, the content is 15 parts by mass.
  • thermal polymerization initiator examples include a thermal radical generator that generates a radical as the active species.
  • thermal radical generators include benzoyl peroxide, tert-butyl monooxy benzoate, azobisisobutyronitrile, acetyl chloride, lauryl peroxide, tert_butinoreperacetate, cuminoreperoxide, tert _Bucino Leperoki Side, tert butylhydride peroxide, 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy 2,4-dimethylvaleronitrile), etc. Single or a combination of two or more Can be mentioned.
  • the addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. The reason for this is that when the amount added is less than 0.01 parts by mass, the curing reaction becomes insufficient and the scratch resistance and the scratch resistance after immersion in an aqueous alkali solution may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20 parts by mass, the refractive index of the cured film increases and the antireflection effect may decrease.
  • the additive amount of the thermal polymerization initiator it is more preferable to set the additive amount of the thermal polymerization initiator to 0.05 to 15 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. To: More preferably, the value is within the range of 15 parts by mass.
  • an organic solvent it is preferable to further add an organic solvent to the curable resin composition.
  • an organic solvent an alcohol solvent having 1 to 8 carbon atoms, a ketone solvent having 3 to 10 carbon atoms, and an ester solvent having 3 to 10 carbon atoms can be preferably used.
  • Methyl ethyl ketone, methanol, ethanol, t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol ether ether, propylene glycol monopropyl ether and the like are particularly preferable examples.
  • These organic solvents can be used singly or in combination of two or more.
  • the addition amount of the organic solvent is not particularly limited, but it is preferably 100 to 100,000 parts by mass with respect to 100 parts by mass of the composition other than the organic solvent. The reason is that when the addition amount is less than 100 parts by mass, it may be difficult to adjust the viscosity of the curable resin composition. On the other hand, when the addition amount exceeds 100,000 parts by mass, the curable resin composition may be difficult to adjust. This is because the storage stability of the composition may be decreased, or the viscosity may be excessively decreased to make handling difficult. [0086] (F) Additive
  • the curable resin composition includes a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, a plasticizer, as long as the objects and effects of the present invention are not impaired.
  • An additive such as an agent, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler other than the component (B), a pigment, and a dye may be further contained.
  • the curable resin composition used in the present invention comprises the above (A) ethylenically unsaturated group-containing fluoropolymer and the above (B) component, or, if necessary, the above (C) component, (D) component, It can be prepared by adding (E) an organic solvent and (F) an additive and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a triple roll. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start temperature of the thermal polymerization initiator.
  • the curable resin composition When the curable resin composition is cured by heating, it is preferably heated at a temperature in the range of 30 to 200 ° C for 1 to 180 minutes. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.
  • the antireflection film of the present invention can be produced by including a low refractive index layer comprising a cured film of the curable resin composition on a substrate. Further, the antireflection film can include a high refractive index layer, a medium refractive index layer, a hard coat layer, an antistatic layer, and the like below the low refractive index layer.
  • FIG. 1 shows the force and the antireflection coating 10. As shown in FIG. 1, an antistatic layer 14, a hard coat layer 16, and a low refractive index layer 18 are laminated on a substrate 12.
  • a high refractive index layer (not shown) may be further provided between the hard coat layer 16 and the low refractive index layer 18.
  • the low refractive index layer 18 may be formed directly on the antistatic layer 14 without providing the hard coat layer 16.
  • the low refractive index layer is composed of a cured film obtained by curing the curable resin composition. Since the configuration and the like of the curable resin composition are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the low refractive index layer will be described below.
  • the refractive index of the cured film obtained by curing the curable resin composition (the refractive index of Na-D line (589 nm), measuring temperature 25 ° C), that is, the refractive index of the low refractive index film is 1 45 or less is preferable. This is because when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be significantly reduced when combined with a high refractive index film.
  • the refractive index of the low refractive index film is 1 ⁇ 44 or less.
  • the other low refractive index films exceed 1.45. It may be a value.
  • the refractive index difference with respect to the high refractive index layer is a value of 0.05 or more because a better antireflection effect can be obtained.
  • the reason for this is that if the difference in refractive index between the low refractive index layer and the high refractive index layer is less than 0.05, the synergistic effect of these antireflective film layers cannot be obtained, and instead the antireflective effect. This is because there is a case where the value decreases. Therefore, it is more preferable to set the difference in refractive index between the low refractive index layer and the high refractive index layer to a value within the range of 0.:! To 0.5. More preferably, the value is within the range.
  • the thickness of the low refractive index layer is not particularly limited, and is preferably 50 to 300 nm, for example.
  • the reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as a base may decrease, whereas when the thickness exceeds 300 nm, optical interference does not occur. This is because the antireflection effect may be reduced, and therefore the thickness of the low refractive index layer is more preferably 50 to 250 nm, more preferably 60 to 200 nm.
  • the total thickness may be 50 to 300 nm.
  • the curable composition for forming the high refractive index layer is not particularly limited.
  • a film forming component an epoxy resin, a phenol resin, a melamine resin, an alkyd resin, a cyanate resin, an acrylic resin. It is preferable to include one kind alone or a combination of two or more kinds of resin, polyester resin, urethane resin, siloxane resin and the like. This is because these resins can form a strong thin film as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
  • the refractive index of these resins alone is usually 1.45 to: 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles.
  • metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, ⁇ ⁇ particles, antimony-doped ZnO, A1-doped ⁇ particles, and phosphorus-doped tin oxide ( ⁇ ) particles.
  • ATO antimony-doped tin oxide
  • ITO tin-doped indium oxide
  • ⁇ ⁇ particles antimony-doped ZnO
  • A1-doped ⁇ particles antimony-doped ZnO
  • phosphorus-doped tin oxide ( ⁇ ) particles phosphorus-doped tin oxide ( ⁇ ) particles.
  • ZrO particles TiO particles, silica-coated Ti
  • Examples include 2 2 2 2 3 2 2 2 particles.
  • Antimony-doped tin oxide (AT) particles, tin-doped indium oxide (IT) particles, A1-doped ⁇ particles, phosphorus-doped tin oxide ( ⁇ ) particles, and Al 2 O 3 / ZrO-coated Ti 0 particles are preferable. These metal oxide particles are one kind alone or
  • a hard coat layer or an antistatic layer can be given to the high refractive index layer.
  • a force capable of using a curable composition capable of thermal curing, ultraviolet curing, and electron beam curing an ultraviolet curable composition having good productivity is more preferably used.
  • the thickness of the high refractive index layer is not particularly limited, but is preferably 50-30, OOOnm, for example.
  • the reason for this is that when the thickness of the high refractive index layer is less than 50 nm, when combined with the low refractive index layer, the antireflection effect may decrease the adhesion to the substrate, while the thickness This is because if the thickness exceeds 30, OOOnm, optical interference may occur and the antireflection effect may be reduced.
  • the thickness of the high refractive index layer is more preferably from 50 to 1: OOOnm, and more preferably from 60 to 500 nm.
  • the thickness S of a high refractive index layer shall be 50-300 nm, and force S is used.
  • the constituent material of the hard coat layer used for the antireflection film of the present invention is not particularly limited.
  • examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds.
  • silica particles and metal oxide particles can be added to increase scratch resistance, and an antioxidant and a light stabilizer can be added to avoid alteration of the cured product layer.
  • antioxidants and light stabilizers include, for example, Sumitizer 1 BHT, Summitizer 1 S, Summitizer 1 BP_76, Summitizer 1 MDP_S, Summitizer 1 GM, Summitizer 1 B BM-S, Summitizer 1 WX — R, Sumilyzer NW, Sumilyzer One BP—179, Sumilyzer One BP—101, Sumilyzer One GA_80, Sumilyzer One TNP, Sumilyzer One TPP_R, Sumilyzer P—16 (above, manufactured by Sumitomo Chemical Co., Ltd.), Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (Ciba 'Specialty' Chemicals), Funkrill FA_711M, FA-712HM (Hitachi Chemical Industries, Ltd.) Etc.
  • the thickness of the hard coat layer is not particularly limited, but is preferably set to:! To 50 ⁇ 1 to: more preferably set to ⁇ ⁇ , .
  • the reason for this is that when the thickness of the hard coat layer is less than ⁇ m, the adhesion of the antireflection film to the substrate may not be improved, whereas the thickness exceeds 50 xm. This is because it may be difficult to form a uniform layer.
  • the conductive layer is as described above and will not be described in detail here, by providing the conductive layer, conductivity is imparted to the stacked body, and static electricity is generated and dust and the like are prevented from attaching.
  • the type of base material used for the antireflection film is not particularly limited.
  • Preferable examples include triacetyl cellulose, polyethylene terephthalate resin (Lumirror, etc.
  • an antireflection film containing these base materials it is excellent in the field of application of a wide range of antireflection films such as color lenses in camera lens units, television (CRT) screen display units, and liquid crystal display devices. An antireflection effect can be obtained.
  • the obtained hydroxyl group-containing fluoropolymer 1 was subjected to measurement of the polystyrene-equivalent number average molecular weight by gel permeation chromatography 1 and the fluorine content by the alizarin complexone method.
  • the proportion of each monomer component constituting the hydroxyl group-containing fluoropolymer 1 was determined from the NMR analysis results of both —NMR and 13 C—NMR, the elemental analysis results, and the fluorine content. The results are shown in Table 2.
  • VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (8) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000.
  • NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the above formula (13).
  • a hydroxyl group-containing fluoropolymer was synthesized in the same manner as in Production Example 1 except that the amounts of ethyl vinyl ether and hydroxyethyl vinyl ether were changed as shown in Table 1. This is designated as hydroxyl-containing fluoropolymer 2. The ratio of each monomer component is shown in Table 2.
  • tetraethoxysilane (Toray Dow Corning Silicone Co., Ltd., AY43-101) 64.85g, ethanolanol 692.72g, N, N-dimethylenoacetamide 40.OOg
  • 200.OOg of 25% aqueous ammonia in water at night was added.
  • the solution was allowed to react at 50 ° C for 6 hours with stirring, and further, 43 g of butyltrimethoxysilane (Toray 'Dowcoung' Silicone Co., Ltd., SZ6300) was added and reacted at 50 ° C for 2 hours. .
  • the average particle size and specific surface area were measured in the same manner as in Production Example 5. Table 4 shows the measurement results.
  • porous silica particles (B-4) In a quartz separable flask, tetraethoxysilane 106 ⁇ 24g, methanolol 420 ⁇ 49g, 1,2-butaneji-nore 200. After OOg was calorie-free and evenly mixed, 10% aqueous solution of ammonia 100.OOg And 160.00 g of ultrapure water were added. After that, the solution was allowed to react at 30 ° C for 12 hours while stirring, and further added with 28 g of Atalyloxypropyltrimethoxysilane (Toray 'Dow Corning. Silicone Co., Ltd., AY43-310M) at 60 ° C. Reacted for hours.
  • Atalyloxypropyltrimethoxysilane Toray 'Dow Corning. Silicone Co., Ltd., AY43-310M
  • the average particle size and specific surface area were measured in the same manner as in Production Example 5. Table 4 shows the measurement results.
  • a 0.1% aqueous solution (1000.00 g) was added, stirred and allowed to stand.
  • the upper layer separated into two layers was separated, and concentrated to a solid content concentration of 5% by a rotary evaporator to obtain a porous silica particle solution (B-5).
  • the average particle size and specific surface area were measured in the same manner as in Production Example 5. Table 4 shows the measurement results.
  • NK Ester A _TMM_ 3LM_N pentaerythritol tri Atari rate 60 mass 0/0 and pentaerythritol Atari rate 40% by weight in the reaction solution.
  • NK Ester A _TMM_ 3LM_N pentaerythritol tri Atari rate 60 mass 0/0 and pentaerythritol Atari rate 40% by weight in the reaction solution.
  • participating in the reaction (Only pentaerythritol triatallylate having a hydroxyl group.) 549 parts were added dropwise at 30 ° C over 1 hour, and then stirred at 60 ° C for 10 hours to obtain a reaction solution.
  • the product in this reaction solution that is, the amount of residual isocyanate in the organic compound having a polymerizable unsaturated group was measured by FT-IR, and it was 0.1% by mass or less, and each reaction was performed almost quantitatively. I confirmed that.
  • the absorption peak of 2550 Kaiser characteristic of mercapto groups in the raw material
  • the absorption peak of 2260 Kaiser characteristic of the raw isocyanate compound
  • Ginoleconia particles (UEP-100 (manufactured by Daiichi Rare Elemental Chemical Co., Ltd.) (Partial particle size 10 to 30 nm)) 300 parts of methyl ethyl ketone (MEK) 700 parts, and 168 hours with glass beads The glass beads were removed to obtain 950 parts of zirconia-dispersed sol. After weighing 2g of the zirconia dispersion sol in an aluminum dish, it was dried on a hot plate at 120 ° C for 1 hour and weighed to obtain a solid content of 30%.
  • UDP-100 manufactured by Daiichi Rare Elemental Chemical Co., Ltd.
  • MEK methyl ethyl ketone
  • a composition containing the specific organic compound synthesized in Production Example 10 (S-1) 0.86 g, dipentaerythritol hexaatalylate (DPHA) 13.4 g, p-methoxyphenolanol 016 g, 0.033 g of ion-exchanged water was stirred at 60 ° C for 3 hours, then added with 0.333 g of orthoformate methyl ester and further heated and stirred at the same temperature for 1 hour to obtain surface-modified dinoleconia particles. 14.6 g of the dispersion 1 was obtained.
  • composition containing polymerizable unsaturated groups produced in Production Example 10 (S-1) 2. 32 parts, silica particle sol (methylethylketone silica sol, MEK_ST, Nissan Chemical Industries, Ltd., number average particle size 0 022 xm, silica concentration 30%) 91. 3 parts (27 parts as silica particles), 0.112 parts of ion-exchanged water, and 0.01 part of p-methoxyphenol were mixed at 60 ° C for 4 hours. After the stirring, 1.36 parts of onoletoformic acid methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain reactive particles (dispersion liquid (S-3)).
  • silica particle sol methylethylketone silica sol, MEK_ST, Nissan Chemical Industries, Ltd., number average particle size 0 022 xm, silica concentration 30%
  • This dispersion (S—3) 98 ⁇ 6 g, composition (S—2) 3 ⁇ 4 g, 1-hydroxycyclohexyl phenyl ketone 2 ⁇ lg, Irgacure 907 (2-methyl-1 [4 (methylthio) phenyl ] —2—Morpholinopropane 1-one, Ciba 'Specialty' Chemicals) 1 ⁇ 2g, Dipentaerythritol Hexaatalylate (DPHA) 3 ⁇ 2g, Tinuvin 144 (Bis (1, 2, 2, 6, 6-Pentamethyl-4-piperidinyl) [(3,5-Di-tert-butyl-4-hydroxyphenyl) methyl] butyl malonate, manufactured by Tinoku 'Specialty' Chemicals) 3.7 g, mixed with 6 g hexanone in the mouth, containing silica particles 148 g of a composition for hard coat layer (H-2: solid content concentration
  • FeCl as oxidizing agent, methyl alcohol, 2-butyl alcohol and ethyl acetate
  • the catalyst solution prepared above was spin-coated on the surface of Arton film (trade name, manufactured by JSR, film thickness: 100 ⁇ m), and the obtained catalyst coating film was dried at 60 ° C. for 3 minutes.
  • the polyester film on which the hard coat layer and the catalyst coating film were formed was placed in a CV D chamber designed to produce a saturated 3,4_ethylenedioxythiophene monomer. After 3,4_ethylenedioxythiophene was polymerized for 30 seconds, it was washed with methanol solvent to remove unreacted materials, and a film (b_1) with a conductive layer was prepared.
  • a film (b_2) having a conductive layer was prepared in the same manner as in Example 14 except that a triacetyl cellulose film (manufactured by LFO, film thickness 80 ⁇ m) was used instead of the Arton film.
  • the composition for dinoleconia-containing hard coat layer prepared in Production Example 12 (H-1: solid content concentration 30%) is applied to a wire bar coater ( # 7) was applied and dried in an oven at 80 ° C for 1 minute to form a coating film.
  • a hard coat layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.9 mj / cm 2 using a high-pressure mercury lamp in air.
  • the film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument, it was 3 ⁇ m.
  • the composition for silica particle-containing hard coat layer (H-2: solid content concentration 50%) prepared in Production Example 13 was applied to a wire bar coater ( # 12) and dried in an oven at 80 ° C for 1 minute to form a coating film.
  • ultraviolet rays were irradiated under a light irradiation condition of 0.6 mj / cm 2 using a high-pressure mercury lamp in the air to form a hard coat layer.
  • the film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument, it was 5 ⁇ m.
  • This curable resin composition was applied onto a silicon wafer by a spin coater so that the thickness after drying was about 0.1 lxm, and then a light of 0.5 mj / cm 2 was applied using a high-pressure mercury lamp under nitrogen. It was cured by irradiation with ultraviolet rays under irradiation conditions. With respect to the obtained cured film, the refractive index (n 25 ) at a wavelength of 589 nm at 25 ° C. was measured using an ellipsometer. Table the results
  • a curable resin composition was obtained in the same manner as in Production Example 19 except that the composition in Table 5 was followed. More The refractive index of the curable resin composition obtained in the same manner as in Production Example 19 was measured. The results are shown in Table 5.
  • An antireflection film was obtained in the same manner as in Example 1 except that Arton film (trade name, manufactured by JSR, film thickness 100 ⁇ m) was used instead of film (b_1) having a conductive layer (antistatic layer). It was.
  • Arton film trade name, manufactured by JSR, film thickness 100 ⁇ m
  • a laminated film was obtained in the same manner as in Example 1 except that the curable resin composition prepared in Production Example 19 was used.
  • Abrasion resistance test 1 (Cloth abrasion resistance test)
  • the surfaces of the antireflection films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were reciprocated using a cellulose nonwoven fabric impregnated with ethanol (trade name Bencot S-2, Asahi Kasei Sen Co., Ltd.). By rubbing by hand 200 times, the scratch resistance of the antireflection film surface was visually evaluated according to the following criteria. The results are shown in Table 5.
  • A The sample surface for evaluation is intact.
  • ⁇ The surface of the sample for evaluation is fine, scratched, or distorted.
  • ⁇ The surface of the sample for evaluation is damaged.
  • Steel wool resistance test of antireflection films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was carried out by the following method.
  • steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded with a load of 200 g.
  • Gakushin type friction fastness tester AB-301, manufactured by Tester Sangyo Co., Ltd.
  • Example:! ⁇ 7 and comparative example:! ⁇ 4 Fingerprints were applied to the surface of the antireflection film prepared in 4 and the surface of the film was wiped off with a non-woven fabric (Bencot S_2, Asahi Kasei Fibers Co., Ltd.). It was. Contamination resistance was evaluated according to the following criteria. The results are shown in Table 5.
  • the anti-reflective properties of the anti-reflective coatings prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were compared with the spectral reflectance measuring device (self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090 , Manufactured by Hitachi, Ltd.), the reflectance at a wavelength of 550 nm was measured and evaluated. Specifically, the reflectance of the antireflection film is measured using the reflectance of the deposited aluminum film as a reference (100%). When the reflectance at the wavelength of 550 nm is 1% or less, it exceeds ⁇ , and exceeds 1%. X.
  • the surface resistance of the antireflection film prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was measured using a high resistance meter (Agilent 4339B) and a resiliency cell (Agilent 16008B) at an applied voltage of 100 V, and the surface When the resistance value is less than 10 1Q Q / mouth, it is marked as ⁇ , and when the resistance value is more than 10 1 ° 0 / b, X is marked as X
  • the antireflection film of the present invention is useful as an antireflection film having excellent antistatic properties, scratch resistance and stain resistance.

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Abstract

Disclosed is an antireflective film comprising a conductive layer and a low-refractive index layer arranged on a base. The conductive layer is formed through vapor phase polymerization of a monomer such as pyrrole or thiophene, while the low-refractive index layer is made of a cured product of a curable resin composition containing the following components (A) and (B1). (A) A fluorine-containing polymer having an ethylenically unsaturated group. (B1) Porous silica particles composed of hydrolysis products and/or hydrolysis-condensation products of silicon compounds represented by the formulae (1) and (2) below and having an average particle diameter of 5-50 nm. R1hSiX4-h (1) R2jSiX4-j (2) (In the above formulae, R1 represents an alkyl group having 1-8 carbon atoms; Xs independently represent an alkoxy group having 1-4 carbon atoms or the like; h represents an integer of 0-1; R2 represents an alkenyl group having 2-8 carbon atoms, an acryloxyalkyl group having 4-8 carbon atoms or a methacryloxyalkyl group having 5-8 carbon atoms; and j represents an integer of 1-3.)

Description

明 細 書  Specification
反射防止膜  Anti-reflection coating
技術分野  Technical field
[0001] 本発明は、反射防止膜に関する。より詳細には、帯電防止性、耐擦傷性及び耐汚 染性に優れた反射防止膜に関する。  [0001] The present invention relates to an antireflection film. More specifically, the present invention relates to an antireflection film excellent in antistatic properties, scratch resistance and stain resistance.
背景技術  Background art
[0002] 液晶表示パネル、冷陰極線管パネル、プラズマディスプレー等の各種表示パネル において、外光の映りを防止し、画質を向上させるために、低屈折率性、耐擦傷性、 塗工性及び耐汚染性に優れた硬化物からなる低屈折率層を含む反射防止膜が求 められている。  In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, low refractive index properties, scratch resistance, coating properties, There is a demand for an antireflection film including a low refractive index layer made of a cured product having excellent contamination properties.
これら表示パネルにおいては、付着した指紋、埃等を除去するため表面をエタノー ル等を含侵したガーゼで拭くことが多ぐ耐擦傷性が求められている。また、付着した 指紋、埃等が容易に拭き取れる耐汚染性も求められてレ、る。  These display panels are required to have scratch resistance that is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like. There is also a need for anti-contamination that can easily wipe off attached fingerprints and dust.
特に、液晶表示パネルにおいては、反射防止膜は、偏光板と貼り合わせた状態で 液晶ユニット上に設けられている。また、基材としては、例えば、トリァセチルセルロー ス等が用いられているが、このような基材を用いた反射防止膜では、偏光板と貼り合 わせる際の密着性を増すために、通常、アルカリ水溶液でケン化を行う必要がある。 従って、液晶表示パネルの用途においては、耐久性において、特に、耐アルカリ性 に優れた反射防止膜が求められている。  In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, as the base material, for example, triacetyl cellulose is used, but in the antireflection film using such a base material, in order to increase the adhesion when bonded to the polarizing plate, Usually, it is necessary to saponify with an alkaline 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.
[0003] 反射防止膜の低屈折率層用材料として、例えば、水酸基含有含フッ素重合体を含 むフッ素樹脂系塗料が知られている（例えば、特許文献:!〜 3)。 [0003] As a material for a low refractive index layer of an antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known (for example, Patent Documents:! To 3).
しかし、このようなフッ素樹脂系塗料では、塗膜を硬化させるために、水酸基含有含 フッ素重合体と、メラミン樹脂等の硬化剤とを、酸触媒下、加熱して架橋させる必要が あり、加熱条件によっては、硬化時間が過度に長くなり、使用できる基材の種類が限 定されてしまうという問題があった。  However, in such a fluororesin-based paint, it is necessary to heat and crosslink a hydroxyl group-containing fluoropolymer and a curing agent such as melamine resin in the presence of an acid catalyst in order to cure the coating film. Depending on the conditions, there is a problem that the curing time becomes excessively long and the types of base materials that can be used are limited.
また、得られた塗膜についても、耐候性には優れているものの、耐擦傷性や耐久性 に乏しいという問題があった。 [0004] そこで、上記の問題点を解決するため、少なくとも 1個のイソシァネート基と少なくと も 1個の付加重合性不飽和基とを有するイソシァネート基含有不飽和化合物と水酸 基含有含フッ素重合体とを、イソシァネート基の数/水酸基の数の比が 0. 01〜： 1. 0 の割合で反応させて得られる不飽和基含有含フッ素ビニル重合体を含む塗料用組 成物が提案されている（例えば、特許文献 4)。 Also, the obtained coating film has a problem that it has poor weather resistance but poor scratch resistance and durability. [0004] Therefore, in order to solve the above problems, an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition-polymerizable unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. A composition for coatings containing an unsaturated group-containing fluorinated vinyl polymer obtained by reacting a polymer with an isocyanate group at a ratio of the number of isocyanate groups to the number of hydroxyl groups of 0.01 to 1.0 is proposed. (For example, Patent Document 4).
[0005] しかし、上記特許文献 4では、不飽和基含有含フッ素ビニル重合体を調製する際に[0005] However, in Patent Document 4 described above, when preparing a fluorine-containing vinyl polymer containing an unsaturated group,
、水酸基含有含フッ素重合体の全ての水酸基を反応させるのに十分な量のイソシァ ネート基含有不飽和化合物を用いず、積極的に当該重合体中に未反応の水酸基を 残存させるものであった。 In addition, an isocyanate group-containing unsaturated compound in an amount sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluoropolymer was not used, and unreacted hydroxyl groups were actively left in the polymer. .
このため、このような重合体を含む塗料用組成物は、低温、短時間での硬化を可能 とするものの、残存した水酸基を反応させるために、メラミン樹脂等の硬化剤をさらに 用いて硬化させる必要があった。さらに、上記公報で得られた塗膜は、塗工性、耐擦 傷性についても十分とはいえないという課題があった。  Therefore, a coating composition containing such a polymer can be cured at a low temperature in a short time, but is further cured using a curing agent such as a melamine resin in order to react the remaining hydroxyl group. There was a need. Furthermore, the coating film obtained in the above publication has a problem that it is not sufficient in coating property and scratch resistance.
[0006] 特許文献 1 :特開昭 57— 34107号公報 [0006] Patent Document 1: Japanese Patent Laid-Open No. 57-34107
特許文献 2 :特開昭 59— 189108号公報  Patent Document 2: JP 59-189108 A
特許文献 3 :特開昭 60— 67518号公報  Patent Document 3: JP-A-60-67518
特許文献 4 :特開昭 61— 296073号公報  Patent Document 4: JP-A-61-296073
[0007] 本発明は、上記の課題を鑑みてなされたものであり、特に、帯電防止性、耐擦傷性 及び耐汚染性に優れた反射防止膜を提供することを目的とする。 [0007] The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an antireflection film excellent in antistatic property, scratch resistance, and contamination resistance.
発明の開示  Disclosure of the invention
[0008] 本発明によれば、以下の反射防止膜が提供される。  [0008] According to the present invention, the following antireflection film is provided.
1.基材上に、  1. On the substrate,
ピロ一ノレ、チォフェン、フラン、セレノフェン及び 3, 4_エチレンジォキシチォフェン 並びにこれらの誘導体からなる群から選択される少なくとも一種の単量体を気相重合 して形成された導電層、並びに、  A conductive layer formed by vapor-phase polymerization of at least one monomer selected from the group consisting of pyrrolinole, thiophene, furan, selenophene and 3,4_ethylenedioxythiophene and derivatives thereof; and ,
下記成分 (A)及び (B1) :  The following components (A) and (B1):
(A)エチレン性不飽和基含有含フッ素重合体、  (A) an ethylenically unsaturated group-containing fluoropolymer,
(B1)下記式（1)で表されるケィ素化合物及び式（2)で表されるケィ素化合物の加 水分解物及び/又は加水分解縮合物からなり、平均粒径が 5〜50nmである多孔質 シリカ粒子 (B1) Addition of a key compound represented by the following formula (1) and a key compound represented by the formula (2) Porous silica particles comprising a hydrolyzate and / or hydrolysis condensate and having an average particle size of 5 to 50 nm
R1 SiX · · · (1) R 1 SiX (1)
h 4-h  h 4-h
R2 SiX · · · (2) R 2 SiX (2)
j 4-j  j 4-j
(R1は炭素数 1〜8のアルキル基、 Xはそれぞれ独立に炭素数 1〜4のアルコキシ基、 ハロゲノ基、イソシァネート基（_N = C =〇）、カルボキシル基、炭素数 2〜4のアル キルォキシカルボニル基又は炭素数 1〜4のアルキルアミノ基、 hは 0〜 1の整数を示 す。 R2は炭素数 2〜8のアルケニル基、炭素数 4〜8のアタリロキシアルキル基又は炭 素数 5〜8のメタクリロキシアルキル基、 jは 1〜3の整数を示す。尚、式（1)の X及び式 (2)の Xは同一であっても異なっていてもよレ、。 ）、 (R 1 is an alkyl group having 1 to 8 carbon atoms, X is independently an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group (_N = C = 0), a carboxyl group, an alkyl group having 2 to 4 carbon atoms. A siloxycarbonyl group or an alkylamino group having 1 to 4 carbon atoms, h is an integer of 0 to 1. R 2 is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms, or A methacryloxyalkyl group having 5 to 8 carbon atoms, j represents an integer of 1 to 3. X in formula (1) and X in formula (2) may be the same or different. ),
を含む硬化性樹脂組成物の硬化物からなる低屈折率層、 A low refractive index layer comprising a cured product of a curable resin composition containing
を有する反射防止膜。 An antireflection film.
2.基材上に、 2. On the base material
ピロ一ノレ、チォフェン、フラン、セレノフェン及び 3, 4—エチレンジォキシチォフェン 並びにこれらの誘導体からなる群から選択される少なくとも一種の単量体を気相重合 して形成された導電層、並びに、  A conductive layer formed by vapor-phase polymerization of at least one monomer selected from the group consisting of pyronole, thiophene, furan, selenophene and 3,4-ethylenedioxythiophene and derivatives thereof; and ,
下記成分 (A)及び (B2) :  The following ingredients (A) and (B2):
(A)エチレン性不飽和基含有含フッ素重合体、  (A) an ethylenically unsaturated group-containing fluoropolymer,
(B2)下記式（1)で表されるケィ素化合物、式 (2)で表されるケィ素化合物及び式（ 3)で表されるケィ素化合物の加水分解物及び/又は加水分解縮合物からなり、平 均粒径が 5〜50nmである多孔質シリカ粒子  (B2) a key compound represented by the following formula (1), a key compound represented by the formula (2) and a hydrolyzate and / or a hydrolyzed condensate of the key compound represented by the formula (3) Porous silica particles having an average particle diameter of 5 to 50 nm
R1 SiX •••(l) R 1 SiX ••• (l)
h 4-h  h 4-h
R2 SiX ' ■••(2) R 2 SiX '■ •• (2)
j 4-j  j 4-j
R3 SiX •••(3) R 3 SiX ••• (3)
k 4 k  k 4 k
(R1は炭素数 1〜8のアルキル基、 Xはそれぞれ独立に炭素数 1〜4のアルコキシ基、 ハロゲノ基、イソシァネート基（_N = C =〇）、カルボキシル基、炭素数 2〜4のアル キルォキシカルボニル基又は炭素数 1〜4のアルキルアミノ基、 hは 0〜 1の整数を示 す。 R2は炭素数 2〜8のアルケニル基、炭素数 4〜8のアタリロキシアルキル基又は炭 素数 5〜8のメタクリロキシアルキル基、 jは 1〜3の整数を示す。 R3は炭素数 1〜12の フッ素置換アルキル基、 kは 1〜3の整数を示す。尚、式（1)の X、式（2)の X及び式（(R 1 is an alkyl group having 1 to 8 carbon atoms, X is independently an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group (_N = C = 0), a carboxyl group, an alkyl group having 2 to 4 carbon atoms. A siloxycarbonyl group or an alkylamino group having 1 to 4 carbon atoms, h is an integer of 0 to 1. R 2 is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms, or Charcoal A methacryloxyalkyl group having a prime number of 5 to 8, j represents an integer of 1 to 3; R 3 represents a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and k represents an integer of 1 to 3. X in formula (1), X in formula (2) and formula (
3)の Xは、同一であっても異なっていてもよレ、。）、 X in 3) can be the same or different. ),
を含む硬化性樹脂組成物の硬化物からなる低屈折率層、 A low refractive index layer comprising a cured product of a curable resin composition containing
を有する反射防止膜。 An antireflection film.
3.前記多孔質シリカ粒子 (B1)が、前記式（1)で表されるケィ素化合物及び式 (2)で 表されるケィ素化合物の合計を 100モル％としたとき、前記加水分解物及び/又は 加水分解縮合物が、式（1)で表されるケィ素化合物 67〜99モル％及び式（2)で表 されるケィ素化合物 33〜1モル％の反応物からなる、上記 1に記載の反射防止膜。 3. When the porous silica particles (B1) have a total of 100 mol% of the key compound represented by the formula (1) and the key compound represented by the formula (2), the hydrolyzate And / or the hydrolysis condensate comprises a reactant of 67 to 99 mol% of the key compound represented by formula (1) and 33 to 1 mol% of the key compound represented by formula (2). The antireflection film described in 1.
4.前記多孔質シリカ粒子 (B2)が、前記式（1)で表されるケィ素化合物、式 (2)で表 されるケィ素化合物及び式（3)で表されるケィ素化合物の合計を 100モル％としたと き、前記加水分解物及び Z又は加水分解縮合物が、式（1)で表されるケィ素化合物 60〜98モル％、式（2)で表されるケィ素化合物:!〜 30モル％及び式（3)で表される ケィ素化合物 1〜20モル％の反応物からなる、上記 2に記載の反射防止膜。 4. The porous silica particles (B2) are a total of the key compound represented by the formula (1), the key compound represented by the formula (2), and the key compound represented by the formula (3). Is 100 mol%, the hydrolyzate and Z or hydrolysis condensate are 60 to 98 mol% of the key compound represented by the formula (1) and the key compound represented by the formula (2). 3. The antireflection film as described in 2 above, comprising a reactant of 30 mol% and 1 to 20 mol% of a key compound represented by the formula (3):
5.前記式（1)で表されるケィ素化合物において、 hが 0である、上記:!〜 4のいずれ かに記載の反射防止膜。  5. The antireflection film according to any one of the above:! To 4, wherein h is 0 in the key compound represented by the formula (1).
6.前記多孔質シリカ粒子（B1)又は（B2)力 水、炭素数 1〜3のアルコール、塩基 性化合物、並びに酸アミド、ジオール及びジオールの半エーテルからなる群から選 ばれる少なくとも 1種の存在下で加水分解及び/又は加水分解縮合されたものであ る上記 1〜5のいずれかに記載の反射防止膜。  6. Existence of at least one selected from the group consisting of the porous silica particles (B1) or (B2) water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and half ethers of diols. 6. The antireflection film according to any one of 1 to 5, which is hydrolyzed and / or hydrolyzed and condensed below.
7.前記エチレン性不飽和基含有含フッ素重合体 (A)が、  7.The ethylenically unsaturated group-containing fluoropolymer (A)
1個のイソシァネート基と、少なくとも 1個のエチレン性不飽和基とを含有する化合物 と、  A compound containing one isocyanate group and at least one ethylenically unsaturated group;
水酸基含有含フッ素重合体と、  A hydroxyl group-containing fluoropolymer,
をイソシァネート基 Z水酸基のモル比が 1. 1〜： 1. 9の割合で反応させて得られる エチレン性不飽和基含有含フッ素重合体である上記:!〜 6のいずれかに記載の反射 防止膜。  Is an ethylenically unsaturated group-containing fluoropolymer obtained by reacting an isocyanate group with a molar ratio of Z hydroxyl group of 1.1 to 1.9. film.
8.前記水酸基含有含フッ素重合体が、下記構造単位 (a)、（b)及び (c)の合計 100 モル％に対して、構造単位（a) 20〜70モル％、構造単位（b) 10〜70モル％及び構 造単位（c) 5〜70モル％の割合で含んでなり、かつ、 8. The hydroxyl group-containing fluoropolymer has a total of 100 structural units (a), (b) and (c) below: And the structural unit (a) 20 to 70 mol%, the structural unit (b) 10 to 70 mol% and the structural unit (c) 5 to 70 mol% with respect to mol%, and
ゲルパーミエーシヨンクロマトグラフィーで測定したポリスチレン換算数平均分子量 が 5, 000-500, 000である上記 7に記載の反射防止膜。  8. The antireflection film according to 7 above, wherein the polystyrene-reduced number average molecular weight measured by gel permeation chromatography is 5,000-500,000.
(a)下記式 (4)で表される構造単位  (a) Structural unit represented by the following formula (4)
(b)下記式（5)で表される構造単位  (b) Structural unit represented by the following formula (5)
(c)下記式 (6)で表される構造単位  (c) Structural unit represented by the following formula (6)
[化 1] [Chemical 1]
F R4 FR 4
一 C一一 C ( 4 )  One C One One C (4)
F F  F F
[式（4)中、 R4はフッ素原子、フルォロアルキル基又は— OITで表される基（R5はァ ルキル基又はフルォロアルキル基を示す）を示す] [In the formula (4), R 4 represents a fluorine atom, a fluoroalkyl group or a group represented by —OIT (R 5 represents an alkyl group or a fluoroalkyl group)]
[化 2]  [Chemical 2]
Figure imgf000007_0001
Figure imgf000007_0001
[式（5)中、 は水素原子又はメチル基を、 R7はアルキル基、— (CH )—OR8若し [In the formula (5), is a hydrogen atom or a methyl group, R 7 is an alkyl group, — (CH 2) —OR 8 or
2  2
くは— OCOR8で表される基（ はアルキル基又はグリシジル基を、 Xは 0又は 1の数 を示す）、カルボキシル基又はアルコキシカルボ二ル基を示す] Or — a group represented by OCOR 8 (represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]
[化 3] [Chemical 3]
Figure imgf000007_0002
Figure imgf000007_0002
[式（6)中、 R9は水素原子又はメチル基を、 R1Qは水素原子又はヒドロキシアルキル 基を、 Vは 0又は 1の数を示す] 9.前記水酸基含有含フッ素重合体が、さらに、前記構造単位 (a)、 （b)及び (c)の合 計 100モル部に対して、ァゾ基含有ポリシロキサン化合物に由来する下記構造単位 (d) 0.：!〜 10モル部を含む上記 8に記載の反射防止膜。 [In the formula (6), R 9 represents a hydrogen atom or a methyl group, R 1Q represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1] 9. The following structural unit derived from an azo group-containing polysiloxane compound with respect to a total of 100 mole parts of the structural units (a), (b), and (c), wherein the hydroxyl group-containing fluoropolymer (d) 0 .: The antireflection film as described in 8 above, containing 10 to 10 mole parts.
(d)下記一般式 (7)で表される構造単位  (d) Structural unit represented by the following general formula (7)
[化 4]  [Chemical 4]
Figure imgf000008_0001
Figure imgf000008_0001
[一般式（7)中、 R11及び R12は、同一でも異なっていてもよぐ水素原子、アルキル 基、ハロゲン化アルキル基又はァリール基を示す] [In the general formula (7), R 11 and R 12 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
10.さらに、導電層と低屈折率層との間に、ハードコート層を有する上記 1〜9のいず れかに記載の反射防止膜。  10. The antireflection film according to any one of 1 to 9, further comprising a hard coat layer between the conductive layer and the low refractive index layer.
[0009] 本発明の反射防止膜によれば、優れた耐擦傷性及び耐汚染性が得られる。 [0009] According to the antireflection film of the present invention, excellent scratch resistance and stain resistance can be obtained.
図面の簡単な説明  Brief Description of Drawings
[0010] [図 1]本発明の反射防止膜の一実施形態に力かる断面図である。 FIG. 1 is a cross-sectional view of an antireflection film according to an embodiment of the present invention.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0011] 本発明の反射防止膜の実施形態について以下説明する。 [0011] An embodiment of the antireflection film of the present invention will be described below.
[0012] 1.導電層 [0012] 1. Conductive layer
本発明の反射防止膜における導電層は帯電防止層として機能する。気相重合によ り形成される導電層は、例えば特開 2003— 82105号公報に記載された方法等によ つて製造することができ、具体的には導電性ポリマーから形成することができる。即ち 、ベース層に酸化剤を数 μ ΐη単位の厚さで塗布し、単量体 (モノマー）を気体状態で 酸化剤塗膜と接触させることで、重合を進行させ、導電性ポリマー膜を基材上に形成 する。この際、接着力を向上させる意味で、有機溶剤とともにポリウレタン、ポリ塩化ビ ニル、ポリビエルアルコール、メチルセルロース、キトサン等の高分子を併用すること も可能である。  The conductive layer in the antireflection film of the present invention functions as an antistatic layer. The conductive layer formed by gas phase polymerization can be produced by, for example, the method described in JP-A-2003-82105, and can be specifically formed from a conductive polymer. In other words, an oxidant is applied to the base layer with a thickness of several μΐη units, and the monomer (monomer) is brought into contact with the oxidant coating film in a gaseous state, whereby the polymerization proceeds and the conductive polymer film is formed as a base. Form on the material. At this time, in order to improve the adhesive strength, it is also possible to use a polymer such as polyurethane, polyvinyl chloride, polyvinyl alcohol, methylcellulose, chitosan together with an organic solvent.
本発明では、酸化剤が塗布されたベース層上で、単量体を気相重合させて導電性 ポリマーからなる導電層を形成するが、この際の反応温度は、 0〜140°Cであることが 好ましレ、。以下、より詳細に重合方法を説明するが、本発明はこれに限定されない。 In the present invention, the monomer is vapor-phase polymerized on the base layer coated with the oxidizing agent to conduct the A conductive layer made of a polymer is formed, and the reaction temperature at this time is preferably 0 to 140 ° C. Hereinafter, the polymerization method will be described in more detail, but the present invention is not limited thereto.
[0013] 具体的には、まず第 1段階として、ベース層の表面に 0. 5〜： 10質量％の酸化剤を 数 z m単位で塗布する。酸化剤として例えば CuCl、トルエンスルホン酸鉄（ΠΙ)、過 [0013] Specifically, as a first step, 0.5 to 10% by mass of an oxidizing agent is applied to the surface of the base layer in units of several zm. Examples of oxidizing agents include CuCl, iron toluenesulfonate (ΠΙ),
2  2
塩素酸鉄 (111)、 FeCl及び Cu (C10 ) · 6Η〇から構成される群から選択された化合  Compound selected from the group consisting of iron chlorate (111), FeCl and Cu (C10) · 6Η〇
2 4 2 2  2 4 2 2
物が単独又は組合せで使用できる。この際の溶剤条件は使用ベース層の種類によ つて異なるが、例えば、メチルアルコール、 2_ブチルアルコール、ェチルセ口ソルブ 、エチルアルコール、シクロへキサン、アセトン、ェチルアセテート、トルエン及びメチ ルェチルケトンから選択される有機溶剤を用いることができる。これらは、単独又は 2 種以上混合して用いることができ、例えば、メチルアルコール、 2_ブチルアルコール 及びェチルセ口ソルブから構成される有機溶剤を 7 : 2 : 1、 6 : 2 : 2、 6 : 3 : 1、 5 : 3 : 2等 の割合で混合して用いる。酸化剤が塗布されたベース層は、酸化剤の分解を考慮し 、 80°C以下の熱風乾燥機で乾燥させる。  Things can be used alone or in combination. The solvent conditions at this time vary depending on the type of base layer used. The organic solvent used can be used. These can be used alone or in combination of two or more. For example, an organic solvent composed of methyl alcohol, 2_butyl alcohol and ethyl acetate sorb 7: 2: 1, 6: 2: 2, 6: Mix at a ratio of 3: 1, 5: 3: 2, etc. The base layer to which the oxidizing agent is applied is dried with a hot air dryer at 80 ° C. or lower in consideration of decomposition of the oxidizing agent.
[0014] 次に第 2段階として、酸化剤で塗布されたベース層に、ピロール、チォフェン、フラ ン、セレノフェン及び 3, 4—エチレンジォキシチォフェン並びにこれらの誘導体から なる群から選択される単量体を、気化して接触させ、ベース層の表面で重合反応を 行う。この際、単量体を気化させる方法としては、密閉されたチャンバ一内で単量体 を 0〜： 140°Cで蒸留させる方法と、 CVD (Chemical Vapor Deposition)による方法 等が挙げられる。このとき、温度条件と反応時間を調整することが好ましぐ重合反応 は、 10秒〜 40分程度行なわれ、一般的には、単量体の種類に応じて変化するが、 膜厚及び表面抵抗値等が目標値に達するまで行なう。  [0014] Next, as a second step, the base layer coated with the oxidizing agent is selected from the group consisting of pyrrole, thiophene, furan, selenophene, 3,4-ethylenedioxythiophene, and derivatives thereof. The monomer is vaporized and brought into contact, and a polymerization reaction is performed on the surface of the base layer. At this time, examples of the method for vaporizing the monomer include a method in which the monomer is distilled at 0 to 140 ° C. in a sealed chamber, a method by CVD (Chemical Vapor Deposition), and the like. At this time, it is preferable to adjust the temperature conditions and the reaction time, and the polymerization reaction is carried out for about 10 seconds to 40 minutes, and generally varies depending on the type of monomer. Repeat until the resistance value reaches the target value.
[0015] 次に第 3段階として、重合が完了した後、未反応の単量体及び酸化剤を除去する ための洗浄工程を行う。この際の使用溶剤としては、通常メタノール等のアルコール 類を用レ、、場合によっては水で洗浄することもできる。  [0015] Next, as a third stage, after the polymerization is completed, a washing step is performed to remove unreacted monomers and oxidizing agents. As the solvent used in this case, alcohol such as methanol is usually used, and in some cases, it can be washed with water.
[0016] 上記のような一連の工程は、段階的又は連続的に行うことができ、単量体の重合か ら導電膜の形成までは、一連の作業工程で処理することができる。得られた導電性 ポリマーフィルムは、ベース層に対する密着性が良好であり、アルコール溶剤に対す る耐性も十分である。 [0017] 導電層の膜厚は、：!〜 2000nmであることが好ましい。 lnm未満の膜厚では、ピン ホール等が発生しやすぐ膜形成が困難であり、また、表面抵抗も大きくなり、帯電防 止性に劣る恐れがある。また、 2000nmを超える膜厚では、表面抵抗は良好である 、透明性、色調が著しく劣り、反射防止膜としては使用困難な場合がある。特に好 ましい膜厚は、透明性、色調、表面抵抗のバランスの観点から、 5〜300nmである。 また、導電層の表面抵抗は通常 102 Ω /口〜 1012 Ω /口である。 [0016] The series of steps as described above can be performed stepwise or continuously, and from the polymerization of the monomers to the formation of the conductive film, they can be performed in a series of working steps. The obtained conductive polymer film has good adhesion to the base layer and has sufficient resistance to alcohol solvents. [0017] The thickness of the conductive layer is preferably:! -2000 nm. If the film thickness is less than 1 nm, pinholes or the like are generated, and it is difficult to form a film immediately. Further, the surface resistance is increased and the antistatic property may be deteriorated. On the other hand, when the film thickness exceeds 2000 nm, the surface resistance is good, but the transparency and color tone are extremely inferior, making it difficult to use as an antireflection film. A particularly preferred film thickness is 5 to 300 nm from the viewpoint of the balance of transparency, color tone, and surface resistance. The surface resistance of the conductive layer is usually 10 2 Ω / port to 10 12 Ω / port.
[0018] 2.硬化性樹脂組成物  [0018] 2. Curable resin composition
本発明で使用される硬化性樹脂組成物は、下記の成分 (A)〜(F)を含み得る。こ れらの成分のうち、（A)及び（B)は必須成分であり、（C)〜（F)は適宜含むことので きる任意成分である。  The curable resin composition used in the present invention may contain the following components (A) to (F). Among these components, (A) and (B) are essential components, and (C) to (F) are optional components that can be appropriately contained.
(A)エチレン性不飽和基含有含フッ素重合体  (A) Ethylenically unsaturated group-containing fluoropolymer
(B)下記第一の多孔質シリカ粒子（B1)又は下記第二の多孔質シリカ粒子（B2) [第一の多孔質シリカ粒子 (B1) ]  (B) The following first porous silica particles (B1) or the following second porous silica particles (B2) [First porous silica particles (B1)]
下記式（1)で表されるケィ素化合物及び式（2)で表されるケィ素化合物の加水分 解物及び/又は加水分解縮合物からなり、平均粒径が 5〜50nmである多孔質シリ 力粒子  A porous material having an average particle diameter of 5 to 50 nm, comprising a hydrolyzate and / or a hydrolyzed condensate of a key compound represented by the following formula (1) and a key compound represented by the formula (2) Siri force particles
R1 SiX · · · (1) R 1 SiX (1)
h 4-h  h 4-h
R2 SiX · · · (2) R 2 SiX (2)
j 4-j  j 4-j
[第二の多孔質シリカ粒子 (B2) ]  [Second porous silica particle (B2)]
下記式（1)で表されるケィ素化合物、式（2)で表されるケィ素化合物及び式（3)で 表されるケィ素化合物の加水分解物及び/又は加水分解縮合物からなり、平均粒 径が 5〜50nmである多孔質シリカ粒子  It comprises a key compound represented by the following formula (1), a key compound represented by the formula (2) and a hydrolyzate and / or a hydrolytic condensate of the key compound represented by the formula (3), Porous silica particles having an average particle size of 5 to 50 nm
R1 SiX •••(l) R 1 SiX ••• (l)
h 4-h  h 4-h
R2 SiX ' ■••(2) R 2 SiX '■ •• (2)
j 4-j  j 4-j
R3 SiX •••(3) R 3 SiX ••• (3)
k 4 k  k 4 k
上記式（1)〜（3)中、
Figure imgf000010_0001
R2、 X、 h、 j、 kは上記の通りである。 In the above formulas (1) to (3),
Figure imgf000010_0001
R 2 , X, h, j, and k are as described above.
(C)少なくとも 2個以上の（メタ）アタリロイル基を含有する多官能 (メタ）アタリレート化 合物及び/又は少なくとも 1個以上の（メタ）アタリロイル基を含有する含フッ素 (メタ) アタリレートイ匕合物 (C) a polyfunctional (meth) atallylate compound containing at least two or more (meth) atalyloyl groups and / or a fluorine-containing (meth) containing at least one or more (meth) atalyloyl groups Atre relay toy compound
(D)活性エネルギー線の照射又は熱により活性種を発生する化合物  (D) Compounds that generate active species upon irradiation with active energy rays or heat
(E)有機溶媒  (E) Organic solvent
(F)添加剤  (F) Additive
これらの成分について以下説明する。  These components will be described below.
[0020] (A)エチレン性不飽和基含有含フッ素重合体 [0020] (A) Ethylenically unsaturated group-containing fluoropolymer
エチレン性不飽和基含有含フッ素重合体は、 1個のイソシァネート基と少なくとも 1 個のエチレン性不飽和基とを含有する化合物と、水酸基含有含フッ素重合体とを、ィ ソシァネート基 Z水酸基のモル比が 1. 1〜： 1. 9の割合で反応させて得られる。  The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by combining a compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer. It is obtained by reacting at a ratio of 1.1 to 1.9.
[0021] (1) 1個のイソシァネート基と、少なくとも 1個のエチレン性不飽和基とを含有する化合 物 [0021] (1) Compound containing one isocyanate group and at least one ethylenically unsaturated group
1個のイソシァネート基と、少なくとも 1個のエチレン性不飽和基とを含有する化合物 としては、分子内に、 1個のイソシァネート基と、少なくとも 1個のエチレン性不飽和基 を含有している化合物であれば特に制限されるものではない。  As a compound containing one isocyanate group and at least one ethylenically unsaturated group, a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule If it is, it will not be restrict | limited in particular.
尚、イソシァネート基を 2個以上含有すると、水酸基含有含フッ素重合体と反応させ る際にゲルィヒを起こす可能性がある。  When two or more isocyanate groups are contained, there is a possibility of causing gelich when reacting with a hydroxyl group-containing fluoropolymer.
また、上記エチレン性不飽和基として、後述する硬化性樹脂組成物をより容易に硬 化させることができることから、（メタ）アタリロイル基を有する化合物がより好ましレ、。 このような化合物としては、 2— (メタ）アタリロイルォキシェチルイソシァネート、 2— ( メタ）アタリロイルォキシプロピルイソシァネート、 1 , 1—ビス [ (メタ）アタリロイルォキシ メチル]ェチルイソシァネートの一種単独又は二種以上の組み合わせが挙げられる。  Moreover, since the curable resin composition mentioned later can be hardened more easily as the said ethylenically unsaturated group, the compound which has a (meth) taroloyl group is more preferable. Examples of such compounds include 2- (meth) ataryloxychetyl isocyanate, 2- (meth) ataryloxypropyl isocyanate, 1,1-bis [(meth) ataryloxymethyl ] Ethyl isocyanate is a single type or a combination of two or more types.
[0022] 尚、このような化合物は、ジイソシァネート及び水酸基含有 (メタ）アタリレートを反応 させて合成することあでさる。 [0022] Such a compound can be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
ジイソシァネートの例としては、 2，4_トリレンジイソシァネート、イソホロンジイソシァ ネート、キシリレンジイソシァネート、メチレンビス（4—シクロへキシルイソシァネアート )、 1 , 3 _ビス（イソシァネートメチル）シクロへキサンが好ましい。  Examples of diisocyanates include 2,4_tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylisocyanate), 1,3_bis (isocyanate) Methyl) cyclohexane is preferred.
[0023] 水酸基含有 (メタ）アタリレートの例としては、 2—ヒドロキシェチル (メタ）アタリレート 、ペンタエリスリトールトリ（メタ）アタリレートが好ましレ、。 尚、水酸基含有多官能 (メタ）アタリレートの市販品としては、例えば、大阪有機化 学（株）製 商品名 HEA、 日本化薬（株）製 商品名 KAYARAD DPHA、 PET[0023] Examples of the hydroxyl group-containing (meth) acrylate are 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate. 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 KAYARAD DPHA, PET
— 30、東亞合成（株）製 商品名 ァロニックス M— 215、 M— 233、 M— 305、 M— 30, manufactured by Toagosei Co., Ltd. Product names Aronix M-215, M-233, M-305, M
— 400等を入手することができる。 — 400 mag can be obtained.
[0024] (2)水酸基含有含フッ素重合体 (2) Hydroxyl group-containing fluoropolymer
水酸基含有含フッ素重合体は、好ましくは、下記構造単位 (a)、（b)及び (c)を含ん でなる。  The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
(a)下記式 (4)で表される構造単位。  (a) A structural unit represented by the following formula (4).
(b)下記式（5)で表される構造単位。  (b) A structural unit represented by the following formula (5).
(c)下記式 (6)で表される構造単位。  (c) A structural unit represented by the following formula (6).
[0025] [化 5] [0025] [Chemical 5]
Figure imgf000012_0001
Figure imgf000012_0001
[式（4)中、 R4はフッ素原子、フルォロアルキル基又は— OR5で表される基（R5はァ ルキル基又はフルォロアルキル基を示す）を示す] [In the formula (4), R 4 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR 5 (R 5 represents an alkyl group or a fluoroalkyl group)]
[0026] [化 6] [0026] [Chemical 6]
H R6 HR 6
H Rf HR f
[式（5)中、 R6は水素原子又はメチル基を、 R7はアルキル基、— (CH )—OR8若し [In the formula (5), R 6 is a hydrogen atom or a methyl group, R 7 is an alkyl group, — (CH 2) —OR 8 or
2  2
くは— OCOR8で表される基（R8はアルキル基又はグリシジル基を、 Xは 0又は 1の数 を示す）、カルボキシル基又はアルコキシカルボ二ル基を示す] Or a group represented by OCOR 8 (R 8 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]
[化 7]  [Chemical 7]
Figure imgf000012_0002
[式（6)中、 は水素原子又はメチル基を、 R1Qは水素原子又はヒドロキシアルキル 基を、 Vは 0又は 1の数を示す]
Figure imgf000012_0002
[In the formula (6), represents a hydrogen atom or a methyl group, R 1Q represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]
[0028] (i)構造単位 (a) [0028] (i) Structural unit (a)
上記式（4)において、 R4及び R5のフルォロアルキル基としては、トリフルォロメチル 基、パーフルォロェチル基、パーフルォロプロピル基、パーフルォロブチル基、パー フルォ口へキシル基、パーフルォロシクロへキシル基等の炭素数 1〜6のフルォロア ルキル基が挙げられる。また、 R5のアルキル基としては、メチノレ基、ェチル基、プロピ ル基、ブチル基、へキシル基、シクロへキシル基等の炭素数 1〜6のアルキル基が挙 げられる。 In the above formula (4), the fluoroalkyl group of R 4 and R 5 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group. And a fluoroalkyl group having 1 to 6 carbon atoms such as a perfluorocyclohexyl group. Examples of the alkyl group for R 5 include alkyl groups having 1 to 6 carbon atoms such as methinole group, ethyl group, propyl group, butyl group, hexyl group, and cyclohexyl group.
[0029] 構造単位（a)は、含フッ素ビニル単量体を重合成分として用いることにより導入する こと力 Sできる。このような含フッ素ビュル単量体としては、少なくとも 1個の重合性不飽 和二重結合と、少なくとも 1個のフッ素原子とを有する化合物であれば特に制限され るものではない。このような例としてはテトラフルォロエチレン、へキサフルォロプロピ レン、 3, 3, 3—トリフルォロプロピレン等のフルォロレフィン類；アルキルパーフルォ ロビニルエーテル又はアルコキシアルキルパーフルォロビニルエーテル類；パーフル ォロ（メチルビニルエーテル）、パーフルォロ（ェチルビニルエーテノレ）、パーフルォロ (プロピルビニルエーテル）、パーフルォロ（ブチルビニルエーテノレ）、パーフルォロ ( イソブチルビュルエーテル）等のパーフルォロ（アルキルビニルエーテル）類；パーフ ノレォロ（プロポキシプロピルビエルエーテノレ）等のパーフルォロ（アルコキシアルキノレ ビュルエーテル）類の一種単独又は二種以上の組み合わせが挙げられる。  [0029] The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such 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 perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers. Perfluoro (alkyl vinyl ethers) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl butyl ether), etc .; Perfluoro (alkoxy alkeno butyl ether) s such as propoxypropyl bietherenole) may be used singly or in combination of two or more.
これらの中でも、へキサフルォロプロピレンとパーフルォロ（アルキルビニルエーテ ノレ）又はパーフルォロ（アルコキシアルキルビュルエーテル）がより好ましぐこれらを 組み合わせて用いることがさらに好ましレ、。  Among these, hexafluoropropylene and perfluoro (alkyl vinyl etherol) or perfluoro (alkoxyalkyl butyl ether) are more preferable, and it is more preferable to use these in combination.
[0030] 尚、構造単位（a)の含有率は、構造単位（a)、（b)及び（c)の合計 100モル％に対 して、 20〜70モノレ％である。この理由は、含有率が 20モル0 /0未満になると、本発明 が意図するところのフッ素含有材料の光学的特徴である、低屈折率の発現が困難と なる場合があるためであり、一方、含有率が 70モル％を超えると、水酸基含有含フッ 素重合体の有機溶剤への溶解性、透明性、又は基材への密着性が低下する場合が あるためである。 [0030] The content of the structural unit (a) is 20 to 70 mono% with respect to a total of 100 mol% of the structural units (a), (b) and (c). This is because if the content is less than 20 mole 0/0, which is the optical characteristics of the fluorine-containing material when the present invention is intended, it may be a case where the expression of the low refractive index becomes difficult, whereas If the content exceeds 70 mol%, the solubility of the hydroxyl group-containing fluorine-containing polymer in an organic solvent, transparency, or adhesion to a substrate may decrease. Because there is.
また、このような理由により、構造単位 (a)の含有率を、構造単位 (a)、 (b)及び (c) の合計 100モノレ0 /0に対して、 25〜65モノレ0 /0とするの力 Sより好ましく、 30〜60モノレ0 /0 とするのがさらに好ましい。 Moreover, such a reason, the content of the structural units (a), the total 100 Monore 0/0 of the structural units (a), (b) and (c), and 25 to 65 Monore 0/0 more preferably the force S to, more preferably to 30-60 Monore 0/0.
[0031] (ii)構造単位 (b) [0031] (ii) Structural unit (b)
式（5)において、 R7又は R8のアルキル基としては、メチノレ基、ェチル基、プロピル 基、へキシル基、シクロへキシル基、ラウリル基等の炭素数 1〜 12のアルキル基が挙 げられ、 R'のアルコキシカルボニル基としては、メトキシカルボニル基、エトキシカノレ ボニル基等が挙げられる。 In the formula (5), examples of the alkyl group represented by R 7 or R 8 include alkyl groups having 1 to 12 carbon atoms such as a methinole group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. Examples of the alkoxycarbonyl group for R ′ include a methoxycarbonyl group and an ethoxycananol group.
[0032] 構造単位 (b)は、上述の置換基を有するビニル単量体を重合成分として用いること により導入すること力 Sできる。このようなビュル単量体の例としては、メチルビュルエー テノレ、ェチノレビニノレエーテノレ、 n—プロピノレビニノレエーテノレ、イソプロピノレビニノレエ一 テル、 n—ブチルビュルエーテル、イソブチルビュルエーテル、 tert—ブチルビュル エーテノレ、 n—ペンチノレビニノレエーテノレ、 n—へキシノレビニノレエーテノレ、 n—ォクチ ノレビエルエーテル、 n—ドデシルビニルエーテル、 2—ェチルへキシルビニルエーテ ノレ、シクロへキシルビニルエーテル等のアルキルビニルエーテルもしくはシクロアル キルビュルエーテル類；ェチルァリルエーテル、ブチルァリルエーテル等のァリルェ 一テル類；酢酸ビュル、プロピオン酸ビュル、酪酸ビニル、ビバリン酸ビュル、力プロ ン酸ビエル、バーサチック酸ビエル、ステアリン酸ビニル等のカルボン酸ビエルエステ ル類；メチル (メタ）アタリレート、ェチル (メタ）アタリレート、 n—ブチル (メタ）アタリレー ト、イソブチル (メタ）アタリレート、 2—メトキシェチル (メタ）アタリレート、 2—エトキシェ チル (メタ）アタリレート、 2 - (n_プロボキシ）ェチル (メタ）アタリレート等の（メタ）ァク リル酸エステル類；（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、ィタコン酸等 の不飽和カルボン酸類等の一種単独又は二種以上の組み合わせが挙げられる。 [0032] The structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component. Examples of such bur monomers include methyl buule tenole, ethino levinino ree tenole, n- propino levino lee tenole, isopropino levino renol ether, n-butyl butyl ether, isobutyl butyl ether. , Tert-butyl butyl etherate, n-pentinorevininore etherenore, n-hexenolevinoreetherenore, n-octenorebiether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc. Alkyl vinyl ethers or cycloalkyl butyl ethers; alkyl ethers such as ethyl allyl ether, butyl allyl ether; butyl acetate, butyl propionate, vinyl butyrate, bisvalinate, bispropionate, versaic acid bisels , Steari Carboxylate biesters such as vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n -butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (Meth) acrylic acid esters such as 2-ethoxyethyl (meth) acrylate, 2- (n_propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, One kind alone or a combination of two or more kinds of unsaturated carboxylic acids such as itaconic acid can be mentioned.
[0033] 尚、構造単位 (b)の含有率は、構造単位（a)、（b)及び（c)の合計 100モル％に対 して、 10〜70モル％である。この理由は、含有率が 10モル％未満になると、水酸基 含有含フッ素重合体の有機溶剤への溶解性が低下する場合があるためであり、一方 、含有率が 70モル％を超えると、水酸基含有含フッ素重合体の透明性、及び低反射 率性等の光学特性が低下する場合があるためである。 [0033] The content of the structural unit (b) is 10 to 70 mol% with respect to a total of 100 mol% of the structural units (a), (b) and (c). This is because if the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, Transparency and low reflection of fluorine-containing polymer This is because the optical characteristics such as efficiency may deteriorate.
また、このような理由により、構造単位 (b)の含有率を、構造単位 (a)、 (b)及び (c) の合計 100モノレ0 /0に対して、 20〜60モノレ0 /0とするの力 Sより好ましく、 30〜60モノレ0 /0 とするのがさらに好ましい。 Moreover, such a reason, the content of the structural units (b), the total 100 Monore 0/0 of the structural units (a), (b) and (c), 20 to 60 Monore 0/0 more preferably the force S to, more preferably to 30-60 Monore 0/0.
[0034] (iii)構造単位 (c) [0034] (iii) Structural unit (c)
式（6)において、 R1Qのヒドロキシアルキル基としては、 2—ヒドロキシェチル基、 2 _ ヒドロキシプロピル基、 3—ヒドロキシプロピル基、 4—ヒドロキシブチル基、 3—ヒドロキ シブチル基、 5—ヒドロキシペンチル基、 6—ヒドロキシへキシル基等が挙げられる。 In formula (6), R 1Q hydroxyalkyl groups include 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 5-hydroxypentyl. Group, 6-hydroxyhexyl group and the like.
[0035] 構造単位（c)は、水酸基含有ビニル単量体を重合成分として用いることにより導入 すること力 Sできる。このような水酸基含有ビュル単量体の例としては、 2—ヒドロキシェ チノレビニノレエーテノレ、 3—ヒドロキシプロピノレビニノレエーテノレ、 2—ヒドロキシプロピノレ ビニノレエーテノレ、 4—ヒドロキシブチノレビニノレエーテノレ、 3—ヒドロキシブチノレビ二ノレ エーテル、 5—ヒドロキシペンチルビニルエーテル、 6—ヒドロキシへキシルビニルェ 一テル等の水酸基含有ビニルエーテル類、 2—ヒドロキシェチルァリルエーテル、 4 ーヒドロキシブチルァリルエーテル、グリセロールモノアリルエーテル等の水酸基含有 ァリルエーテル類、ァリルアルコール等が挙げられる。 [0035] The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl-containing bur monomers include 2-hydroxyethylenovininoleetenore, 3-hydroxypropinorevininoleetenore, 2-hydroxypropinorevininoleetenore, 4-hydroxybutinolebi Hydroxyl-containing vinyl ethers such as ninoleatenole, 3-hydroxybutynolebinino ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl aryl ether, 4-hydroxybutyl aryl ether And hydroxyl group-containing aryl ethers such as glycerol monoallyl ether, aryl alcohol and the like.
また、水酸基含有ビエル単量体としては、上記以外にも、 2—ヒドロキシェチル (メタ )アタリレート、 2—ヒドロキシブチル (メタ）アタリレート、 2—ヒドロキシプロピル (メタ）ァ タリレート、力プロラタトン（メタ）アタリレート、ポリプロピレングリコール（メタ）アタリレー ト等を用いることができる。  In addition to the above, the hydroxyl group-containing vinyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, force prolatathone ( (Meth) acrylate, polypropylene glycol (meth) atrelate, etc. can be used.
[0036] 尚、構造単位（c)の含有率を、構造単位（a)、（b)及び（c)の合計 100モル％に対 して、 5〜70モル％とすることが好ましレ、。この理由は、含有率が 5モル％未満になる と、水酸基含有含フッ素重合体の有機溶剤への溶解性が低下する場合があるため であり、一方、含有率が 70モル％を超えると、水酸基含有含フッ素重合体の透明性 、及び低反射率性等の光学特性が低下する場合があるためである。 [0036] The content of the structural unit (c) is preferably 5 to 70 mol% with respect to the total of 100 mol% of the structural units (a), (b) and (c). ,. The reason for this is that when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
また、このような理由により、構造単位（c)の含有率を、構造単位（a)、（b)及び（c) の合計 100モノレ0 /0に対して、 5〜40モノレ0 /0とするの力 Sより好ましく、 5〜30モノレ0 /0と するのがさらに好ましい。 [0037] (iv)構造単位 (d)及び構造単位 (e) Moreover, such a reason, the content of the structural unit (c), the total 100 Monore 0/0 of the structural units (a), (b) and (c), and 5-40 Monore 0/0 more preferably the force S for further preferably 5 to 30 Monore 0/0. [0037] (iv) Structural unit (d) and structural unit (e)
水酸基含有含フッ素重合体は、さらに下記構造単位 (d)を含んで構成することも好 ましい。  The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).
[0038] (d)下記式（7)で表される構造単位。  [0038] (d) A structural unit represented by the following formula (7).
[化 8]  [Chemical 8]
Figure imgf000016_0001
Figure imgf000016_0001
[式（7)中、 R11及び R12は、同一でも異なっていてもよぐ水素原子、アルキル基、 ハロゲン化アルキル基又はァリール基を示す] [In the formula (7), R 11 and R 12 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
[0039] 式（7)において、 R11又は R12のアルキル基としては、メチノレ基、ェチル基、プロピノレ 基等の炭素数 1〜3のアルキル基力 S、ハロゲン化アルキル基としてはトリフルォロメチ ル基、パーフルォロェチル基、パーフルォロプロピル基、パーフルォロブチル基等の 炭素数 1〜4のフルォロアルキル基等力 ァリール基としてはフエ二ル基、ベンジル基 、ナフチル基等がそれぞれ挙げられる。 In the formula (7), the alkyl group of R 11 or R 12 is an alkyl group having 1 to 3 carbon atoms such as a methinole group, an ethyl group, or a propinole group, and the halogenated alkyl group is a trifluoromethyl group. , Perfluoroethyl groups, perfluoropropyl groups, perfluorobutyl groups, etc. Fluoroalkyl groups having 1 to 4 carbon atoms, etc. The aryl groups are phenyl groups, benzyl groups, naphthyl groups, etc. Can be mentioned.
[0040] 構造単位（d)は、前記式（7)で表されるポリシロキサンセグメントを有するァゾ基含 有ポリシロキサン化合物を用いることにより導入することができる。このようなァゾ基含 有ポリシロキサン化合物の例としては、下記式（8)で表される化合物が挙げられる。  [0040] The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (7). An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (8).
[0041] [化 9]  [0041] [Chemical 9]
Figure imgf000016_0002
Figure imgf000016_0002
[式（8)中、 R13〜R16は、同一でも異なっていてもよぐ水素原子、アルキル基又はシ ァノ基を示し、 R17〜R2°は、同一でも異なっていてもよぐ水素原子又はアルキル基 を示し、 p、 qiま：!〜 6の数、 s、 tiま 0〜6の数、 yiま:!〜 200の数、 ζίま:!〜 20の数を示 す。 ] [In the formula (8), R 13 to R 16 represent the same or different hydrogen atoms, alkyl groups or cyan groups, and R 17 to R 2 ° may be the same or different. P, qi: number of! ~ 6, s, ti number of 0-6, yi number:! ~ 200 number, ζί number:! ~ 20 number . ]
[0042] 式（8)で表される化合物を用いた場合には、構造単位（d)は、下記構造単位（e)の 一部として水酸基含有含フッ素重合体に含まれる。 [0042] When the compound represented by the formula (8) is used, the structural unit (d) is represented by the following structural unit (e): As part, it is contained in a hydroxyl group-containing fluoropolymer.
[0043] (e)下記式（9)で表される構造単位。  [0043] (e) A structural unit represented by the following formula (9).
[化 10]  [Chemical 10]
R14 R17 R18 R13 R 14 R 17 R 18 R 13
― C I— (CH2)qCONH(CH2)s― S Ii-(OSIi)y{CH2)tNHCO(CH2)p— C I ( g ) -CI- (CH 2 ) q CONH (CH 2 ) s -S Ii- (OSIi) y (CH 2 ) t NHCO (CH 2 ) p -CI (g)
R16 R19 R2。 R15 R 16 R 19 R 2 . R 15
[式（9)中、 R13〜R16、 R17〜R2°、 p、 q、 s、 t及び yは、上記式（8)と同じである。 ] [0044] 式（8) , (9)におレ、て、 R13〜R16のアルキル基としては、メチノレ基、ェチル基、プロ ピル基、へキシル基、シクロへキシル基等の炭素数 1〜 12のアルキル基が挙げられ、[In the formula (9), R 13 to R 16 , R 17 to R 2 °, p, q, s, t and y are the same as in the above formula (8). ] [0044] Equation (8), Te me, (9), the alkyl group of R 13 to R 16, Mechinore group, Echiru group, propyl group, hexyl group, carbon atoms such as cyclohexyl group And an alkyl group having a number of 1 to 12,
R17〜R2°のアルキル基としてはメチル基、ェチル基、プロピル基等の炭素数:!〜 3の アルキル基が挙げられる。 Examples of the alkyl group of R 17 to R 2 ° include alkyl groups having! To 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.
[0045] 本発明において、上記式 (8)で表されるァゾ基含有ポリシロキサン化合物としては、 下記式（10)で表される化合物が特に好ましい。 In the present invention, the azo group-containing polysiloxane compound represented by the above formula (8) is particularly preferably a compound represented by the following formula (10).
[0046] [化 11] [0046] [Chemical 11]
Figure imgf000017_0001
Figure imgf000017_0001
[式（10)中、 y及び zは、上記式（8)と同じである。 ]  [In the formula (10), y and z are the same as in the above formula (8). ]
[0047] 尚、構造単位（d)の含有率は、構造単位（a)、（b)及び（c)の合計 100モル部に対 して、 0. 1〜： 10モル部とすることが好ましい。この理由は、含有率が 0. 1モル部未満 になると、硬化後の塗膜の表面滑り性が低下し、塗膜の耐擦傷性が低下する場合が あるためであり、一方、含有率が 10モル部を超えると、水酸基含有含フッ素重合体の 透明性に劣り、コート材として使用する際に、塗布時にハジキ等が発生し易くなる場 合があるためである。 [0047] The content of the structural unit (d) may be 0.1 to 10 mole parts with respect to a total of 100 mole parts of the structural units (a), (b) and (c). preferable. The reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing is lowered, and the scratch resistance of the coated film may be lowered. When the amount exceeds 10 mol parts, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating.
また、このような理由により、構造単位 (d)の含有率を、構造単位 (a)、 (b)及び (c) の合計 100モノレ咅に対して、 0. ：!〜 5モノレ咅とするの力 Sより好ましく、 0.：!〜 3モノレ咅 とするのがさらに好ましい。同じ理由により、構造単位（e)の含有率は、その中に含ま れる構造単位 (d)の含有率を上記範囲にするよう決定することが望ましレ、。 For this reason, the content of the structural unit (d) is set to 0.:! To 5 monolayers with respect to a total of 100 monolayers of the structural units (a), (b) and (c). More preferably, the force S is 0.:! To 3 monolayers. For the same reason, the content of structural unit (e) is included in it It is desirable to determine the content of the structural unit (d) to be within the above range.
[0048] (V)構造単位 (f)  [0048] (V) structural unit (f)
水酸基含有含フッ素重合体は、さらに下記構造単位 (f)を含んで構成することも好 ましい。  The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (f).
[0049] (f)下記式（11)で表される構造単位。  [0049] (f) A structural unit represented by the following formula (11).
[化 12]  [Chemical 12]
( 1 1 )(1 1)
Figure imgf000018_0001
Figure imgf000018_0001
[式（11)中、 R21は乳化作用を有する基を示す] [In formula (11), R 21 represents a group having an emulsifying action]
[0050] 式（11)において、 R21の乳化作用を有する基としては、疎水性基及び親水性基の 双方を有し、かつ、親水性基がポリエチレンオキサイド、ポリプロピレンオキサイド等の ポリエーテル構造である基が好ましレ、。 In the formula (11), the group having an emulsifying action of R 21 has both a hydrophobic group and a hydrophilic group, and the hydrophilic group has a polyether structure such as polyethylene oxide and polypropylene oxide. A certain group is preferred.
[0051] このような乳化作用を有する基の例としては下記式（12)で表される基が挙げられる  [0051] Examples of such a group having an emulsifying action include a group represented by the following formula (12).
[化 13] [Chemical 13]
( 1 2 )(1 2)
Figure imgf000018_0002
Figure imgf000018_0002
[式（12)中、 nは 1〜20の数、 mは 0〜4の数、 uは 3〜50の数を示す]  [In formula (12), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]
構造単位 (f)は、反応性乳化剤を重合成分として用いることにより導入することがで きる。このような反応性乳化剤としては、下記式（13)で表される化合物が挙げられる  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (13).
[0053] [化 14] [0053] [Chemical 14]
Figure imgf000018_0003
[式（13)中、 n、 m及び uは、上記式（12)と同様である]
Figure imgf000018_0003
[In the formula (13), n, m and u are the same as the above formula (12)]
[0054] 尚、構造単位（a)、（b)及び（c)の合計 100モル部に対して、構造単位 (f)の含有 率を、 0.：!〜 5モル部とすることが好ましい。この理由は、含有率が 0. 1モル部以上 になると、水酸基含有含フッ素重合体の溶剤への溶解性が向上し、一方、含有率が 5モル部以下であれば、硬化性樹脂組成物の粘着性が過度に増加せず、取り扱い が容易になり、コート材等に用いても耐湿性が低下しないためである。  [0054] The content of the structural unit (f) is preferably 0.:! To 5 mol parts with respect to a total of 100 mol parts of the structural units (a), (b) and (c). . The reason is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, when the content is 5 mol part or less, the curable resin composition is used. This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
また、このような理由により、構造単位 (f)の含有率を、構造単位（a)、（b)及び (c) の合計 100モノレ咅 こ対して、 0. ：!〜 3モノレ咅 Bとするの力 Sより好ましく、 0. 2〜3モノレ咅 とするのがさらに好ましい。  For this reason, the content of the structural unit (f) is changed from 0.:! To 3 monolayers B for a total of 100 monolayers of the structural units (a), (b) and (c). More preferably, it is more preferably 0.2 to 3 monolayers.
[0055] (vi)分子量  [0055] (vi) Molecular weight
水酸基含有含フッ素重合体は、ゲルパーミエーシヨンクロマトグラフィーで、テトラヒ ドロフランを溶剤として測定したポリスチレン換算数平均分子量が 5, 000-500, 00 0であることが好ましい。この理由は、数平均分子量が 5, 000未満になると、水酸基 含有含フッ素重合体の機械的強度が低下する場合があるためであり、一方、数平均 分子量が 500， 000を超えると、後述する硬化性樹脂組成物の粘度が高くなり、薄膜 コーティングが困難となる場合があるためである。  The hydroxyl group-containing fluoropolymer preferably has a polystyrene equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography using tetrahydrofuran as a solvent. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.
また、このような理由により、水酸基含有含フッ素重合体のポリスチレン換算数平均 分子量を 10, 000〜300, 000とするの力 Sより好ましく、 10, 000〜： 100, 000とする のがさらに好ましい。  For these reasons, the hydroxyl-containing fluoropolymer has a polystyrene equivalent number average molecular weight of 10,000 to 300,000, more preferably S, more preferably 10,000 to 100,000. .
[0056] (3)反応モル比  [0056] (3) Reaction molar ratio
エチレン性不飽和基含有含フッ素重合体は、上述した、 1個のイソシァネート基と、 少なくとも 1個のエチレン性不飽和基とを含有する化合物と、水酸基含有含フッ素重 合体とを、イソシァネート基 Z水酸基のモル比が 1. 1〜： 1. 9の割合で反応させて得 られる。この理由は、モル比が 1. 1未満になると耐擦傷性及び耐久性が低下する場 合があるためであり、一方、モル比が 1. 9を超えると、硬化性樹脂組成物の塗膜のァ ルカリ水溶液浸漬後の耐擦傷性が低下する場合があるためである。  The ethylenically unsaturated group-containing fluorine-containing polymer comprises the above-mentioned compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. It is obtained by reacting at a molar ratio of 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. On the other hand, if the molar ratio exceeds 1.9, the coating film of the curable resin composition may be used. This is because the scratch resistance after immersion in an alkaline solution may be reduced.
また、このような理由により、イソシァネート基 Z水酸基のモル比を、 1. 1〜： 1. 5とす るのが好ましぐ 1. 2〜1.5とするのがより好ましい。 [0057] 硬化性樹脂組成物における、（A)成分の添カ卩量については、特に制限されるもの ではないが、有機溶剤以外の組成物全量に対して通常 1〜95質量％である。この理 由は、添加量が 1質量％未満となると、硬化性樹脂組成物の硬化塗膜の屈折率が高 くなり、十分な反射防止効果が得られない場合があるためであり、一方、添加量が 95 質量％を超えると、硬化性樹脂組成物の硬化塗膜の耐擦傷性が得られなレ、場合が あるためである。 For this reason, the molar ratio of the isocyanate group Z hydroxyl group is preferably 1.1 to 1.5, and more preferably 1.2 to 1.5. [0057] The amount of the additive (A) added in the curable resin composition is not particularly limited, but is usually 1 to 95% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 1% by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. This is because if the addition amount exceeds 95% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
また、このような理由から、 （A)成分の添力卩量を 2〜90質量％とするのがより好まし く、 3〜85質量％の範囲内の値とするのがさらに好ましい。  For this reason, it is more preferable that the amount of added force of the component (A) is 2 to 90% by mass, and it is more preferable that the value is within the range of 3 to 85% by mass.
[0058] (B)多孔質シリカ粒子 [0058] (B) Porous silica particles
本発明で使用される硬化性樹脂組成物には、当該硬化性樹脂組成物の硬化膜の 耐擦傷性、特にスチールウールに対する耐擦傷性を改善する目的で多孔質シリカ粒 子（B)を配合する。多孔質シリカ粒子（B)として、第一の多孔質シリカ粒子（B1)又は 第二の多孔質シリカ粒子 (B2)を使用する。第一の多孔質シリカ粒子 (B1)は下記式 (1)で表されるケィ素化合物及び下記式（2)で表されるケィ素化合物の、加水分解 及び/又は加水分解縮合により得られる。即ち、式（1)で表されるケィ素化合物をカロ 水分解及び/又は加水分解縮合し、かつ式（2)で表されるケィ素化合物を加水分解 及び/又は加水分解縮合することにより得られる。式（1)で表されるケィ素化合物及 び式（2)で表されるケィ素化合物は、混合して同時に加水分解及び/又は加水分 解縮合してもよいし、式（1)で表されるケィ素化合物を加水分解及び/又は加水分 解縮合し、ついで、式（2)で表されるケィ素化合物を加えてさらに加水分解及び/又 は加水分解縮合してもよい。第二の多孔質シリカ粒子（B2)は、下記式（1)で表され るケィ素化合物、下記式（2)で表されるケィ素化合物及び下記式（3)で表されるケィ 素化合物の加水分解及び Z又は加水分解縮合により得られる。即ち、式（1)で表さ れるケィ素化合物を加水分解及び Z又は加水分解縮合し、かつ式（2)で表されるケ ィ素化合物を加水分解及び Z又は加水分解縮合し、かつ式（3)で表されるケィ素化 合物を加水分解及び Z又は加水分解縮合することにより得られる。式（1)で表される ケィ素化合物、式（2)で表されるケィ素化合物及び式 (3)で表されるケィ素化合物は 、混合して同時に加水分解及び Z又は加水分解縮合してもよいし、式（1)で表され るケィ素化合物を加水分解及び/又は加水分解縮合し、ついで、式（2)で表される ケィ素化合物及び式（3)で表されるケィ素化合物を加えてさらに加水分解及び/又 は加水分解縮合してもよい。 The curable resin composition used in the present invention is blended with porous silica particles (B) for the purpose of improving the scratch resistance of the cured film of the curable resin composition, particularly the scratch resistance against steel wool. To do. As the porous silica particles (B), the first porous silica particles (B1) or the second porous silica particles (B2) are used. The first porous silica particles (B1) are obtained by hydrolysis and / or hydrolysis condensation of a key compound represented by the following formula (1) and a key compound represented by the following formula (2). That is, it is obtained by subjecting the key compound represented by the formula (1) to carohydrolysis and / or hydrolysis condensation, and hydrolyzing and / or hydrolytic condensation of the key compound represented by the formula (2). It is done. The key compound represented by the formula (1) and the key compound represented by the formula (2) may be mixed and simultaneously hydrolyzed and / or hydrolyzed or condensed. The represented key compound may be hydrolyzed and / or hydrolyzed and condensed, and then the key compound represented by the formula (2) may be added for further hydrolysis and / or hydrolytic condensation. The second porous silica particle (B2) is composed of a key compound represented by the following formula (1), a key compound represented by the following formula (2), and a key compound represented by the following formula (3). Obtained by hydrolysis of Z and Z or hydrolytic condensation. That is, hydrolysis and Z or hydrolytic condensation of the key compound represented by the formula (1), and hydrolysis and Z or hydrolytic condensation of the key compound represented by the formula (2) It is obtained by hydrolysis and Z or hydrolysis condensation of the key compound represented by (3). The key compound represented by the formula (1), the key compound represented by the formula (2) and the key compound represented by the formula (3) are mixed and simultaneously hydrolyzed and Z or hydrolyzed and condensed. Or expressed by formula (1) Hydrolyzing and / or hydrolytically condensing the key compound, then adding the key compound represented by formula (2) and the key compound represented by formula (3) to further hydrolyze and / or Hydrolysis condensation may be performed.
R1 SiX •••(l) R 1 SiX ••• (l)
h 4-h  h 4-h
R2 SiX ' ■••(2) R 2 SiX '■ •• (2)
j 4-j  j 4-j
R3 SiX •••(3) R 3 SiX ••• (3)
k 4-k  k 4-k
[0059] 式（1)中、 R1は炭素数 1〜8のアルキル基であり、好ましくは炭素数 1〜4のアルキ ル基であり、より好ましくはメチル基、ェチル基、プロピル基である。 In the formula (1), R 1 is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group. .
式（1)、（2)及び（3)中、 Xはそれぞれ独立に炭素数 1〜4のアルコキシ基、ハロゲ ノ基、イソシァネート基、カルボキシル基、炭素数 2〜4のアルキルォキシカルボニル 基又は炭素数 1〜4のアルキルアミノ基であり、好ましくはアルコキシ基、ハロゲノ基で あり、より好ましくはアルコキシ基である。また、式（1)、（2)及び（3)の Xは、同一でも 異なってもよい。  In the formulas (1), (2) and (3), each X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, a carboxyl group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, or An alkylamino group having 1 to 4 carbon atoms, preferably an alkoxy group or a halogeno group, more preferably an alkoxy group. In the formulas (1), (2) and (3), X may be the same or different.
式（1)中、 hは 0〜：!の整数であり、好ましくは 0である。  In the formula (1), h is an integer of 0 to:!, Preferably 0.
式（1)で表される化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン 、テトラブトキシシラン、テトラクロロシラン、メチルトリクロロシラン、メチルトリメトキシシ ラン、メチルトリエトキシシラン、ェチルトリクロロシラン、ェチルトリメトキシシラン、ェチ ルトリエトキシシラン等を挙げることができる。  Examples of the compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrachlorosilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, etyltrichlorosilane, Examples include titrimethoxysilane and ethyltriethoxysilane.
[0060] 式（2)中、 R2は炭素数 2〜8のアルケニル基、炭素数 4〜8のアタリロキシアルキル 基又は炭素数 5〜8のメタクリロキシアルキル基であり、好ましくはビエル基、ァリル基 、アタリロキシェチル基、アタリロキシプロピル基、アタリロキシブチル基、メタクリロキシ ェチル基、メタクリロキシプロピル基、メタクリロキシブチル基である。 In the formula (2), R 2 is an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably a Bier group, An aryl group, an attaryloxychetyl group, an attaryloxypropyl group, an attaryloxybutyl group, a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxybutyl group.
式（2)中、 jは 1〜3の整数であり、好ましくは 1〜2である。  In the formula (2), j is an integer of 1 to 3, preferably 1 to 2.
式（2)で表される化合物としては、例えば、ビュルトリメトキシシラン、ビュルトリェトキ シシラン、ビュルトリクロロシラン、アタリロキシプロピルトリメトキシシラン、メタクリロキシ プロピルトリメトキシシラン等を挙げることができる。  Examples of the compound represented by the formula (2) include butyltrimethoxysilane, butyltrioxysilane, butyltrichlorosilane, attaryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.
式（2)で示される化合物を使用することで、多孔質シリカ粒子はエチレン性不飽和 基を含むものとすることができる。エチレン性不飽和基を含むことにより、硬化性組成 物を硬化せしめた硬化膜を有する本発明の反射防止膜の耐擦傷性が向上する。 By using the compound represented by the formula (2), the porous silica particles can contain an ethylenically unsaturated group. Curable composition by containing ethylenically unsaturated groups The scratch resistance of the antireflection film of the present invention having a cured film obtained by curing the product is improved.
[0061] 式（3)中、 R3は炭素数 1〜： 12のフッ素置換アルキル基であり、好ましくは炭素数 3 〜 12のフッ素置換アルキル基であり、より好ましくは炭素数 3〜： 10のフッ素置換アル キノレ基である。 In the formula (3), R 3 is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, preferably a fluorine-substituted alkyl group having 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms. A fluorine-substituted alkynole group.
式（3)中、 kは 1〜3の整数であり、好ましくは 1〜2である。  In the formula (3), k is an integer of 1 to 3, preferably 1 to 2.
式（3)で表される化合物としては、例えば、 3， 3， 3 _トリフルォロプロピルトリメトキ シシラン、 2 _パーフルォ口へキシルメチルトリメトキシシラン、 2 _パーフルォ口へキ パーフルォロォクチルェチルトリエトキシシラン、 3， 3—ジ（トリフルォロメチル）_ 3_ フルォロプロピルトリエトキシシラン等を挙げることができる。  Examples of the compound represented by the formula (3) are 3, 3, 3_trifluoropropyltrimethoxysilane, 2_perfluorohexylmethyltrimethoxysilane, 2_perfluorohexoxyperfluorooctyl. Ethyltriethoxysilane, 3,3-di (trifluoromethyl) _3_fluoropropyltriethoxysilane, and the like.
式（3)で示される化合物を使用することで、多孔質シリカ粒子は含フッ素アルキル 基を含むものとすることができる。含フッ素アルキル基を含むことにより、硬化性組成 物を硬化せしめた硬化膜の耐汚染性を向上させることができる。  By using the compound represented by the formula (3), the porous silica particles can contain a fluorine-containing alkyl group. By including the fluorine-containing alkyl group, the stain resistance of the cured film obtained by curing the curable composition can be improved.
尚、式（1)で表されるケィ素化合物、式（2)で表されるケィ素化合物及び式（3)で 表されるケィ素化合物は、それぞれ、 2種以上用いてもよい。  Two or more types of the key compound represented by the formula (1), the key compound represented by the formula (2), and the key compound represented by the formula (3) may be used.
[0062] 第一の多孔質シリカ粒子（B1)において、式（1)で表されるケィ素化合物及び式（2 )で表されるケィ素化合物の合計を 100モル％としたとき、式（1)で表されるケィ素化 合物/式（2)で表されるケィ素化合物は、好ましくは、 67〜99/：!〜 33 (モル0 /0)、 より好ましくは 70〜98/2〜30 (モル％)の割合で加水分解及び/又は加水分解縮 合される。 [0062] In the first porous silica particles (B1), when the total of the key compound represented by the formula (1) and the key compound represented by the formula (2) is 100 mol%, the formula ( Kei fluorinated compounds represented by 1) / Kei-containing compound represented by the formula (2) is preferably 67-99 / :! to 33 (mol 0/0), more preferably 70 to 98 / Hydrolyzed and / or hydrolyzed and condensed at a ratio of 2 to 30 (mol%).
第二の多孔質シリカ粒子（B2)において、式（1)で表されるケィ素化合物、式（2)で 表されるケィ素化合物及び（3)で表されるケィ素化合物の合計を 100モル％としたと き、式（1)で表されるケィ素化合物/式（2)で表されるケィ素化合物 Z式 (3)で表さ れるケィ素化合物は、好ましくは、 60〜98/：!〜 30Z：!〜 20 (モノレ0 /0)、より好ましく は 65〜96Z2〜20Z2〜： 15 (モノレ％)の割合で加水分解及び Z又は加水分解縮合 される。 In the second porous silica particle (B2), the total of the key compound represented by formula (1), the key compound represented by formula (2), and the key compound represented by (3) is 100. When the mol% is used, the key compound represented by the formula (1) / the key compound represented by the formula (2) Z the key compound represented by the formula (3) is preferably 60 to 98. / :! ~ 30Z:! ~ 20 ( Monore 0/0), more preferably 65~96Z2~20Z2~: 15 is hydrolyzed and Z or hydrolytic condensation at a ratio of (Monore%).
[0063] 本発明で使用される第一及び第二の多孔質シリカ粒子 (Bl) , (B2)は、平均粒径 力 〜 50nmであり、好ましくは 5〜45nmであり、より好ましくは 5〜40nmである。平 均粒径は、数平均粒径であり、透過型電子顕微鏡観察像により測定する。また、「多 孔質」とは、比表面積が 50〜： 1000m2/gであること、好ましくは 50〜800m2/gで あり、より好ましくは 100〜800m2/gであることを意味する。比表面積は、 BET法に より測定する。 [0063] The first and second porous silica particles (Bl) and (B2) used in the present invention have an average particle size force of ~ 50 nm, preferably 5 to 45 nm, more preferably 5 to 40 nm. flat The average particle diameter is a number average particle diameter, and is measured by a transmission electron microscope observation image. Moreover, the "multi-porous", the specific surface area is 50 to: be 1000 m 2 / g, preferably 50 to 800 m 2 / g, it means that more preferably 100~800m 2 / g . The specific surface area is measured by the BET method.
平均粒径が上記範囲内であれば、得られる塗膜の可視光領域での散乱が抑制で きる。また、多孔質化であることにより、密度が低下し、このような多孔質シリカ粒子を 含む膜の屈折率が低くなる。  If the average particle size is within the above range, scattering of the obtained coating film in the visible light region can be suppressed. In addition, due to the porous structure, the density is lowered, and the refractive index of the film containing such porous silica particles is lowered.
[0064] 多孔質シリカ粒子 (B)は、以下に説明する製造方法により得られる。  [0064] The porous silica particles (B) are obtained by the production method described below.
第一又は第二の多孔質シリカ粒子（Bl) , (B2)は、水、炭素数 1〜3のアルコール 、塩基性化合物、並びに酸アミド、ジオール及びジオールの半エーテルから選ばれ る少なくとも 1種の存在下で、それぞれ、上記式（1)で表されるケィ素化合物及び式（ 2)で表されるケィ素化合物、又は上記式（1)で表されるケィ素化合物、式 (2)で表さ れるケィ素化合物及び式（3)で表されるケィ素化合物を、加水分解及び/又は加水 分解縮合して製造できる。  The first or second porous silica particles (Bl) and (B2) are at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and half ethers of diols. In the presence of a key compound represented by the above formula (1) and a key compound represented by the formula (2), or a key compound represented by the above formula (1), the formula (2) It can be produced by hydrolyzing and / or hydrolytically condensing the key compound represented by the formula (1) and the key compound represented by the formula (3).
[0065] 塩基性化合物として、例えばァミン化合物が用いられ、具体例として、ピリジン、ピロ ール、ピぺラジン、ピロリジン、ピぺリジン、ピコリン、モノエタノールァミン、ジエタノー ノレアミン、ジメチルモノエタノールァミン、モノメチルジェタノールァミン、トリエタノール ァミン、ジァザビシクロオクラン、ジァザビシクロノナン、ジァザビシクロウンデセン、テト ラメチルアンモニゥムハイド口オキサイド、テトラェチルアンモニゥムハイド口オキサイド 、テトラプロピルアンモニゥムハイド口オキサイド、テトラプチルアンモニゥムハイドロォ キサイド、アンモニア、メチノレアミン、ェチルァミン、プロピルァミン、ブチルァミン、 N, N—ジメチルァミン、 N， N—ジェチルァミン、 N, N—ジプロピルァミン、 N， N—ジブ チノレアミン、トリメチルァミン、トリエチノレアミン、トリプロピノレアミン、トリブチルァミン等 を挙げることができる。好ましくはアンモニア、エタノールァミン、水酸化テトラメチルァ ミン等が用いられる。  [0065] As the basic compound, for example, an amine compound is used. Specific examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethylanolamine, dimethylmonoethanolamine. , Monomethyljetanolamine, triethanolamine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydride mouth oxide, tetraethylammonium hydride mouth oxide , Tetrapropyl ammonium hydroxide, tetraptyl ammonium hydroxide, ammonia, methinoreamine, ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N-jetylamine, N, N-dipropylamine, N, N —Jib Noreamin, Torimechiruamin, triethyl Chino rare Ming, tripropinoin rare Min, can be mentioned Toribuchiruamin like. Preferably, ammonia, ethanolamine, tetramethylamine hydroxide or the like is used.
これらの塩基性化合物は、 1種あるいは 2種以上を同時に使用してもよい。  These basic compounds may be used alone or in combination of two or more.
[0066] 酸アミド、ジオール又はジオールの半エーテルは、水及びアルコールと相溶性を有 することが好ましい。 酸アミドとして、例えば N, N—ジメチルホルムアミド、 N, N—ジメチルァセトアミド、[0066] The acid amide, diol or diol half ether is preferably compatible with water and an alcohol. Examples of acid amides include N, N-dimethylformamide, N, N-dimethylacetamide,
N—メチルピロリドン等が用いられ、好ましくは N, N—ジメチルホルムアミド、 N, N— ジメチルァセトアミドが用いられる。 N-methylpyrrolidone or the like is used, and N, N-dimethylformamide, N, N-dimethylacetamide is preferably used.
[0067] ジオールとして、例えばエチレングリコール、プロピレングリコール、 1， 2_ブタンジ オール等が用いられ、好ましくはエチレングリコール、プロピレングリコールが用いら れる。ジオールの半エーテルとして、例えばエチレングリコールモノメチルエーテル、 プロピレングリコールモノメチルエーテルが用いられる。  [0067] As the diol, for example, ethylene glycol, propylene glycol, 1,2-butanediol and the like are used, and preferably ethylene glycol and propylene glycol are used. For example, ethylene glycol monomethyl ether or propylene glycol monomethyl ether is used as the half ether of the diol.
本発明で使用される多孔質シリカ粒子は、合成時に酸アミド、ジオール又はジォー ルの半エーテルを共存させることで粒子を多孔質化することができる。  The porous silica particles used in the present invention can be made porous by the coexistence of acid amide, diol or diol half ether during synthesis.
[0068] 反応液中の式（1)のケィ素化合物及び（2)のケィ素化合物の合計濃度、又は式（1 )〜（3)のケィ素化合物の合計濃度は、完全加水分解縮合物換算で通常 0. 5〜： 10 質量％、好ましくは:!〜 8質量％である。ここで、「完全加水分解縮合物換算」とは、ケ ィ素化合物が完全に加水分解縮合したと仮定して計算した理論値であり、式（1)の ケィ素化合物及び（2)のケィ素化合物の X、又は式（1)〜（3)のケィ素化合物の Xを 、 Xの 1/2モルの酸素原子に置換した場合の質量に相当する。粒子合成時のケィ 素化合物の濃度を上記範囲にすることで、粒子の粗大化を防ぎ、平均粒径 5〜50n mの粒子とできる。  [0068] The total concentration of the key compound of formula (1) and the key compound of formula (2) or the total concentration of the key compounds of formulas (1) to (3) in the reaction solution is a complete hydrolysis condensate. Usually in terms of conversion: 0.5 to 10% by mass, preferably:! To 8% by mass. Here, “in terms of fully hydrolyzed condensate” is a theoretical value calculated on the assumption that the key compound has been completely hydrolyzed and condensed, and includes the key compound of formula (1) and the key of formula (2). This corresponds to the mass in the case where X of the elemental compound or X of the compound of the formulas (1) to (3) is substituted with an oxygen atom of 1/2 mol of X. By making the concentration of the silicon compound during particle synthesis within the above range, coarsening of the particles can be prevented and particles with an average particle size of 5 to 50 nm can be obtained.
式（1)のケィ素化合物及び式（2)のケィ素化合物、又は式（1)のケィ素化合物、式 (2)のケィ素化合物及び式（3)のケィ素化合物は同時に混合して加水分解及び/ 又は加水分解縮合させてもよぐまた、水、炭素数 1〜3のアルコール、塩基性化合 物、並びに酸アミド、ジオール及びジオールの半エーテルから選ばれる少なくとも 1 種の存在下で、式（1)で表されるケィ素化合物を加水分解及び/又は加水分解縮 合し、ついで、それぞれ、式（2)で表されるケィ素化合物、又は式（2)で表されるケィ 素化合物及び式（3)で表されるケィ素化合物を加えてさらに加水分解及び Z又は加 水分解縮合させてもよい。  The key compound of formula (1) and the key compound of formula (2), or the key compound of formula (1), the key compound of formula (2) and the key compound of formula (3) are mixed simultaneously. In the presence of at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and half ethers of diols. The key compound represented by formula (1) is hydrolyzed and / or hydrolyzed and condensed, and then the key compound represented by formula (2) or the key represented by formula (2), respectively. An elemental compound and a key compound represented by the formula (3) may be added, followed by hydrolysis and Z or hydrolytic condensation.
[0069] 加水分解及び/又は加水分解縮合の反応温度は、使用するアルコール及び酸ァ ミド類の沸点及び反応時間を考慮して任意に決めることができる。反応時間は式（1) で表されるケィ素化合物、式（2)で表されるケィ素化合物及び式（3)で表されるケィ 素化合物の種類、反応速度、塩基の種類と量等に依存してその最適値は変化する 性質のものであり、限定されない。 [0069] The reaction temperature of hydrolysis and / or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of the alcohol and acid amide to be used. The reaction time is represented by the formula (1), the formula (2), the formula (3) and the formula (3). The optimum value depends on the type of elemental compound, reaction rate, type and amount of base, etc., and is not limited.
得られた加水分解及び/又は加水分解縮合反応液に有機溶媒を加え、さらに必 要に応じて不要な成分を蒸留や液液抽出等の方法で除去することにより、多孔質シ リカ粒子が有機溶媒に分散した分散液を得ることができる。  By adding an organic solvent to the obtained hydrolysis and / or hydrolysis-condensation reaction liquid, and removing unnecessary components by a method such as distillation or liquid-liquid extraction as necessary, the porous silica particles are made organic. A dispersion liquid dispersed in a solvent can be obtained.
[0070] また、分散媒は、水あるいは有機溶媒が好ましい。有機溶媒としては、メタノーノレ、 イソプロピノレアノレコーノレ、エチレングリコーノレ、ブタノーノレ、エチレングリコーノレモノプ 口ピルエーテル等のアルコール類；メチルェチルケトン、メチルイソブチルケトン等の ケトン類；トルエン、キシレン等の芳香族炭化水素類；ジメチルホルムアミド、ジメチル ァセトアミド、 N_メチルピロリドン等のアミド類；酢酸ェチル、酢酸ブチル、 Ί—ブチ 口ラタトン等のエステル類；テトラヒドロフラン、 1 , 4_ジォキサン等のエーテル類等の 有機溶剤を挙げることができ、これらの中で、アルコール類及びケトン類が好ましい。 これら有機溶剤は、単独で、又は 2種以上混合して分散媒として使用することができ る。 [0070] The dispersion medium is preferably water or an organic solvent. Examples of the organic solvent include methanols, isopropylenoreconoles, ethylene glycolanols, butanols, ethyleneglycolone monopropyl ethers, and the like; ketones such as methyl ethyl ketone and methyl isobutyl ketone; toluene, xylene and the like Aromatic hydrocarbons; Amides such as dimethylformamide, dimethylacetamide, N_methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, Ί - butarate ratatones ; Ethers such as tetrahydrofuran, 1, 4_dioxane, etc. Organic solvents can be mentioned, and among these, alcohols and ketones are preferable. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
[0071] 多孔質シリカ粒子（Β)の樹脂組成物中における配合量は、有機溶剤以外の組成物 全量に対して通常 5〜99質量％配合され、 10〜98質量％が好ましぐ 15〜97質量 %がさらに好ましい。 5質量％未満であると、硬化膜としたときの硬度が不十分となる ことがあり、 99質量％を超えると、十分な膜の強度が得られないことがある。尚、粒子 の量は、固形分を意味し、粒子が溶剤分散液の形態で用いられるときは、その配合 量には溶剤の量を含まない。  [0071] The amount of the porous silica particles (Β) in the resin composition is usually 5 to 99% by mass, preferably 10 to 98% by mass, based on the total amount of the composition other than the organic solvent. More preferred is 97% by mass. If it is less than 5% by mass, the hardness of the cured film may be insufficient, and if it exceeds 99% by mass, sufficient film strength may not be obtained. The amount of particles means solid content, and when the particles are used in the form of a solvent dispersion, the amount of the solvent does not include the amount of solvent.
[0072] (C)少なくとも 2個以上の（メタ）アタリロイル基を含有する多官能 (メタ）アタリレートイ匕 合物及び/又は少なくとも 1個以上の（メタ）アタリロイル基を含有する含フッ素 (メタ） アタリレートイ匕合物  [0072] (C) a polyfunctional (meth) attalytoyl compound containing at least two or more (meth) attaroyl groups and / or a fluorine-containing (meta) containing at least one (meth) attalyloyl groups ) Atre relay toy compound
硬化性樹脂組成物には、必要に応じて、少なくとも 2個以上の（メタ）アタリロイル基 を含有する多官能 (メタ）アタリレート化合物及び Ζ又は少なくとも 1個以上の（メタ）ァ クリロイル基を含有する含フッ素 (メタ）アタリレートイ匕合物を添加することもできる。  The curable resin composition contains a polyfunctional (meth) acrylate compound containing at least two or more (meth) attaroyl groups and Ζ or at least one (meth) acryloyl group as required. It is also possible to add a fluorine-containing (meth) atareto toy compound.
[0073] (1)少なくとも 2個以上の（メタ）アタリロイル基を含有する多官能 (メタ）アタリレートイ匕 合物 この化合物については、分子内に少なくとも 2個以上の（メタ）アタリロイル基を含有 する化合物であれば特に制限されるものではない。このような例としては、ネオペンチ ルグリコールジ（メタ）アタリレート、トリメチロールプロパントリ（メタ）アタリレート、ペンタ エリスリトーノレトリ（メタ）アタリレート、トリメチロールェタントリ（メタ）アタリレート、ペンタ エリスリトールテトラ（メタ）アタリレート、ジペンタエリスリトールテトラ（メタ）アタリレート、 アルキル変性ジペンタエリスリトールテトラ（メタ）アタリレート、ジペンタエリスリトール ペンタ（メタ）アタリレート、アルキル変性ジペンタエリスリトールペンタ（メタ）アタリレー ト、ジペンタエリスリトールへキサ（メタ）アタリレート、力プロラタトン変性ジペンタエリス リトールへキサ（メタ）アタリレート、ジトリメチロールプロパンテトラ（メタ）アタリレート、「[0073] (1) A polyfunctional (meth) atareto toy compound containing at least two (meth) atalyloyl groups The compound is not particularly limited as long as it is a compound containing at least two (meth) atallyloyl groups in the molecule. Examples include neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, penta erythritol nortri (meth) acrylate, trimethylol ethane tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) ate relay , Dipentaerythritol hexa (meth) acrylate, force prolatatone modified dipentaerythritol hex (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate,
U- 15HAJ (商品名、新中村化学社製）等の一種単独又は二種以上の組み合わせ が挙げられる。 One type or a combination of two or more types such as U-15HAJ (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
尚、これらのうち、ネオペンチルグリコールジ（メタ）アタリレート、ジペンタエリスリトー ルへキサ（メタ）アタリレート、ペンタエリスリトールテトラ（メタ）アタリレート、ジペンタエリ スリトールペンタ（メタ）アタリレート及び力プロラタトン変性ジペンタエリスリトールへキ サ (メタ）アタリレートが特に好ましい。  Of these, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and force prolatatatone. Modified dipentaerythritol hexa (meth) acrylate is particularly preferred.
[0074] (2)少なくとも 1個以上の（メタ）アタリロイル基を含有する含フッ素 (メタ）アタリレートイ匕 合物 [0074] (2) Fluorine-containing (meth) ataretoy compound containing at least one (meth) attarylyl group
この化合物については、少なくとも 1個以上の（メタ）アタリロイル基を含有する含フッ 素 (メタ）アタリレー H匕合物であれば特に制限されるものではなレ、。このような例として 、パーフルォロォクチルェチル（メタ）アタリレート、ォクタフルォロペンチル（メタ）ァク リレート、トリフルォロェチル (メタ）アタリレート等が挙げられる。これらは、単独で或い は 2種以上組み合わせて使用することができる。  This compound is not particularly limited as long as it is a fluorine-containing (meth) atreyl H compound containing at least one (meth) attalyloyl group. Examples thereof include perfluorooctyl cetyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
[0075] (C)成分の添カ卩量については、特に制限されるものではなレ、が、有機溶剤以外の 組成物全量 100質量部に対して通常 0〜90質量部である。この理由は、添加量が 9 0質量部を超えると、硬化性樹脂組成物の硬化塗膜の屈折率が高くなり、十分な反 射防止効果が得られない場合があるためである。 [0075] The amount of the additive (C) added is not particularly limited, but is usually 0 to 90 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. The reason for this is that when the addition amount exceeds 90 parts by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained.
また、このような理由から、 （C)成分の添力卩量を 80質量部以下とするのがより好まし く、 60質量部以下の添カ卩量とするのがさらに好ましい。 [0076] (D)活性エネルギー線の照射又は熱により活性種を発生する化合物 本願発明では、活性エネルギー線の照射又は熱により活性種を発生する化合物を 添加することもできる。活性エネルギー線の照射又は熱により活性種を発生する化合 物は、硬化性樹脂組成物を硬化させるために用いられる。 For this reason, it is more preferable that the amount of added force of the component (C) is 80 parts by mass or less, and it is more preferable that the amount of added force is 60 parts by mass or less. (D) Compound that generates active species by irradiation of active energy rays or heat In the present invention, a compound that generates active species by irradiation of active energy rays or heat can also be added. A compound that generates active species upon irradiation with active energy rays or heat is used to cure the curable resin composition.
[0077] (1)活性エネルギー線の照射により活性種を発生する化合物 [0077] (1) Compound that generates active species upon irradiation with active energy rays
活性エネルギー線の照射により活性種を発生する化合物（以下「光重合開始剤」と いう。）としては、活性種として、ラジカルを発生する光ラジカル発生剤等が挙げられ る。  Examples of compounds that generate active species upon irradiation with active energy rays (hereinafter referred to as “photopolymerization initiators”) include photoradical generators that generate radicals as active species.
尚、活性エネルギー線とは、活性種を発生する化合物を分解して活性種を発生さ せることのできるエネルギー線と定義される。このような活性エネルギー線としては、 可視光、紫外線、赤外線、 X線、 ひ線、 j3線、 γ線等の光エネルギー線が挙げられる 。ただし、一定のエネルギーレベルを有し、硬化速度が速ぐし力 照射装置が比較 的安価で、小型な観点から、紫外線を使用することが好ましい。  The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, strands, j3 rays, and γ rays. However, it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, increasing the curing speed, and relatively low cost of the irradiation apparatus and relatively small size.
[0078] (i)種類 [0078] (i) Kind
光ラジカル発生剤の例としては、例えばァセトフエノン、ァセトフエノンべンジルケタ ール、アントラキノン、 1— (4—イソプロピルフエ二ル）一 2—ヒドロキシ一 2—メチルプ 口パン 1 オン、カルバゾール、キサントン、 4 クロ口べンゾフエノン、 4, 4'ージァ ミノべンゾフエノン、 1 , 1ージメトキシデォキシベンゾイン、 3, 3 '—ジメチルー 4ーメト キシベンゾフエノン、チォキサントン、 2, 2—ジメトキシ 2—フエニノレアセトフエノン、 1— (4—ドデシルフェニル） 2—ヒドロキシ一 2—メチルプロパン一 1—オン、 2—メ チルー 1一〔4 （メチルチオ）フエニル〕 2—モルフォリノプロパン 1 オン、トリフ ェニルァミン、 2, 4, 6 _トリメチルベンゾィルジフエニルホスフィンオキサイド、 1—ヒド 口キシシクロへキシルフェニルケトン、 2—ヒドロキシ一 2_メチル _ 1 _フエニルプロ パン一 1 _オン、フルォレノン、フルオレン、ベンズアルデヒド、ベンゾインェチルエー テル、ベンゾインプロピルエーテル、ベンゾフエノン、ミヒラーケトン、 3 _メチルァセト フエノン、 3， 3' , 4, 4 '—テトラ（tert—ブチルパーォキシカルボ二ノレ）ベンゾフエノン (BTTB)、 2- (ジメチルァミノ）— 1 _〔4_ (モルフオリニル）フヱニル〕 _ 2—フヱニル メチル） _ 1—ブタノン、 4_ベンゾィル一4'—メチルジフエ二ルサルファイド、ベンジ ノレ、又は BTTBとキサンテン、チォキサンテン、クマリン、ケトクマリン、その他の色素 増感剤との組み合わせ等を挙げることができる。 Examples of photoradical generators include, for example, acetophenone, acetophenone benzil ketal, anthraquinone, 1- (4-isopropylphenyl) 1-2-hydroxy-1-2-methylpropanepanone, carbazole, xanthone, 4 Benzophenone, 4, 4'-amino minobenzophenone, 1,1-dimethoxydeoxybenzoin, 3, 3'-dimethyl-4-methoxybenzophenone, thixanthone, 2,2-dimethoxy 2-phenenoreacetophenone, 1- (4-Dodecylphenyl) 2-hydroxy-1-2-methylpropane-1-one, 2-methyl-1-1-1 [4 (methylthio) phenyl] 2-morpholinopropane 1-one, triphenylamine, 2, 4, 6 _Trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2- Droxyl 2_methyl _ 1 _phenylpropylene 1_one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3_methylacetophenone, 3, 3 ', 4, 4' — Tetra (tert-butylperoxycarboninole) benzophenone (BTTB), 2- (dimethylamino) — 1 _ [4_ (morpholinyl) phenyl] _ 2-phenylmethyl) _ 1-butanone, 4_benzoyl 1 ' Methyldiphenyl sulfide, benzy Nore or combinations of BTTB and xanthene, thixanthene, coumarin, ketocoumarin, and other dye sensitizers.
[0079] これらの光重合開始剤のうち、 2, 2—ジメトキシー 2—フエニルァセトフエノン、 2—ヒ ドロキシ _ 2—メチル一 1 _フエニルプロパン一 1 _オン、 1—ヒドロキシシクロへキシ ノレフエ二ルケトン、 2， 4, 6 _トリメチルベンゾィルジフエニルホスフィンオキサイド、 2 —メチノレ一 1 _〔4_ (メチルチオ）フエニル〕 _ 2_モルフォリノプロパン一 1—オン、 2 - (ジメチルァミノ）— 1 _〔4_ (モルフオリニル）フエニル〕 _ 2—フエ二ルメチル）— 1 —ブタノン等が好ましぐさらに好ましくは、 1—ヒドロキシシクロへキシルフヱ二ルケト ン、 2—メチル一 1 _〔4_ (メチルチオ）フエニル〕 _ 2 _モルフォリノプロパン一 1—ォ ン、 2 _ (ジメチルァミノ）一 1 _〔4_ (モルフオリニル）フエニル〕 _ 2 _フエニルメチル ) _ 1—ブタノン等を挙げることができる。  [0079] Among these photopolymerization initiators, 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxyoxy-2-methyl-1 1-phenylpropane-1-one, 1-hydroxycyclohexyl Norenyl diketone, 2, 4, 6 _Trimethylbenzoyldiphenylphosphine oxide, 2 —Methylolone 1 _ [4_ (methylthio) phenyl] _ 2_morpholinopropane 1-one, 2- (dimethylamino) — 1 _ [4_ (morpholinyl) phenyl] _ 2 -phenylmethyl) -1 -butanone is preferred, more preferably 1-hydroxycyclohexylphenylketone, 2-methyl mono 1 _ [4_ (methylthio) phenyl ] _ 2 _ morpholinopropane 1-one, 2 _ (dimethylamino) 1 _ [4_ (morpholinyl) phenyl] _ 2 _phenylmethyl) _ 1-butanone, etc. .
[0080] (ii)添加量  [0080] (ii) Amount added
光重合開始剤の添加量は特に制限されるものではないが、有機溶剤以外の組成 物全量 100質量部に対して、 0. 01〜20質量部とするのが好ましい。この理由は、添 加量が 0. 01質量部未満となると、硬化反応が不十分となり耐擦傷性、アルカリ水溶 液浸漬後の耐擦傷性が低下する場合があるためである。一方、光重合開始剤の添 加量が 20質量部を超えると、硬化膜の屈折率が増加し反射防止効果が低下する場 合があるためである。  The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. The reason for this is that when the addition amount is less than 0.01 parts by mass, the curing reaction becomes insufficient and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, if the addition amount of the photopolymerization initiator exceeds 20 parts by mass, the refractive index of the cured film may increase and the antireflection effect may decrease.
また、このような理由から、光重合開始剤の添加量を、有機溶剤以外の組成物全量 100質量部に対して 0. 05〜： 15質量部とすることがより好ましぐ 0.：!〜 15質量部と することがさらに好ましい。  For these reasons, it is more preferable that the addition amount of the photopolymerization initiator is 0.05 to 15 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. More preferably, the content is 15 parts by mass.
[0081] (2)熱により活性種を発生する化合物 [0081] (2) Compound that generates active species by heat
熱により活性種を発生する化合物（以下「熱重合開始剤」という。）としては、活性種 として、ラジカルを発生する熱ラジカル発生剤等が挙げられる。  Examples of the compound that generates an active species by heat (hereinafter referred to as “thermal polymerization initiator”) include a thermal radical generator that generates a radical as the active species.
[0082] (i)種類 [0082] (i) Kind
熱ラジカル発生剤の例としては、ベンゾィルパーオキサイド、 tert—ブチル一ォキシ ベンゾエート、ァゾビスイソブチロニトリル、ァセチルパーオキサイド、ラウリルパーォキ サイド、 tert_ブチノレパーアセテート、クミノレパーオキサイド、 tert_ブチノレパーォキ サイド、 tert ブチルハイド口パーオキサイド、 2, 2 '—ァゾビス（2, 4—ジメチルバレ ロニトリル）、 2, 2 '—ァゾビス（4ーメトキシ 2, 4 ジメチルバレロニトリル）等の一種 単独又は二種以上の組み合わせを挙げることができる。 Examples of thermal radical generators include benzoyl peroxide, tert-butyl monooxy benzoate, azobisisobutyronitrile, acetyl chloride, lauryl peroxide, tert_butinoreperacetate, cuminoreperoxide, tert _Bucino Leperoki Side, tert butylhydride peroxide, 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy 2,4-dimethylvaleronitrile), etc. Single or a combination of two or more Can be mentioned.
[0083] (ii)添加量 [0083] (ii) Amount added
熱重合開始剤の添加量についても特に制限されるものではないが、有機溶剤以外 の組成物全量 100質量部に対して、 0. 01〜20質量部とするのが好ましレ、。この理 由は、添加量が 0. 01質量部未満となると、硬化反応が不十分となり耐擦傷性、アル カリ水溶液浸漬後の耐擦傷性が低下する場合があるためである。一方、光重合開始 剤の添加量が 20質量部を超えると、硬化膜の屈折率が増加し反射防止効果が低下 する場合があるためである。  The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. The reason for this is that when the amount added is less than 0.01 parts by mass, the curing reaction becomes insufficient and the scratch resistance and the scratch resistance after immersion in an aqueous alkali solution may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20 parts by mass, the refractive index of the cured film increases and the antireflection effect may decrease.
また、このような理由から、有機溶剤以外の組成物全量 100質量部に対して熱重合 開始剤の添力卩量を 0. 05〜： 15質量部とするのがより好ましぐ 0. 1〜： 15質量部の範 囲内の値とするのがさらに好ましい。  For this reason, it is more preferable to set the additive amount of the thermal polymerization initiator to 0.05 to 15 parts by mass with respect to 100 parts by mass of the total composition other than the organic solvent. To: More preferably, the value is within the range of 15 parts by mass.
[0084] (E)有機溶媒 [0084] (E) Organic solvent
硬化性樹脂組成物には、さらに有機溶媒を添加することが好ましい。このように有 機溶媒を添加することにより、薄膜の反射防止膜を均一に形成することができる。こ のような有機溶媒としては、炭素数 1〜8のアルコール系、炭素数 3〜： 10のケトン系、 炭素数 3〜： 10のエステル系の有機溶媒が好ましく使用でき、メチルイソプチルケトン 、メチルェチルケトン、メタノーノレ、エタノール、 tーブタノール、イソプロパノール、プロ ピレンダリコールモノメチルエーテル、プロピレングリコールェチルエーテル、プロピレ ングリコールモノプロピルエーテル等が特に好ましい例として挙げられる。これらの有 機溶媒は一種単独又は二種以上の組み合わせで使用できる。  It is preferable to further add an organic solvent to the curable resin composition. Thus, by adding an organic solvent, a thin antireflection film can be formed uniformly. As such an organic solvent, an alcohol solvent having 1 to 8 carbon atoms, a ketone solvent having 3 to 10 carbon atoms, and an ester solvent having 3 to 10 carbon atoms can be preferably used. Methyl ethyl ketone, methanol, ethanol, t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol ether ether, propylene glycol monopropyl ether and the like are particularly preferable examples. These organic solvents can be used singly or in combination of two or more.
[0085] 有機溶媒の添加量についても特に制限されるものではなレ、が、有機溶剤以外の組 成物 100質量部に対し、 100〜100，000質量部とするのが好ましレ、。この理由は、 添加量が 100質量部未満となると、硬化性樹脂組成物の粘度調整が困難となる場合 があるためであり、一方、添カ卩量が 100,000質量部を超えると、硬化性樹脂組成物 の保存安定性が低下したり、あるいは粘度が低下しすぎて取り扱いが困難となる場合 があるためである。 [0086] (F)添加剤 [0085] The addition amount of the organic solvent is not particularly limited, but it is preferably 100 to 100,000 parts by mass with respect to 100 parts by mass of the composition other than the organic solvent. The reason is that when the addition amount is less than 100 parts by mass, it may be difficult to adjust the viscosity of the curable resin composition. On the other hand, when the addition amount exceeds 100,000 parts by mass, the curable resin composition may be difficult to adjust. This is because the storage stability of the composition may be decreased, or the viscosity may be excessively decreased to make handling difficult. [0086] (F) Additive
硬化性樹脂組成物には、本発明の目的や効果を損なわない範囲において、光増 感剤、重合禁止剤、重合開始助剤、レべリング剤、濡れ性改良剤、界面活性剤、可 塑剤、紫外線吸収剤、酸化防止剤、帯電防止剤、シランカップリング剤、 （B)成分以 外の無機充填剤若しくは顔料、染料等の添加剤をさらに含有させることもできる。  The curable resin composition includes a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, a plasticizer, as long as the objects and effects of the present invention are not impaired. An additive such as an agent, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler other than the component (B), a pigment, and a dye may be further contained.
[0087] 次に、本発明で使用される硬化性樹脂組成物の調製方法及び硬化条件を説明す る。 [0087] Next, a preparation method and curing conditions for the curable resin composition used in the present invention will be described.
本発明で使用される硬化性樹脂組成物は、上記 (A)エチレン性不飽和基含有含 フッ素重合体及び上記 (B)成分、又は必要に応じて上記（C)成分、（D)成分、（E) 有機溶剤、及び (F)添加剤をそれぞれ添加して、室温又は加熱条件下で混合するこ とにより調製すること力 Sできる。具体的には、ミキサ、ニーダー、ボールミル、三本ロー ル等の混合機を用いて、調製することができる。ただし、加熱条件下で混合する場合 には、熱重合開始剤の分解開始温度以下で行うことが好ましレ、。  The curable resin composition used in the present invention comprises the above (A) ethylenically unsaturated group-containing fluoropolymer and the above (B) component, or, if necessary, the above (C) component, (D) component, It can be prepared by adding (E) an organic solvent and (F) an additive and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a triple roll. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start temperature of the thermal polymerization initiator.
[0088] 硬化性樹脂組成物の硬化条件についても特に制限されるものではないが、例えば 活性エネルギー線を用いた場合、露光量を 0. 01〜10j/cm2の範囲内の値とする のが好ましい。 [0088] There is no particular limitation on the curing conditions of the curable resin composition, for example, when using the active energy rays, to a value within the range of exposure amount of 0. 01~10j / cm 2 Is preferred.
この理由は、露光量が 0. 01j/cm2未満となると、硬化不良が生じる場合があるた めであり、一方、露光量が lOj/cm2を超えると、硬化時間が過度に長くなる場合が あるためである。 This is because when the exposure dose is less than 0.01 j / cm 2 , curing failure may occur. On the other hand, when the exposure dose exceeds lOj / cm 2 , the curing time may become excessively long. Because there is.
また、このような理由により、露光量を 0.：!〜 5j/cm2の範囲内の値とするのがより 好ましぐ 0. 3〜3j/cm2の範囲内の値とするのがより好ましい。 Moreover, these reasons, however, it falls is more preferred instrument 0. 3~3j / cm 2 to a value within the range of exposure amount of 0.:!~ 5j / cm 2 More preferred.
[0089] また、硬化性樹脂組成物を、加熱して硬化させる場合には、 30〜200°Cの範囲内 の温度で、 1〜： 180分間加熱するのが好ましい。このように加熱することにより、基材 等を損傷することなぐより効率的に耐擦傷性に優れた反射防止膜を得ることができ る。 [0089] When the curable resin composition is cured by heating, it is preferably heated at a temperature in the range of 30 to 200 ° C for 1 to 180 minutes. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.
また、このような理由から、 50〜： 180°Cの範囲内の温度で、 2〜： 120分間加熱する のがより好ましく、 80〜： 150°Cの範囲内の温度で、 5〜60分間加熱するのがさらに好 ましい。 [0090] 3.反射防止膜 For this reason, it is more preferable to heat at a temperature in the range of 50 to 180 ° C for 2 to 120 minutes, and for a temperature in the range of 80 to 150 ° C for 5 to 60 minutes. Even more preferred is heating. [0090] 3. Antireflection film
基材上に、上記硬化性樹脂組成物の硬化膜からなる低屈折率層を含んで、本発 明の反射防止膜を作製できる。さらに、この反射防止膜は、低屈折率層の下に、高 屈折率層、中屈折率層、ハードコート層、帯電防止層等を含むことができる。  The antireflection film of the present invention can be produced by including a low refractive index layer comprising a cured film of the curable resin composition on a substrate. Further, the antireflection film can include a high refractive index layer, a medium refractive index layer, a hard coat layer, an antistatic layer, and the like below the low refractive index layer.
図 1に、力、かる反射防止膜 10を示す。図 1に示すように、基材 12の上に、帯電防止 層 14、ハードコート層 16及び低屈折率層 18が積層されている。  FIG. 1 shows the force and the antireflection coating 10. As shown in FIG. 1, an antistatic layer 14, a hard coat layer 16, and a low refractive index layer 18 are laminated on a substrate 12.
また、ハードコート層 16と低屈折率層 18の間に、さらに、高屈折率層（図示せず。 ) を設けてもよい。  Further, a high refractive index layer (not shown) may be further provided between the hard coat layer 16 and the low refractive index layer 18.
さらに、ハードコート層 16を設けずに、帯電防止層 14の上に、直接、低屈折率層 18 を形成してもよい。  Further, the low refractive index layer 18 may be formed directly on the antistatic layer 14 without providing the hard coat layer 16.
[0091] (1)低屈折率層 [0091] (1) Low refractive index layer
低屈折率層は、硬化性樹脂組成物を硬化して得られる硬化膜から構成される。硬 化性樹脂組成物の構成等については、上述の通りであるため、ここでの具体的な説 明は省略するものとし、以下、低屈折率層の屈折率及び厚さについて説明する。  The low refractive index layer is composed of a cured film obtained by curing the curable resin composition. Since the configuration and the like of the curable resin composition are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the low refractive index layer will be described below.
[0092] 硬化性樹脂組成物を硬化して得られる硬化膜の屈折率 (Na— D線（589nm)の屈 折率、測定温度 25°C)、即ち、低屈折率膜の屈折率を 1. 45以下とすることが好まし レ、。この理由は、低屈折率膜の屈折率が 1. 45を超えると、高屈折率膜と組み合わせ た場合に、反射防止効果が著しく低下する場合があるためである。 [0092] The refractive index of the cured film obtained by curing the curable resin composition (the refractive index of Na-D line (589 nm), measuring temperature 25 ° C), that is, the refractive index of the low refractive index film is 1 45 or less is preferable. This is because when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be significantly reduced when combined with a high refractive index film.
従って、低屈折率膜の屈折率を 1 · 44以下とするのがより好ましぐ 1. 43以下とす るのがさらに好ましい。  Therefore, it is more preferable that the refractive index of the low refractive index film is 1 · 44 or less.
尚、低屈折率膜を複数層設ける場合には、そのうちの少なくとも一層が上述した範 囲内の屈折率の値を有していればよぐ従って、その他の低屈折率膜は 1. 45を超え た値であってもよい。  When providing a plurality of low refractive index films, it is sufficient that at least one of them has a refractive index value within the above-mentioned range. Therefore, the other low refractive index films exceed 1.45. It may be a value.
[0093] また、低屈折率層を設ける場合、より優れた反射防止効果が得られることから、高屈 折率層との間の屈折率差を 0. 05以上の値とするのが好ましい。この理由は、低屈折 率層と、高屈折率層との間の屈折率差が 0. 05未満の値となると、これらの反射防止 膜層での相乗効果が得られず、却って反射防止効果が低下する場合があるためで ある。 従って、低屈折率層と、高屈折率層との間の屈折率差を 0.：!〜 0. 5の範囲内の値 とするのがより好ましぐ 0. 15-0. 5の範囲内の値とするのがさらに好ましい。 [0093] Further, when a low refractive index layer is provided, it is preferable to set the refractive index difference with respect to the high refractive index layer to a value of 0.05 or more because a better antireflection effect can be obtained. The reason for this is that if the difference in refractive index between the low refractive index layer and the high refractive index layer is less than 0.05, the synergistic effect of these antireflective film layers cannot be obtained, and instead the antireflective effect. This is because there is a case where the value decreases. Therefore, it is more preferable to set the difference in refractive index between the low refractive index layer and the high refractive index layer to a value within the range of 0.:! To 0.5. More preferably, the value is within the range.
[0094] 低屈折率層の厚さについても特に制限されるものではなレ、が、例えば、 50〜300n mであることが好ましい。この理由は、低屈折率層の厚さが 50nm未満となると、下地 としての高屈折率膜に対する密着力が低下する場合があるためであり、一方、厚さが 300nmを超えると、光干渉が生じて反射防止効果が低下する場合があるためである 従って、低屈折率層の厚さを 50〜250nmとするのがより好ましぐ 60〜200nmと するのがさらに好ましい。 [0094] The thickness of the low refractive index layer is not particularly limited, and is preferably 50 to 300 nm, for example. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as a base may decrease, whereas when the thickness exceeds 300 nm, optical interference does not occur. This is because the antireflection effect may be reduced, and therefore the thickness of the low refractive index layer is more preferably 50 to 250 nm, more preferably 60 to 200 nm.
尚、より高い反射防止性を得るために、低屈折率層を複数層設けて多層構造とす る場合には、その合計した厚さを 50〜300nmとすればよい。  In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be 50 to 300 nm.
[0095] (2)高屈折率層 [0095] (2) High refractive index layer
高屈折率層を形成するための硬化性組成物としては、特に制限されるものでない 、被膜形成成分として、エポキシ系樹脂、フエノール系樹脂、メラミン系樹脂、アル キド系樹脂、シァネート系樹脂、アクリル系樹脂、ポリエステル系樹脂、ウレタン系榭 脂、シロキサン樹脂等の一種単独又は二種以上の組み合わせを含むことが好ましレヽ 。これらの樹脂であれば、高屈折率層として、強固な薄膜を形成することができ、結 果として、反射防止膜の耐擦傷性を著しく向上させることができるためである。  The curable composition for forming the high refractive index layer is not particularly limited. As a film forming component, an epoxy resin, a phenol resin, a melamine resin, an alkyd resin, a cyanate resin, an acrylic resin. It is preferable to include one kind alone or a combination of two or more kinds of resin, polyester resin, urethane resin, siloxane resin and the like. This is because these resins can form a strong thin film as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
し力 ながら、通常、これらの樹脂単独での屈折率は 1. 45〜： 1. 62であり、高い反 射防止性能を得るには十分で無い場合がある。そのため、高屈折率の無機粒子、例 えば金属酸化物粒子を配合することがより好ましレ、。金属酸化物粒子の具体例として は、アンチモンドープ酸化錫（ATO)粒子、錫ドープ酸化インジウム（IT〇）粒子、 Ζη Ο粒子、アンチモンドープ ZnO、 A1ドープ Ζη〇粒子、リンドープ酸化錫（ΡΤΟ)粒子 、 ZrO粒子、 TiO粒子、シリカ被覆 TiO粒子、 Al O /ZrO被覆 TiO粒子、 CeO  However, the refractive index of these resins alone is usually 1.45 to: 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles. Specific examples of metal oxide particles include antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, Ζη Ο particles, antimony-doped ZnO, A1-doped ΖηΖ particles, and phosphorus-doped tin oxide (ΡΤΟ) particles. , ZrO particles, TiO particles, silica-coated TiO particles, Al 2 O 3 / ZrO-coated TiO particles, CeO
2 2 2 2 3 2 2 2 粒子等を挙げることができる。好ましくは、アンチモンドープ酸化錫 (AT〇)粒子、錫 ドープ酸化インジウム（IT〇）粒子、 A1ドープ ΖηΟ粒子、リンドープ酸化錫（ΡΤΟ)粒 子、 Al O /ZrO被覆 Ti〇粒子である。これらの金属酸化物粒子は、一種単独又は Examples include 2 2 2 2 3 2 2 2 particles. Antimony-doped tin oxide (AT) particles, tin-doped indium oxide (IT) particles, A1-doped ΖηΟ particles, phosphorus-doped tin oxide (ΡΤΟ) particles, and Al 2 O 3 / ZrO-coated Ti 0 particles are preferable. These metal oxide particles are one kind alone or
2 3 2 2 2 3 2 2
二種以上の組み合わせで使用することができる。 また、高屈折率層にハードコート層や帯電防止層の機能を持たせることもできる。ま た、硬化形態としては、熱硬化、紫外線硬化、電子線硬化できる硬化性組成物を用 いることができる力 より好適には生産性の良好な紫外線硬化性組成物が用いられる It can be used in a combination of two or more. Moreover, the function of a hard coat layer or an antistatic layer can be given to the high refractive index layer. Moreover, as a curing form, a force capable of using a curable composition capable of thermal curing, ultraviolet curing, and electron beam curing, an ultraviolet curable composition having good productivity is more preferably used.
[0096] 高屈折率層の厚さは特に制限されるものではなレ、が、例えば、 50-30, OOOnmで あることが好ましい。この理由は、高屈折率層の厚さが 50nm未満となると、低屈折率 層と組み合わせた場合に、反射防止効果ゃ基材に対する密着力が低下する場合が あるためであり、一方、厚さが 30， OOOnmを超えると、光干渉が生じて逆に反射防止 効果が低下する場合があるためである。 [0096] The thickness of the high refractive index layer is not particularly limited, but is preferably 50-30, OOOnm, for example. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, when combined with the low refractive index layer, the antireflection effect may decrease the adhesion to the substrate, while the thickness This is because if the thickness exceeds 30, OOOnm, optical interference may occur and the antireflection effect may be reduced.
従って、高屈折率層の厚さを 50〜： 1 , OOOnmとするの力より好ましく、 60〜500nm とするのがさらに好ましい。  Therefore, the thickness of the high refractive index layer is more preferably from 50 to 1: OOOnm, and more preferably from 60 to 500 nm.
また、より高い反射防止性を得るために、高屈折率層を複数層設けて多層構造とす る場合には、その合計した厚さを 50〜30, OOOnmとすれば良レ、。  In addition, in order to obtain higher antireflection properties, when a multilayer structure is formed by providing a plurality of high refractive index layers, it is good if the total thickness is 50-30, OOOnm.
尚、高屈折率層と基材との間にハードコート層を設ける場合には、高屈折率層の厚 さを 50〜300nmとすること力 Sでさる。  In addition, when providing a hard-coat layer between a high refractive index layer and a base material, the thickness S of a high refractive index layer shall be 50-300 nm, and force S is used.
[0097] (3)ハードコート層 [0097] (3) Hard coat layer
本発明の反射防止膜に用いるハードコート層の構成材料については特に制限され るものでない。このような材料としては、シロキサン樹脂、アクリル樹脂、メラミン樹脂、 エポキシ樹脂等の一種単独又は二種以上の組み合わせを挙げることができる。また 、耐擦傷性を増すために、シリカ粒子や、金属酸化物粒子を添加することもできるし、 硬化物層の変質を避けるために、酸化防止剤や光安定剤を添加することができる。  The constituent material of the hard coat layer used for the antireflection film of the present invention is not particularly limited. Examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds. In addition, silica particles and metal oxide particles can be added to increase scratch resistance, and an antioxidant and a light stabilizer can be added to avoid alteration of the cured product layer.
[0098] 酸化防止剤や光安定剤の具体例としては、例えば、スミライザ一 BHT、スミライザ 一 S、スミライザ一 BP_ 76、スミライザ一 MDP_ S、スミライザ一 GM、スミライザ一 B BM— S、スミライザ一 WX— R、スミライザ一 NW、スミライザ一 BP— 179、スミライザ 一 BP— 101、スミライザ一 GA_80、スミライザ一 TNP、スミライザ一 TPP_R、スミラ ィザー P— 16 (以上、住友化学 (株）製）、チヌビン 770、チヌビン 765、チヌビン 144 、チヌビン 622、チヌビン 111、チヌビン 123、チヌビン 292 (チバ'スペシャルティ'ケ ミカルズ (株）製）、ファンクリル FA_ 711M、 FA—712HM (日立化成工業（株）製） 等が挙げられる。 [0098] Specific examples of antioxidants and light stabilizers include, for example, Sumitizer 1 BHT, Summitizer 1 S, Summitizer 1 BP_76, Summitizer 1 MDP_S, Summitizer 1 GM, Summitizer 1 B BM-S, Summitizer 1 WX — R, Sumilyzer NW, Sumilyzer One BP—179, Sumilyzer One BP—101, Sumilyzer One GA_80, Sumilyzer One TNP, Sumilyzer One TPP_R, Sumilyzer P—16 (above, manufactured by Sumitomo Chemical Co., Ltd.), Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (Ciba 'Specialty' Chemicals), Funkrill FA_711M, FA-712HM (Hitachi Chemical Industries, Ltd.) Etc.
[0099] ハードコート層の厚さについても特に制限されるものではなレ、が、：!〜 50 μ ΐηとする のが好ましぐ 1〜： ίθ μ ΐηとするのがより好ましレ、。この理由は、ハードコート層の厚さ 力 μ m未満となると、反射防止膜の基材に対する密着力を向上させることができな い場合があるためであり、一方、厚さが 50 x mを超えると、均一に形成するのが困難 となる場合があるためである。  [0099] The thickness of the hard coat layer is not particularly limited, but is preferably set to:! To 50 μΐη 1 to: more preferably set to ίθ μΐη, . The reason for this is that when the thickness of the hard coat layer is less than μm, the adhesion of the antireflection film to the substrate may not be improved, whereas the thickness exceeds 50 xm. This is because it may be difficult to form a uniform layer.
[0100] (4)導電層  [0100] (4) Conductive layer
導電層は上記の通りでありここでは詳細な説明はしないが、導電層を設けることで、 積層体に導電性を付与し、静電気が生じて埃等が付着するのを防止する。  Although the conductive layer is as described above and will not be described in detail here, by providing the conductive layer, conductivity is imparted to the stacked body, and static electricity is generated and dust and the like are prevented from attaching.
[0101] (5)基材 [0101] (5) Base material
反射防止膜に用いる基材の種類は特に制限されるものではないが、例えば、トリア セチルセルロース、ポリエチレンテレフタレート樹脂（東レ（株)製ルミラー等）、ガラス 、ポリカーボネート樹脂、アクリル樹脂、スチリル樹脂、ァリレート樹脂、ノルボルネン 系樹脂 CJSR (株)製アートン、 日本ゼオン (株)製ゼォネックス等）、メチルメタクリレー ト /スチレン共重合体樹脂、ポリオレフイン樹脂等の各種透明プラスチック板、フィノレ ム等を挙げることができる。好ましくは、トリァセチルセルロース、ポリエチレンテレフタ レート樹脂 (東レ (株)製ルミラー等）、ノルボルネン系樹脂 CISR (株)製アートン等)を 例示できる。これらの基材を含む反射防止膜とすることにより、カメラのレンズ部、テレ ビ（CRT)の画面表示部、あるいは液晶表示装置におけるカラーフィルタ一等の広範 な反射防止膜の利用分野において、優れた反射防止効果を得ることができる。  The type of base material used for the antireflection film is not particularly limited. For example, triacetyl cellulose, polyethylene terephthalate resin (Lumirror, etc. manufactured by Toray Industries, Inc.), glass, polycarbonate resin, acrylic resin, styryl resin, arylate Resin, norbornene resin CJSR, Arton manufactured by Nippon Zeon Co., Ltd., ZEONEX manufactured by Nippon Zeon Co., Ltd.), methyl methacrylate / styrene copolymer resin, polyolefin resin, etc. . Preferable examples include triacetyl cellulose, polyethylene terephthalate resin (Lumirror, etc. manufactured by Toray Industries, Inc.), norbornene-based resin CISR, Arton, etc.). By using an antireflection film containing these base materials, it is excellent in the field of application of a wide range of antireflection films such as color lenses in camera lens units, television (CRT) screen display units, and liquid crystal display devices. An antireflection effect can be obtained.
[0102] [実施例] [0102] [Example]
以下、実施例を示して本発明をさらに詳細に説明するが、本発明の範囲はこれら実 施例の記載に限定されるものではない。また、実施例中、各成分の配合量は特に記 載のない限り、「部」は質量部を、「％」は質量％を意味している。  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the description of these examples. In the examples, unless otherwise specified, the “part” means part by mass and “%” means mass%, unless otherwise specified.
[0103] (製造例 1) [0103] (Production Example 1)
水酸基含有含フッ素重合体 1の合成  Synthesis of hydroxyl-containing fluoropolymer 1
内容積 2. 0リットルの電磁攪拌機付きステンレス製オートクレープを窒素ガスで十 分置換した後、酢酸ェチノレ 400g、パーフルォロ（プロピルビュルエーテル） 53. 2g、 ェチルビニルエーテル 36. lg、ヒドロキシェチルビニルエーテル 44. 0g、過酸化ラウ ロイノレ 1. 00g、上記式（8)で表されるァゾ基含有ポリジメチルシロキサン (VPS 1001 (商品名）、和光純薬工業 (株)製) 6. 0g及びノニオン性反応性乳化剤 (NE— 30 (商 品名）、旭電化工業 (株)製） 20. 0gを仕込み、ドライアイス—メタノールで _ 50°Cま で冷却した後、再度窒素ガスで系内の酸素を除去した。 A 2.0-liter stainless steel autoclave with a magnetic stirrer was thoroughly replaced with nitrogen gas, then 400 g of ethynole acetate, 53.2 g of perfluoro (propyl butyl ether), Ethyl vinyl ether 36. lg, Hydroxy ethyl vinyl ether 44.0 g, Lauro oleore peroxide 1.00 g, azo group-containing polydimethylsiloxane represented by the above formula (8) (VPS 1001 (trade name), Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.) 6.0 g and nonionic reactive emulsifier (NE-30 (trade name), Asahi Denka Kogyo Co., Ltd.) 20.0 g were charged and cooled to _50 ° C with dry ice-methanol After that, oxygen in the system was removed again with nitrogen gas.
[0104] 次いでへキサフルォロプロピレン 120. 0gを仕込み、昇温を開始した。オートクレー ブ内の温度が 60°Cに達した時点での圧力は 5. 3 X 105Paを示した。その後、 70°C で 20時間攪拌下に反応を継続し、圧力が 1. 7 X 105Paに低下した時点でオートタレ ーブを水冷し、反応を停止させた。室温に達した後、未反応モノマーを放出してォー トクレーブを開放し、固形分濃度 26. 4%のポリマー溶液を得た。得られたポリマー溶 液をメタノールに投入しポリマーを析出させた後、メタノールにて洗浄し、 50°Cにて真 空乾燥を行い 220gの水酸基含有含フッ素重合体を得た。これを水酸基含有含フッ 素重合体 1とする。使用した単量体と溶剤を表 1に示す。 [0104] Next, 12.0 g of hexafluoropropylene was charged, and the temperature increase was started. When the temperature in the autoclave reached 60 ° C, the pressure was 5.3 X 10 5 Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and when the pressure dropped to 1.7 × 10 5 Pa, the auto-turve was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released to open the autoclave, and a polymer solution having a solid content concentration of 26.4% was obtained. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer. This is designated as a hydroxyl-containing fluorine-containing polymer 1. Table 1 shows the monomers and solvents used.
得られた水酸基含有含フッ素重合体 1に付き、ゲルパーミエーシヨンクロマトグラフィ 一によるポリスチレン換算数平均分子量及びァリザリンコンプレクソン法によるフッ素 含量をそれぞれ測定した。また、 — NMR、 13C— NMRの両 NMR分析結果、元 素分析結果及びフッ素含量から、水酸基含有含フッ素重合体 1を構成する各単量体 成分の割合を決定した。結果を表 2に示す。 The obtained hydroxyl group-containing fluoropolymer 1 was subjected to measurement of the polystyrene-equivalent number average molecular weight by gel permeation chromatography 1 and the fluorine content by the alizarin complexone method. In addition, the proportion of each monomer component constituting the hydroxyl group-containing fluoropolymer 1 was determined from the NMR analysis results of both —NMR and 13 C—NMR, the elemental analysis results, and the fluorine content. The results are shown in Table 2.
[0105] 尚、 VPS1001は、数平均分子量が 7〜9万、ポリシロキサン部分の分子量が約 10 , 000の、上記式（8)で表されるァゾ基含有ポリジメチルシロキサンである。 NE- 30 は、上記式（13)において、 nが 9、 mが 1、 uが 30であるノニオン性反応性乳化剤であ る。  [0105] VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (8) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the above formula (13).
さらに、表 2において、単量体と構造単位との対応関係は以下の通りである。  Furthermore, in Table 2, the correspondence between the monomer and the structural unit is as follows.
単量体 構造単位  Monomer structural unit
へキサフノレオ口プロピレン （a)  Hexafnoreo propylene (a)
パーフルォロ（プロピルビュルエーテル） (a) Perfluoro (propyl butyl ether) ( a )
ェチノレビニノレエーテノレ (b)  Echinorevinino reetenore (b)
ヒドロキシェチノレビニノレエーテノレ （c) NE- 30 (f) Hydroxyetino levinino reethenore (c) NE-30 (f)
ポリジメチルシロキサン骨格 （d)  Polydimethylsiloxane skeleton (d)
[0106] (製造例 2) [0106] (Production Example 2)
水酸基含有含フッ素重合体 2の合成  Synthesis of hydroxyl-containing fluoropolymer 2
ェチルビニルエーテル及びヒドロキシェチルビニルエーテルの使用量を表 1のよう に変えた以外は、製造例 1と同様にして水酸基含有含フッ素重合体を合成した。これ を水酸基含有含フッ素重合体 2とする。各単量体成分の割合を表 2に示す。  A hydroxyl group-containing fluoropolymer was synthesized in the same manner as in Production Example 1 except that the amounts of ethyl vinyl ether and hydroxyethyl vinyl ether were changed as shown in Table 1. This is designated as hydroxyl-containing fluoropolymer 2. The ratio of each monomer component is shown in Table 2.
[0107] [表 1] [0107] [Table 1]
Figure imgf000036_0001
Figure imgf000036_0001
[0108] [表 2]  [0108] [Table 2]
Figure imgf000036_0002
Figure imgf000036_0002
[0109] (製造例 3)  [0109] (Production Example 3)
エチレン性不飽和基含有含フッ素重合体 (Α— 1)の合成 電磁攪拌機、ガラス製冷却管及び温度計を備えた容量 1リットルのセパラブルフラ スコに、製造例 1で得られた水酸基含有含フッ素重合体 1を 50.0g、重合禁止剤とし て 2, 6 ジー t ブチルメチルフエノール 0. Olg及びメチルイソブチルケトン（以下、 MIBK) 370gを仕込み、 20°Cで水酸基含有含フッ素重合体 1が MIBKに溶解して、 溶液が透明、均一になるまで攪拌を行った。 Synthesis of fluorine-containing polymer containing ethylenically unsaturated groups (Α— 1) In a separable flask with a capacity of 1 liter equipped with a magnetic stirrer, a glass cooling tube and a thermometer, 50.0 g of the hydroxyl group-containing fluoropolymer 1 obtained in Production Example 1 was used as a polymerization inhibitor and 2, 6 g t-butyl. Methylphenol 0. Olg and 370 g of methyl isobutyl ketone (hereinafter referred to as MIBK) were charged and stirred at 20 ° C. until the hydroxyl group-containing fluoropolymer 1 was dissolved in MIBK and the solution became transparent and uniform.
次いで、この系に、 2 メタクリロイルォキシェチルイソシァネートを 15. lg添加し、 溶液が均一になるまで攪拌した後、ジブチルチンジラウレート 0. lgを添加して反応 を開始し、系の温度を 55〜65°Cに保持し 5時間攪拌を継続することにより、エチレン 性不飽和基含有含フッ素重合体 (A— 1)の MIBK溶液を得た。  Next, 15. lg of 2 methacryloyloxychetyl isocyanate is added to the system, and the mixture is stirred until the solution is homogeneous. Then, 0.1 lg of dibutyltin dilaurate is added to start the reaction, and the temperature of the system is increased. Was maintained at 55 to 65 ° C. and stirring was continued for 5 hours to obtain a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer (A-1).
この溶液をアルミ皿に 2g秤量後、 150°Cのホットプレート上で 5分間乾燥、秤量して 固形分含量を求めたところ、 15. 2質量％であった。使用した化合物、溶剤及び固形 分含量を表 3に示す。  2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.2% by mass. Table 3 shows the compounds, solvents, and solid content used.
[0110] (製造例 4) [0110] (Production Example 4)
エチレン性不飽和基含有含フッ素重合体 (A— 2)の合成  Synthesis of ethylenically unsaturated group-containing fluoropolymer (A-2)
表 3に示すように、製造例 3において、水酸基含有含フッ素重合体の種類、並びに 2—メタクリロイルォキシェチルイソシァネート、 MIBK及びイソシァネート基/水酸基 のモル比を変えた以外は、製造例 3と同様にしてエチレン性不飽和基含有含フッ素 重合体 (A— 2)の MIBK溶液を得た。  As shown in Table 3, in Production Example 3, except that the type of the hydroxyl group-containing fluoropolymer and the molar ratio of 2-methacryloyloxychetyl isocyanate, MIBK, and isocyanate group / hydroxyl group were changed. In the same manner as in 3, a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer (A-2) was obtained.
[0111] [表 3] [0111] [Table 3]
エチレン性 エチレン性 不飽和基含 不飽和基含 組 成 有舍フッ素 有含フッ素 重合体 重合体Ethylenic Ethylene Unsaturated group-containing Unsaturated group-containing Composition Fluorine-containing Fluorine-containing polymer Polymer
A— 1 A— 2 水酸基含有含フッ素重合体 1 5 0. 0 ― 仕 水酸基含有含フッ素重合体 2 5 0. 0 込 A— 1 A— 2 Hydroxyl group-containing fluoropolymer 1 5 0. 0 — Finish Hydroxyl group-containing fluoropolymer 2 5 0.0
み 2 _メタクリロイルォキシェチルイソシァネ一ト 1 5. 1 3. 5 量  2_Methacryloyloxychetyl isocyanate 1 5. 1 3. 5 Quantity
2 , 6—ジ _ t—プチルメチルフ Xノール 0. 0 1 0. 0 1 g  2, 6-di-t-butylmethylphenol X-nor 0. 0 1 0. 0 1 g
ジブチルチンジラウレー卜 0. 1 0. 1 メチルイソブチルケトン 3 7 0 3 0 4 Dibutyltin dilaurate 0. 1 0. 1 Methyl isobutyl ketone 3 7 0 3 0 4
2—メタクリロイルォキシェチルイソシァネートのィソシァ 2-Methacryloyloxychetyl isocyanate isocyanate
ネート基 Z水酸基含有含フッ素重合体の水酸基 1 . 1 1 . 2 Nate group Z Hydroxyl group of hydroxyl group-containing fluoropolymer 1.1 1 1.2
(モル比） (Molar ratio)
固形分含量 （重量％) 1 5. 2 1 5. 3  Solid content (wt%) 1 5. 2 1 5. 3
(製造例 5) (Production Example 5)
多孔質シリカ微粒子 (B— 1)の合成 Synthesis of porous silica fine particles (B— 1)
石英製セパラブルフラスコ中に、テトラエトキシシラン (東レ ·ダウコーニング 'シリコ ーン（株）製、 AY43— 101) 64. 85g、エタノーノレ 692. 72g、 N, N—ジメチノレアセト アミド 40. OOgをカロ免、均一に混合した後、アンモニアの 25%水溶 f夜 200. OOgを添 加した。その後、溶液を攪拌しながら 50°Cで 6時間反応させ、さらにビュルトリメトキシ シラン（東レ'ダウコーユング 'シリコーン（株）製、 SZ6300) 2. 43gを添カロし 50°Cで 2 時間反応させた。反応液を室温まで冷却後、 MIBK1000. 00gとシユウ酸の 0. 1 % 水溶液 1000. 00gとをカ卩え、攪拌、静置した。 2層に分離した上層を取り分け、ロー タリーエバポレーターで固形分濃度 5%となるまで濃縮し、多孔質シリカ粒子溶液（B _ 1)を得た。  In a quartz separable flask, tetraethoxysilane (Toray Dow Corning Silicone Co., Ltd., AY43-101) 64.85g, ethanolanol 692.72g, N, N-dimethylenoacetamide 40.OOg After mixing uniformly, 200.OOg of 25% aqueous ammonia in water at night was added. Then, the solution was allowed to react at 50 ° C for 6 hours with stirring, and further, 43 g of butyltrimethoxysilane (Toray 'Dowcoung' Silicone Co., Ltd., SZ6300) was added and reacted at 50 ° C for 2 hours. . After cooling the reaction solution to room temperature, MIBK1000.00 g and 0.1% aqueous solution of oxalic acid 1000.00 g were added, stirred and allowed to stand. The upper layer separated into two layers was separated, and concentrated to a solid content concentration of 5% with a rotary evaporator to obtain a porous silica particle solution (B — 1).
得られた溶液（B_ 1)の lgにエタノール 10gをカ卩えて混合後、透過型電子顕微鏡 用カーボングリッド上に 1滴を滴下し、次いで室温で 24時間乾燥し、 日本電子社製フ ィールドエミッション電子顕微敏 EM— 2010Fを用いて観察を行い、多孔質シリカ粒 子の平均粒径を測定した。  After adding 10 g of ethanol to the lg of the resulting solution (B_ 1), add 1 drop on the carbon grid for a transmission electron microscope, and then drying at room temperature for 24 hours, field emission made by JEOL Ltd. Observation was performed using electron microscopic EM-2010F, and the average particle size of the porous silica particles was measured.
得られた溶液（B— 1)の 10gをアルミ皿に取り、 150°Cのホットプレート上で 1時間乾 燥し、多孔質シリカ粒子 1の粉末サンプノレを得た。得られた多孔質シリカ粒子粉末の BET比表面積を Quantachrome Instruments社製 AUTOSORB— 1を用いて 測定した。 Take 10 g of the resulting solution (B-1) in an aluminum dish and dry on a hot plate at 150 ° C for 1 hour. It dried and the powder sampnore of the porous silica particle 1 was obtained. The BET specific surface area of the obtained porous silica particle powder was measured using AUTOSORB-1 manufactured by Quantachrome Instruments.
測定結果を表 4に示す。  Table 4 shows the measurement results.
[0113] (製造例 6) [0113] (Production Example 6)
多孔質シリカ微粒子（B— 2)の合成  Synthesis of porous silica particles (B-2)
石英製セパラブルフラスコ中に、テトラメトキシシラン (信越化学工業 (株)製、 KBM -04) 48. 58g、ビニノレトリメトキシシラン 20. 28g、エタノーノレ 328. 14g、エチレング リコーノレ 300. OOgをカロえ、均一に混合した後、テトラメチルアンモニゥムハイドロキサ イドの 1%水溶液 303. OOgを添加した。その後、溶液を攪拌しながら 60°Cで 4時間 反応させた。反応液を室温まで冷却後、酢酸ェチル 1000. 00gとシユウ酸の 0. 1% 水溶液 1000. 00gとをカ卩え、攪拌、静置した。 2層に分離した上層を取り分け、プロ ピレンダリコールモノェチルエーテル 500· 00gをカ卩えた後、ロータリーエバポレータ 一で固形分濃度 5%となるまで濃縮し、多孔質シリカ粒子溶液 (B— 2)を得た。  In a quartz separable flask, 48.58 g of tetramethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM -04), 20.28 g of vinylinotrimethoxysilane, 328.14 g of ethanol, 300.OOg of ethylene glycol After mixing uniformly, 303.OOg of a 1% aqueous solution of tetramethylammonium hydroxide was added. Thereafter, the solution was reacted at 60 ° C. for 4 hours while stirring. After cooling the reaction solution to room temperature, 1000.00 g of ethyl acetate and 1000.00 g of a 0.1% aqueous solution of oxalic acid were added, stirred and allowed to stand. After separating the upper layer separated into two layers, 500 g of propylene glycol monoethyl ether was collected, and concentrated to a solid content concentration of 5% with a rotary evaporator, and the porous silica particle solution (B-2 )
製造例 5と同様に平均粒径と比表面積を測定した。測定結果を表 4に示す。  The average particle size and specific surface area were measured in the same manner as in Production Example 5. Table 4 shows the measurement results.
[0114] (製造例 7) [0114] (Production Example 7)
多孔質シリカ微粒子 (B— 3)の合成  Synthesis of porous silica particles (B-3)
石英製セパラブルフラスコ中に、テトラエトキシシラン 27· 99g、メタノーノレ 838. 05 g、プロピレングリコール 30· 00gを力 Pえ、均一に混合した後、アンモニアの 1%水溶 液 101. 00gを添加した。その後、溶液を攪拌しながら 40°Cで 8時間反応させ、さら にビニルトリメトキシシラン 1. l lg、メタクリロキシプロピルトリメトキシシラン (東レ'ダウ コーユング.シリコーン (株)製、 SZ_ 6030) 1. 85gを添カ卩し 40。Cで 2時間反応させ た。反応液を室温まで冷却後、 MIBK1000. 00gとシユウ酸の 0. 1%水溶液 1000. 00gとを加え、攪拌、静置した。 2層に分離した上層を取り分け、ロータリーエバポレ 一ターで固形分濃度 5%となるまで濃縮し、多孔質シリカ粒子溶液 (B_ 3)を得た。 製造例 5と同様に平均粒径と比表面積を測定した。測定結果を表 4に示す。  In a quartz separable flask, 27.99 g of tetraethoxysilane, 838.05 g of methanol and 30.00 g of propylene glycol were added and mixed uniformly, and then 101.00 g of a 1% aqueous solution of ammonia was added. Then, the solution was reacted for 8 hours at 40 ° C with stirring, and further vinyltrimethoxysilane 1.l lg, methacryloxypropyltrimethoxysilane (Toray Dow Co., Ltd., manufactured by Silicone Co., Ltd., SZ_6030) 1. Add 85g 40. C was allowed to react for 2 hours. After the reaction solution was cooled to room temperature, MIBK 1000.00 g and 0.1% aqueous solution of oxalic acid 1000.00 g were added, and the mixture was stirred and allowed to stand. The upper layer separated into two layers was separated, and concentrated to a solid content concentration of 5% with a rotary evaporator to obtain a porous silica particle solution (B_3). The average particle size and specific surface area were measured in the same manner as in Production Example 5. Table 4 shows the measurement results.
[0115] (製造例 8) [0115] (Production Example 8)
多孔質シリカ微粒子（B— 4)の合成 石英製セパラブルフラスコ中に、テトラエトキシシラン 106· 24g、メタノーノレ 420· 4 9g、 1 , 2—ブタンジ才ーノレ 200. OOgをカロ免、均一に昆合した後、アンモニアの 10% 水溶液 100. OOgと超純水 160. 00gを添カ卩した。その後、溶液を攪拌しながら 30°C で 12時間反応させ、さらにアタリロキシプロピルトリメトキシシラン (東レ'ダウコーニン グ.シリコーン（株）製、 AY43— 310M) 13. 28gを添加し 60°Cで 1時間反応させた。 反応液を室温まで冷却後、プロピレングリコールメチルエーテルアセテート 1000. 00 gとシユウ酸の 0. 1%水溶液 1000. 00gとを加え、攪拌、静置した。 2層に分離した上 層を取り分け、ロータリーエバポレーターで固形分濃度 5%となるまで濃縮し、多孔質 シリカ粒子溶液 (B— 4)を得た。 Synthesis of porous silica particles (B-4) In a quartz separable flask, tetraethoxysilane 106 · 24g, methanolol 420 · 49g, 1,2-butaneji-nore 200. After OOg was calorie-free and evenly mixed, 10% aqueous solution of ammonia 100.OOg And 160.00 g of ultrapure water were added. After that, the solution was allowed to react at 30 ° C for 12 hours while stirring, and further added with 28 g of Atalyloxypropyltrimethoxysilane (Toray 'Dow Corning. Silicone Co., Ltd., AY43-310M) at 60 ° C. Reacted for hours. After cooling the reaction solution to room temperature, 1000.00 g of propylene glycol methyl ether acetate and 1000.00 g of a 0.1% aqueous solution of oxalic acid were added, and the mixture was stirred and allowed to stand. The upper layer separated into two layers was separated, and concentrated to a solid content concentration of 5% with a rotary evaporator to obtain a porous silica particle solution (B-4).
製造例 5と同様に平均粒径と比表面積を測定した。測定結果を表 4に示す。  The average particle size and specific surface area were measured in the same manner as in Production Example 5. Table 4 shows the measurement results.
[0116] (製造例 9) [0116] (Production Example 9)
多孔質シリカ微粒子（B— 5)の合成  Synthesis of porous silica fine particles (B-5)
石英製セパラブルフラスコ中に、テトラエトキシシラン (東レ ·ダウコーニング 'シリコ ーン（株）製八¥43— 101) 50. 96g、エタノーノレ 700. 98g、 N, N—ジメチノレアセト アミド 40. 00gをカロ免、均一に混合した後、アンモニアの 25%7 溶夜 200. 00gを添 カロした。その後、溶液を攪拌しながら 50°Cで 6時間反応させ、さらにビニルトリメトキシ シラン（東レ 'ダウコ一二ング'シリコーン（株）製 SZ6300) 2· l lgと 3, 3, 3—トリフル ォロプロピルトリメトキシシラン (信越化学工業 (株)製 KBM7103) 5· 95gを添加し 5 In a separable flask made of quartz, tetraethoxysilane (Toray Dow Corning's Silicone Co., Ltd. 8 ¥ 43—101) 50.96 g, ethanolate 700.98 g, N, N-dimethylenoacetamide 40.00 g After mixing the mixture uniformly, 200.00 g of 25% ammonia dissolution night was added. After that, the solution was allowed to react at 50 ° C for 6 hours with stirring, and vinyltrimethoxysilane (SZ6300, manufactured by Toray 'Dauco-Ining' Silicone Co., Ltd.) 2 · l lg and 3, 3, 3-trifluoro Add 5 · 95g of propyltrimethoxysilane (KBM7103, Shin-Etsu Chemical Co., Ltd.) 5
0°Cで 2時間反応させた。反応液を室温まで冷却後、 MIBK1000. 00gとシユウ酸のThe reaction was carried out at 0 ° C for 2 hours. After cooling the reaction solution to room temperature, MIBK1000.00g and oxalic acid
0. 1 %水溶液 1000. 00gとをカ卩え、攪拌、静置した。 2層に分離した上層を取り分け 、ロータリーエバポレーターで固形分濃度 5 %となるまで濃縮し、多孔質シリカ粒子溶 液（B— 5)を得た。 A 0.1% aqueous solution (1000.00 g) was added, stirred and allowed to stand. The upper layer separated into two layers was separated, and concentrated to a solid content concentration of 5% by a rotary evaporator to obtain a porous silica particle solution (B-5).
製造例 5と同様に平均粒径と比表面積を測定した。測定結果を表 4に示す。  The average particle size and specific surface area were measured in the same manner as in Production Example 5. Table 4 shows the measurement results.
[0117] [表 4] ケィ素化合物 [0117] [Table 4] Key compound
反応液中 多項質 のケィ素 比表面積  Polymorphic Ca in the reaction solution Specific surface area
製造例 シリカ 粒径  Production example Silica particle size
[nm] ( 1 ) ( 2 ) (2) + (3) 化合物の 粒子 [m2/g [nm] (1) (2) (2) + (3) Compound particles [m 2 / g
[モル％] [モル％] [モル％] 全体濃度'  [Mole%] [Mole%] [Mole%] Total concentration '
[質量 « 製造例 5 B - 1 2 0 1 5 0 9 5 5 2 製造例 6 B - 2 1 5 3 0 0 7 0 3 0 3 製造例 7 B - 3 2 0 2 0 0 Θ 0 1 0 1 製造例 8 B - 4 3 0 2 5 0 9 0 1 0 4 製造例 9 B - 5 2 0 1 2 0 8 6 1 4 2  [Mass «Production Example 5 B-1 2 0 1 5 0 9 5 5 2 Production Example 6 B-2 1 5 3 0 0 7 0 3 0 3 Production Example 7 B-3 2 0 2 0 0 Θ 0 1 0 1 Production Example 8 B-4 3 0 2 5 0 9 0 1 0 4 Production Example 9 B-5 2 0 1 2 0 8 6 1 4 2
*■ ' 全加水分解縮合物換算」 の濃度 (製造例 10)  * ■ Concentration of 'Total hydrolysis condensate' (Production Example 10)
特定有機化合物 (S— 1)の合成 Synthesis of specific organic compound (S-1)
攪拌機付きの容器内のメルカプトプロピルトリメトキシシラン 221部及びジブチルス ズジラウレート 1部の混合溶液に、イソホロンジイソシァネート 222部を、乾燥空気中、 50°Cで 1時間かけて滴下した後、さらに 70°Cで 3時間攪拌した。  To a mixed solution of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyl suddilaurate in a vessel equipped with a stirrer, 222 parts of isophorone diisocyanate was added dropwise in dry air at 50 ° C over 1 hour. The mixture was stirred at 70 ° C for 3 hours.
続いて、この反応溶液中に新中村ィ匕学製 NKエステル A _TMM_ 3LM_N (ぺ ンタエリスリトールトリアタリレート 60質量0 /0とペンタエリスリトールテトラアタリレート 40 質量％からなる。このうち、反応に関与するのは、水酸基を有するペンタエリスリトー ルトリアタリレートのみである。） 549部を 30°Cで 1時間かけて滴下した後、さらに 60°C で 10時間攪拌して反応液を得た。 Subsequently, consisting Shin Nakamura I匕学Ltd. NK Ester A _TMM_ 3LM_N (pentaerythritol tri Atari rate 60 mass 0/0 and pentaerythritol Atari rate 40% by weight in the reaction solution. Of these, participating in the reaction (Only pentaerythritol triatallylate having a hydroxyl group.) 549 parts were added dropwise at 30 ° C over 1 hour, and then stirred at 60 ° C for 10 hours to obtain a reaction solution.
この反応液中の生成物、即ち、重合性不飽和基を有する有機化合物における残存 イソシァネート量を FT— IRで測定したところ、 0. 1質量％以下であり、各反応がほぼ 定量的に行われたことを確認した。生成物の赤外吸収スペクトルは原料中のメルカプ ト基に特徴的な 2550カイザ-の吸収ピ―ク及び原料イソシァネ—ト化合物に特徴的 な 2260カイザ—の吸収ピ―クが消失し、新たにウレタン結合及び S (C =〇）NH— 基に特徴的な1660カィザ—のピ—ク及びァクリロキシ基に特徴的な1720カィザ— のピ一クが観察され、重合性不飽和基としてのアタリロキシ基と一 S (C =〇）NH―、 ウレタン結合を共に有するアタリ口キシ基修飾アルコキシシランが生成していることを 示した。以上により、チォウレタン結合と、ウレタン結合と、アルコキシシリル基と、重合 性不飽和基とを有する化合物 773部と反応に関与しなかったペンタエリスリトールテト ラアタリレート 220部の組成物（S _ 1)を得た。 [0119] (製造例 11) The product in this reaction solution, that is, the amount of residual isocyanate in the organic compound having a polymerizable unsaturated group was measured by FT-IR, and it was 0.1% by mass or less, and each reaction was performed almost quantitatively. I confirmed that. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser, characteristic of mercapto groups in the raw material, and the absorption peak of 2260 Kaiser, characteristic of the raw isocyanate compound, disappeared. A 1660-membered peak characteristic of a urethane bond and a S (C = 0) NH- group and a 1720-membered peak characteristic of an acryloxy group were observed, and an talyloxy group as a polymerizable unsaturated group was observed. And one S (C = 〇) NH- and urethane bond-modified alkoxysilanes are formed. As described above, 773 parts of a compound having a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group, and a composition of 220 parts of pentaerythritol tetraacrylate that was not involved in the reaction (S _ 1) Got. [0119] (Production Example 11)
多官能アタリレートの合成  Synthesis of polyfunctional attalylate
攪拌機付きの容器内のイソホロンジイソシァネート 18. 8部と、ジブチル錫ジラウレ ート 0. 2部とからなる溶液に対し、新中村ィ匕学製 NKエステル A—TMM— 3LM— N (反応に関与するのは、水酸基を有するペンタエリスリトールトリアタリレートのみであ る。） 93部を、 10°C、 1時間の条件で滴下した後、 60°C、 6時間の条件で攪拌し、反 応液とした。  A solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer was added to NK ester A—TMM—3LM—N (reaction) It is only pentaerythritol triatalylate having a hydroxyl group that participates in the reaction.) 93 parts are added dropwise at 10 ° C for 1 hour, and then stirred at 60 ° C for 6 hours. A liquid was used.
製造例 10と同様にして、この反応液中の生成物、即ち、多官能アタリレートにおけ る残存イソシァネート量を FT—IRで測定したところ、 0. 1質量％以下であり、反応が ほぼ定量的に行われたことを確認した。また、分子内に、ウレタン結合、及びアタリ口 ィル基 (重合性不飽和基）とを含むことを確認した。  In the same manner as in Production Example 10, the product in this reaction solution, that is, the amount of residual isocyanate in the polyfunctional acrylate was measured by FT-IR, which was 0.1% by mass or less, and the reaction was almost quantitative. Confirmed that this was done. In addition, it was confirmed that the molecule contains a urethane bond and an attalyl group (polymerizable unsaturated group).
以上により、へキサアタリレートイ匕合物が 75部得られたほか、反応に関与しなかった ペンタエリスリトールテトラアタリレート 37部が混在している組成物（S— 2)を得た。  As a result, 75 parts of hexatateritol toy compound was obtained, and a composition (S-2) in which 37 parts of pentaerythritol tetraatalylate which was not involved in the reaction was mixed was obtained.
[0120] (製造例 12) [0120] (Production Example 12)
ジノレコニァ含有ハードコート層用組成物（H— 1)の調製  Preparation of Ginoleconia-containing composition for hard coat layer (H-1)
ジノレコニァ粒子（第一稀元素化学工業 (株)製 UEP— 100 (—次粒径 10〜30nm) ) 300部をメチルェチルケトン（MEK) 700部に添カロし、ガラスビーズにて 168時間分 散を行い、ガラスビーズを除去してジルコニァ分散ゾル 950部を得た。ジルコニァ分 散ゾルをアルミ皿に 2g秤量後、 120°Cのホットプレート上で 1時間乾燥、秤量して固 形分含量を求めたところ 30%であった。このジルコニァ分散ゾル 100gに、製造例 10 で合成した特定有機化合物を含む組成物（S— 1) 0. 86g、ジペンタエリスリトールへ キサアタリレート（DPHA) 13. 4g、 p—メトキシフエノーノレ 0. 016g、イオン交換水 0. 033gの混合液を 60°C、 3時間撹拌後、オルト蟻酸メチルエステル 0. 332gを添カロし てさらに 1時間同一温度で加熱撹拌することで、表面変性ジノレコニァ粒子の分散液 1 14. 6gを得た。この分散液 114. 6g、製造例 11で合成した組成物（S _ 2) 1. 34g、 1—ヒドロキシシクロへキシルフェニルケトン 1. 26g、ィルガキュア 907 (2—メチル _ 1 - [4- (メチルチオ）フエニル] _ 2_モルフォリノプロパン一 1—オン、チバ 'スぺシャ ノレティ'ケミカノレズ製） 0. 76g、チヌビン 144 (ビス（1 , 2, 2, 6, 6 _ペンタメチノレ _4 ーピペリジニル） [ (3, 5—ジ—tーブチルー 4ーヒドロキシフエニル）メチル]ブチル マロネート、チノく.スペシャルティ.ケミカルズ製） 2· 51g、MEK46. 6gを混合攪拌し 、ジノレコニァ粒子含有ハードコート用組成物（h—:L：固形分濃度 30%)を 167g得た Ginoleconia particles (UEP-100 (manufactured by Daiichi Rare Elemental Chemical Co., Ltd.) (Partial particle size 10 to 30 nm)) 300 parts of methyl ethyl ketone (MEK) 700 parts, and 168 hours with glass beads The glass beads were removed to obtain 950 parts of zirconia-dispersed sol. After weighing 2g of the zirconia dispersion sol in an aluminum dish, it was dried on a hot plate at 120 ° C for 1 hour and weighed to obtain a solid content of 30%. A composition containing the specific organic compound synthesized in Production Example 10 (S-1) 0.86 g, dipentaerythritol hexaatalylate (DPHA) 13.4 g, p-methoxyphenolanol 016 g, 0.033 g of ion-exchanged water was stirred at 60 ° C for 3 hours, then added with 0.333 g of orthoformate methyl ester and further heated and stirred at the same temperature for 1 hour to obtain surface-modified dinoleconia particles. 14.6 g of the dispersion 1 was obtained. 114.6 g of this dispersion, 1.34 g of the composition synthesized in Preparation Example 11 (S _ 2), 1.26 g of 1-hydroxycyclohexyl phenyl ketone, Irgacure 907 (2-methyl _ 1-[4- (methylthio ) Phenyl] _ 2_ Morpholinopropane 1-one, Ciba 'Specialia' made by Chemikanoles) 0.76g, Tinuvin 144 (Bis (1, 2, 2, 6, 6 _Pentamethinore _4 -Piperidinyl) [(3,5-di-tert-butyl-4-hydroxyphenyl) methyl] butyl malonate, Chinoku. Specialty Chemicals) 2 · 51g, MEK46. 6g were mixed and stirred to form a composition for hard coat containing ginoleconia particles 167g of product ( h— : L: solid content concentration 30%)
[0121] (製造例 13) [0121] (Production Example 13)
シリカ粒子含有ハードコート層用組成物（H_ 2)の調製  Preparation of silica particle-containing hard coat layer composition (H_ 2)
製造例 10で製造した重合性不飽和基を含む組成物（S— 1) 2. 32部、シリカ粒子 ゾル (メチルェチルケトンシリカゾル、 日産化学工業 (株)製 MEK_ ST、数平均粒子 径 0. 022 x m、シリカ濃度 30%) 91. 3部（シリカ粒子として 27部）、イオン交換水 0. 12部、及び p メトキシフエノーノレ 0. 01部の混合液を、 60°C、 4時間攪拌後、オノレト 蟻酸メチルエステル 1. 36部を添加し、さらに 1時間同一温度で加熱攪拌することで 反応性粒子 (分散液（S— 3) )を得た。この分散液 (S— 3)をアルミ皿に 2g秤量後、 1 75°Cのホットプレート上で 1時間乾燥、秤量して固形分含量を求めたところ、 30. 7% であった。また、分散液（S— 3)を磁性るつぼに 2g秤量後、 80°Cのホットプレート上 で 30分予備乾燥し、 750°Cのマツフル炉中で 1時間焼成した後の無機残渣より、固 形分中の無機含量を求めたところ、 90%であった。  Composition containing polymerizable unsaturated groups produced in Production Example 10 (S-1) 2. 32 parts, silica particle sol (methylethylketone silica sol, MEK_ST, Nissan Chemical Industries, Ltd., number average particle size 0 022 xm, silica concentration 30%) 91. 3 parts (27 parts as silica particles), 0.112 parts of ion-exchanged water, and 0.01 part of p-methoxyphenol were mixed at 60 ° C for 4 hours. After the stirring, 1.36 parts of onoletoformic acid methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain reactive particles (dispersion liquid (S-3)). 2 g of this dispersion (S-3) was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to obtain a solid content of 30.7%. Also, weigh 2g of the dispersion (S-3) in a magnetic crucible, pre-dry on a hot plate at 80 ° C for 30 minutes, and calcinate in a 750 ° C matsufur furnace for 1 hour. The inorganic content in the form was determined to be 90%.
[0122] この分散液（S— 3) 98· 6g、組成物（S— 2) 3· 4g、 1ーヒドロキシシクロへキシルフ ェニルケトン 2· lg、ィルガキュア 907 (2—メチルー 1 [4 （メチルチオ）フエニル] —2—モルフォリノプロパン一 1—オン、チバ'スペシャルティ'ケミカルズ製） 1 · 2g、ジ ペンタエリスリトールへキサアタリレート（DPHA) 33· 2g、チヌビン 144 (ビス（1 , 2, 2 , 6, 6—ペンタメチルー 4ーピペリジニル） [ (3, 5—ジ tーブチルー 4ーヒドロキシ フエニル）メチル]ブチルマロネート、チノく'スペシャルティ'ケミカルズ製） 3. 7g、シク 口へキサノン 6gを混合攪拌し、シリカ粒子含有ハードコート層用組成物（H— 2 :固形 分濃度 50%)を 148g得た。  [0122] This dispersion (S—3) 98 · 6 g, composition (S—2) 3 · 4 g, 1-hydroxycyclohexyl phenyl ketone 2 · lg, Irgacure 907 (2-methyl-1 [4 (methylthio) phenyl ] —2—Morpholinopropane 1-one, Ciba 'Specialty' Chemicals) 1 · 2g, Dipentaerythritol Hexaatalylate (DPHA) 3 · 2g, Tinuvin 144 (Bis (1, 2, 2, 6, 6-Pentamethyl-4-piperidinyl) [(3,5-Di-tert-butyl-4-hydroxyphenyl) methyl] butyl malonate, manufactured by Tinoku 'Specialty' Chemicals) 3.7 g, mixed with 6 g hexanone in the mouth, containing silica particles 148 g of a composition for hard coat layer (H-2: solid content concentration 50%) was obtained.
[0123] (製造例 14)  [0123] (Production Example 14)
導電層（帯電防止層）を有するフィルム (b— 1)の作製  Preparation of film (b-1) having conductive layer (antistatic layer)
酸化剤としての FeClを、メチルアルコール、 2 _ブチルアルコール及びェチルセ口  FeCl as oxidizing agent, methyl alcohol, 2-butyl alcohol and ethyl acetate
2  2
ソルブがそれぞれ 6： 3： 1の割合で混合された溶剤に 3質量％溶解させて触媒溶液を 調製した。 Dissolve 3% by mass of the solvent in the solvent mixed at a ratio of 6: 3: 1 respectively. Prepared.
アートンフィルム（商品名、 JSR製、膜厚 100 μ m)表面に、前記で調製した触媒溶 液をスピンコーティングした後、得られた触媒塗膜を 60°Cで 3分間乾燥させた。  The catalyst solution prepared above was spin-coated on the surface of Arton film (trade name, manufactured by JSR, film thickness: 100 μm), and the obtained catalyst coating film was dried at 60 ° C. for 3 minutes.
次いでこのハードコート層及び触媒塗膜が形成されたポリエステルフィルムを飽和 状態の 3， 4_エチレンジォキシチォフェン単量体が生成されるように設計された CV Dチャンバ一に載置し、 3， 4_エチレンジォキシチォフェンを 30秒間重合反応させ た後、未反応物を除去するためにメタノール溶剤で洗浄し導電層を有するフィルム（b _ 1)を作製した。  Next, the polyester film on which the hard coat layer and the catalyst coating film were formed was placed in a CV D chamber designed to produce a saturated 3,4_ethylenedioxythiophene monomer. After 3,4_ethylenedioxythiophene was polymerized for 30 seconds, it was washed with methanol solvent to remove unreacted materials, and a film (b_1) with a conductive layer was prepared.
[0124] (製造例 15) [0124] (Production Example 15)
導電層（帯電防止層）を有するフィルム (b— 2)の作製  Production of film (b-2) with conductive layer (antistatic layer)
アートンフィルムの代わりにトリァセチルセルロースフィルム（L〇F〇製、膜厚 80 μ m)を使用した以外は実施例 14と同様の操作で、導電層を有するフィルム（b_ 2)を 作製した。  A film (b_2) having a conductive layer was prepared in the same manner as in Example 14 except that a triacetyl cellulose film (manufactured by LFO, film thickness 80 μm) was used instead of the Arton film.
[0125] (製造例 16) [0125] (Production Example 16)
低屈折率層塗工用ベース (G— 1)の作製  Preparation of low refractive index layer coating base (G-1)
製造例 14で作製した導電層を有するフィルム (b— 1)上に、製造例 12で調製した ジノレコニァ含有ハードコート層用組成物（H— 1：固形分濃度 30%)をワイヤーバーコ ータ（# 7)を用いて塗工し、オーブン中、 80°Cで 1分間乾燥し、塗膜を形成した。次 いで、空気下、高圧水銀ランプを用いて、 0. 9mj/cm2の光照射条件で紫外線を照 射し、ハードコート層を形成した。この基材上のハードコート層の膜厚を触針式表面 形状測定器により測定したところ、 3 μ mであった。 On the film (b-1) having the conductive layer produced in Production Example 14, the composition for dinoleconia-containing hard coat layer prepared in Production Example 12 (H-1: solid content concentration 30%) is applied to a wire bar coater ( # 7) was applied and dried in an oven at 80 ° C for 1 minute to form a coating film. Next, a hard coat layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.9 mj / cm 2 using a high-pressure mercury lamp in air. When the film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument, it was 3 μm.
上記操作により、基材上に導電層及びハードコート層が形成されたベース (G_ 1) を作製した。  By the above operation, a base (G_1) in which a conductive layer and a hard coat layer were formed on a substrate was produced.
[0126] (製造例 17) [0126] (Production Example 17)
低屈折率層塗工用ベース (G— 2)の作製  Preparation of low refractive index coating base (G-2)
製造例 14で作製した導電層を有するフィルム (b_ 1)上に、製造例 13で調製した シリカ粒子含有ハードコート層用組成物（H— 2 :固形分濃度 50%)をワイヤーバーコ ータ（# 12)を用いて塗工し、オーブン中、 80°Cで 1分間乾燥し、塗膜を形成した。 次いで、空気下、高圧水銀ランプを用いて、 0. 6mj/cm2の光照射条件で紫外線を 照射し、ハードコート層を形成した。この基材上のハードコート層の膜厚を触針式表 面形状測定器により測定したところ、 5 μ mであった。 On the film (b_1) having the conductive layer produced in Production Example 14, the composition for silica particle-containing hard coat layer (H-2: solid content concentration 50%) prepared in Production Example 13 was applied to a wire bar coater ( # 12) and dried in an oven at 80 ° C for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.6 mj / cm 2 using a high-pressure mercury lamp in the air to form a hard coat layer. When the film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument, it was 5 μm.
上記操作により、基材上に導電層及びハードコート層が形成されたベース (G_ 2) を作製した。  By the above operation, a base (G_2) in which a conductive layer and a hard coat layer were formed on a substrate was produced.
[0127] (製造例 18) [0127] (Production Example 18)
低屈折率層塗工用ベース (G— 3)の作製  Fabrication of low refractive index coating base (G-3)
導電層を有するフィルム (b— 1 )の代わりに、製造例 15で作製した導電層を有する フィルム (b_ 2)を使用した以外は製造例 17と同様の操作により、基材上に導電層及 びハードコート層が形成されたベース（G— 3)を作製した。  Instead of the film (b-1) having a conductive layer, the same procedure as in Production Example 17 was used except that the film (b_2) having a conductive layer prepared in Production Example 15 was used. And a base (G-3) on which a hard coat layer was formed.
[0128] (製造例 19) [0128] (Production Example 19)
硬化性樹脂組成物の作製  Preparation of curable resin composition
表 5に示すように、製造例 3で得たエチレン性不飽和基含有含フッ素重合体 (A— 1 )の MIBK溶液を 197g (A— 1として 30g)、製造例 5で得られた多孔質シリカ粒子分 散液を1440§ (8—1として70§)、光重合開始剤としてィルガキュァ907 (2—メチル — 1— [4— (メチルチオ）フエニル]— 2—モルフォリノプロパン一 1—オン、チバ 'スぺ シャルティ'ケミカルズ製） 2g及び MIBK903g (上記 A— 1、 B— 1に含まれる溶媒とし て添加した MIBKと合せて 2400g)を、攪拌機をつけたガラス製セパラブルフラスコ に仕込み、 23°Cにて 1時間攪拌し均一な硬化性樹脂組成物を得た。また、製造例 3 の方法により固形分含量を求めた。 As shown in Table 5, 197 g (30 g as A-1) of the MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (A-1) obtained in Production Example 3, and the porous material obtained in Production Example 5 Silica particle dispersion 1440 § (8-1 as 70 § ), Irgacure 907 (2-methyl — 1— [4- (methylthio) phenyl] — 2-morpholinopropane 1-one as photopolymerization initiator, Ciba 'Specialty Chemicals') 2g and MIBK903g (2400g combined with MIBK added as a solvent contained in A-1 and B-1 above) were placed in a glass separable flask equipped with a stirrer. The mixture was stirred at ° C for 1 hour to obtain a uniform curable resin composition. The solid content was determined by the method of Production Example 3.
この硬化性樹脂組成物をスピンコーターによりシリコンウェハー上に、乾燥後の厚さ が約 0. l x mとなるように塗布後、窒素下、高圧水銀ランプを用いて、 0. 5mj/cm2 の光照射条件で紫外線を照射して硬化させた。得られた硬化膜について、エリプソメ 一ターを用いて 25°Cでの波長 589nmにおける屈折率 (n 25)を測定した。結果を表 This curable resin composition was applied onto a silicon wafer by a spin coater so that the thickness after drying was about 0.1 lxm, and then a light of 0.5 mj / cm 2 was applied using a high-pressure mercury lamp under nitrogen. It was cured by irradiation with ultraviolet rays under irradiation conditions. With respect to the obtained cured film, the refractive index (n 25 ) at a wavelength of 589 nm at 25 ° C. was measured using an ellipsometer. Table the results
D  D
5に示す。  Shown in 5.
[0129] (製造例 20〜31) [0129] (Production Examples 20 to 31)
硬化性樹脂組成物の作製  Preparation of curable resin composition
表 5の組成に従った他は、製造例 19と同様にして硬化性樹脂組成物を得た。さら に得られた硬化性樹脂組成物について製造例 19と同様に屈折率を測定した。結果 を表 5に示す。 A curable resin composition was obtained in the same manner as in Production Example 19 except that the composition in Table 5 was followed. More The refractive index of the curable resin composition obtained in the same manner as in Production Example 19 was measured. The results are shown in Table 5.
[0130] (実施例:!〜 7、比較例 1、 2) [0130] (Examples:! To 7, Comparative Examples 1 and 2)
反射防止膜の作製  Preparation of antireflection film
表 5に示すように、製造例 16〜： 18で作製した硬化性樹脂組成物塗工用ベース（G _ 1〜3)上に、製造例 19〜29で作製した硬化性樹脂組成物をワイヤーバーコ一タ（ # 3)を用いて塗工し、オーブン中、 80°Cで 1分間乾燥し、塗膜を形成した。次いで、 窒素下、高圧水銀ランプを用いて、 0. 5mjZcm2の光照射条件で紫外線を照射し、 反射防止膜を作製した。ベース上の硬化物層の膜厚を反射率測定により概算したと ころ約 lOOnmであった。 As shown in Table 5, on the curable resin composition coating base (G_ 1 to 3) produced in Production Examples 16 to 18, the curable resin compositions produced in Production Examples 19 to 29 were wired. Coating was performed using a bar coater (# 3) and dried in an oven at 80 ° C for 1 minute to form a coating film. Next, using a high pressure mercury lamp under nitrogen, ultraviolet rays were irradiated under a light irradiation condition of 0.5 mjZcm 2 to produce an antireflection film. The thickness of the cured product layer on the base was estimated by reflectance measurement and was about lOOnm.
[0131] (比較例 3) [0131] (Comparative Example 3)
導電層（帯電防止層）を有するフィルム（b_ 1)の代わりにアートンフィルム（商品名、 J SR製、膜厚 100 μ m)を用いた以外は実施例 1と同様にして反射防止膜を得た。  An antireflection film was obtained in the same manner as in Example 1 except that Arton film (trade name, manufactured by JSR, film thickness 100 μm) was used instead of film (b_1) having a conductive layer (antistatic layer). It was.
[0132] (比較例 4) [0132] (Comparative Example 4)
製造例 19で作成した硬化性樹脂組成物を用レ、なレ、以外は実施例 1と同様にして積 層膜を得た。  A laminated film was obtained in the same manner as in Example 1 except that the curable resin composition prepared in Production Example 19 was used.
[0133] 得られた反射防止膜について以下の評価を行った。  [0133] The following evaluation was performed on the obtained antireflection film.
(1)耐擦傷性テスト 1 (布擦り耐性テスト）  (1) Abrasion resistance test 1 (Cloth abrasion resistance test)
実施例 1〜 7及び比較例 1〜4で作製した反射防止膜の表面を、エタノールを染み 込ませたセルロース製不織布（商品名ベンコット S— 2、旭化成せんレ、 (株））を用い て往復 200回手で擦り、反射防止膜表面の耐擦傷性を、以下の基準により目視にて 評価した。結果を表 5に示す。  The surfaces of the antireflection films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were reciprocated using a cellulose nonwoven fabric impregnated with ethanol (trade name Bencot S-2, Asahi Kasei Sen Co., Ltd.). By rubbing by hand 200 times, the scratch resistance of the antireflection film surface was visually evaluated according to the following criteria. The results are shown in Table 5.
◎:評価用試料表面が無傷。  A: The sample surface for evaluation is intact.
〇：評価用試料表面に細カ 、傷がっレ、てレ、る。  ◯: The surface of the sample for evaluation is fine, scratched, or distorted.
△：評価用試料表面に傷がっレ、てレ、る。  Δ: The surface of the sample for evaluation is damaged.
X：塗膜の剥離が見られる。  X: Peeling of the coating film is observed.
[0134] (2)耐擦傷性テスト 2 (スチールウール耐性テスト） [0134] (2) Scratch resistance test 2 (Steel wool resistance test)
実施例 1〜 7及び比較例 1〜4で作製した反射防止膜のスチールウール耐性テスト を、次に示す方法で実施した。即ち、スチールウール（ボンスター No. 0000、 日本ス チールウール (株)製)を学振型摩擦堅牢度試験機 (AB-301、テスター産業 (株)製 )に取りつけ、硬化膜の表面を荷重 200gの条件で 10回繰り返し擦過し、当該硬化膜 の表面における傷の発生の有無を、以下の基準により目視で確認した。結果を表 5 に示す。 Steel wool resistance test of antireflection films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 Was carried out by the following method. In other words, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded with a load of 200 g. By repeatedly rubbing 10 times under conditions, the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The results are shown in Table 5.
◎：硬化膜の剥離や傷の発生がほとんど認められなレ、。  (Double-circle): Re, in which almost no peeling or scratching of the cured film was observed
〇：硬化膜に細い傷が認められる。  ◯: A fine scratch is observed in the cured film.
X：硬化膜の一部に剥離が生じ、又は硬化膜の表面に筋状の傷が発生した。  X: Peeling occurred on a part of the cured film, or streak scratches occurred on the surface of the cured film.
[0135] (3)耐汚染性  [0135] (3) Pollution resistance
実施例:!〜 7及び比較例:!〜 4で作製した反射防止膜の塗膜表面に指紋をつけ、 不織布（商品名ベンコット S _ 2、旭化成せんい (株））にて塗膜表面を拭き取った。 耐汚染性を、以下の基準により評価した。結果を表 5に示す。  Example:! ~ 7 and comparative example:! ~ 4 Fingerprints were applied to the surface of the antireflection film prepared in 4 and the surface of the film was wiped off with a non-woven fabric (Bencot S_2, Asahi Kasei Fibers Co., Ltd.). It was. Contamination resistance was evaluated according to the following criteria. The results are shown in Table 5.
◎：きれレ、に拭き取られ塗膜表面の指紋跡が目視で確認できなかった。  (Double-circle): It was wiped off and the fingerprint trace on the coating film surface was not visually confirmed.
〇：塗膜表面の指紋跡がほぼ完全に拭き取られた。  A: The fingerprint trace on the surface of the coating film was almost completely wiped off.
X：拭き取られずに指紋跡が試料表面に残存した。  X: Fingerprint marks remained on the sample surface without being wiped off.
[0136] (4)反射防止性  [0136] (4) Antireflection
実施例 1〜 7及び比較例 1〜4で作製した反射防止膜の反射防止性を、分光反射 率測定装置（大型試料室積分球付属装置 150— 09090を組み込んだ自記分光光 度計 U— 3410、 日立製作所 (株)製）により、波長 550nmの反射率を測定して評価 した。具体的には、アルミの蒸着膜における反射率を基準（100%)として、反射防止 膜の反射率を測定し、波長 550nmにおける反射率が 1 %以下の場合を〇、 1 %を超 える場合を Xとした。  The anti-reflective properties of the anti-reflective coatings prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were compared with the spectral reflectance measuring device (self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090 , Manufactured by Hitachi, Ltd.), the reflectance at a wavelength of 550 nm was measured and evaluated. Specifically, the reflectance of the antireflection film is measured using the reflectance of the deposited aluminum film as a reference (100%). When the reflectance at the wavelength of 550 nm is 1% or less, it exceeds 〇, and exceeds 1%. X.
[0137] (5)帯電防止性  [0137] (5) Antistatic property
実施例 1〜 7及び比較例 1〜4で作成した反射防止膜の表面抵抗をハイレジスタン スメーター（Agilent 4339B)及びレジステイビティセル（Agilent 16008B)を用い、印 可電圧 100Vで測定し、表面抵抗値が 101Q Q /口未満の場合を〇、 101° 0 /ロ以 上の場合を Xとした。 The surface resistance of the antireflection film prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was measured using a high resistance meter (Agilent 4339B) and a resiliency cell (Agilent 16008B) at an applied voltage of 100 V, and the surface When the resistance value is less than 10 1Q Q / mouth, it is marked as ◯, and when the resistance value is more than 10 1 ° 0 / b, X is marked as X
[0138] [表 5]
Figure imgf000048_0001
[0138] [Table 5]
Figure imgf000048_0001
産業上の利用可能性 Industrial applicability
本発明の反射防止膜は、帯電防止性、耐擦傷性及び耐汚染性に優れた反射防止 膜として有用である。  The antireflection film of the present invention is useful as an antireflection film having excellent antistatic properties, scratch resistance and stain resistance.

Claims

請求の範囲 The scope of the claims
[1] 基材上に、  [1] On the substrate,
ピロ一ノレ、チォフェン、フラン、セレノフェン及び 3, 4_エチレンジォキシチォフェン 並びにこれらの誘導体からなる群から選択される少なくとも一種の単量体を気相重合 して形成された導電層、並びに、  A conductive layer formed by vapor-phase polymerization of at least one monomer selected from the group consisting of pyrrolinole, thiophene, furan, selenophene and 3,4_ethylenedioxythiophene and derivatives thereof; and ,
下記成分 (A)及び (B1) :  The following components (A) and (B1):
(A)エチレン性不飽和基含有含フッ素重合体、  (A) an ethylenically unsaturated group-containing fluoropolymer,
(B1)下記式（1)で表されるケィ素化合物及び式（2)で表されるケィ素化合物の加 水分解物及び/又は加水分解縮合物からなり、平均粒径が 5〜50nmである多孔質 シリカ粒子  (B1) It is composed of a key compound represented by the following formula (1) and a hydrolyzate and / or hydrolysis condensate of the key compound represented by formula (2), and the average particle size is 5 to 50 nm. Some porous silica particles
R1 SiX · · · (1) R 1 SiX (1)
h 4-h  h 4-h
R2 SiX · · · (2) R 2 SiX (2)
j 4-j  j 4-j
(R1は炭素数 1〜8のアルキル基、 Xはそれぞれ独立に炭素数 1〜4のアルコキシ基、 ハロゲノ基、イソシァネート基（一 N = C = 0)、カルボキシル基、炭素数 2〜4のアル キルォキシカルボニル基又は炭素数 1〜4のアルキルアミノ基、 hは 0〜 1の整数を示 す。 R2は炭素数 2〜8のアルケニル基、炭素数 4〜8のアタリロキシアルキル基又は炭 素数 5〜8のメタクリロキシアルキル基、 jは 1〜3の整数を示す。尚、式（1)の X及び式 (2)の Xは同一であっても異なっていてもよレ、。）、 (R 1 is an alkyl group having 1 to 8 carbon atoms, X is independently an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group (one N = C = 0), a carboxyl group, and a carbon group having 2 to 4 carbon atoms. An alkylcarbonyl group or an alkylamino group having 1 to 4 carbon atoms, h represents an integer of 0 to 1. R 2 is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms. Or a methacryloxyalkyl group having 5 to 8 carbon atoms, j represents an integer of 1 to 3. X in formula (1) and X in formula (2) may be the same or different, ),
を含む硬化性樹脂組成物の硬化物からなる低屈折率層、  A low refractive index layer comprising a cured product of a curable resin composition containing
を有する反射防止膜。  An antireflection film.
[2] 基材上に、 [2] On the substrate,
ピロ一ノレ、チォフェン、フラン、セレノフェン及び 3, 4_エチレンジォキシチォフェン 並びにこれらの誘導体からなる群から選択される少なくとも一種の単量体を気相重合 して形成された導電層、並びに、  A conductive layer formed by vapor-phase polymerization of at least one monomer selected from the group consisting of pyrrolinole, thiophene, furan, selenophene and 3,4_ethylenedioxythiophene and derivatives thereof; and ,
下記成分 (A)及び (B2) :  The following ingredients (A) and (B2):
(A)エチレン性不飽和基含有含フッ素重合体、  (A) an ethylenically unsaturated group-containing fluoropolymer,
(B2)下記式（1)で表されるケィ素化合物、式 (2)で表されるケィ素化合物及び式（ 3)で表されるケィ素化合物の加水分解物及び/又は加水分解縮合物からなり、平 均粒径が 5〜50nmである多孔質シリカ粒子 (B2) a key compound represented by the following formula (1), a key compound represented by the formula (2) and a hydrolyzate and / or a hydrolyzed condensate of the key compound represented by the formula (3) Made of flat Porous silica particles having an average particle size of 5 to 50 nm
R1 SiX R 1 SiX
h 4-h •••(1)  h 4-h ••• (1)
R2 SiX ' •••(2) R 2 SiX '••• (2)
j 4-j  j 4-j
R3 SiX •••(3) R 3 SiX ••• (3)
k 4-k  k 4-k
(R1は炭素数 1〜8のアルキル基、 Xはそれぞれ独立に炭素数 1〜4のアルコキシ基、 ハロゲノ基、イソシァネート基（_N = C =〇）、カルボキシル基、炭素数 2〜4のアル キルォキシカルボニル基又は炭素数 1〜4のアルキルアミノ基、 hは 0〜 1の整数を示 す。 R2は炭素数 2〜8のアルケニル基、炭素数 4〜8のアタリロキシアルキル基又は炭 素数 5〜8のメタクリロキシアルキル基、 jは 1〜3の整数を示す。 R3は炭素数 1〜12の フッ素置換アルキル基、 kは 1〜3の整数を示す。尚、式（1)の X、式（2)の X及び式（ 3)の Xは、同一であっても異なっていてもよレ、。）、 (R 1 is an alkyl group having 1 to 8 carbon atoms, X is independently an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group (_N = C = 0), a carboxyl group, an alkyl group having 2 to 4 carbon atoms. A siloxycarbonyl group or an alkylamino group having 1 to 4 carbon atoms, h is an integer of 0 to 1. R 2 is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms, or A methacryloxyalkyl group having 5 to 8 carbon atoms, j represents an integer of 1 to 3. R 3 represents a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and k represents an integer of 1 to 3. X in formula (2) and X in formula (3) may be the same or different.),
を含む硬化性樹脂組成物の硬化物からなる低屈折率層、  A low refractive index layer comprising a cured product of a curable resin composition containing
を有する反射防止膜。  An antireflection film.
[3] 前記多孔質シリカ粒子 (B1)が、前記式（1)で表されるケィ素化合物及び式 (2)で 表されるケィ素化合物の合計を 100モル％としたとき、前記加水分解物及び/又は 加水分解縮合物が、式（1)で表されるケィ素化合物 67〜99モル％及び式（2)で表 されるケィ素化合物 33〜1モル％の反応物からなる、請求項 1に記載の反射防止膜  [3] When the porous silica particles (B1) have a total of 100 mol% of the key compound represented by the formula (1) and the key compound represented by the formula (2), the hydrolysis is performed. And / or the hydrolysis condensate comprises a reactant of 67 to 99 mol% of the key compound represented by the formula (1) and 33 to 1 mol% of the key compound represented by the formula (2). Item 1. Antireflection film according to item 1
[4] 前記多孔質シリカ粒子 (B2)が、前記式（1)で表されるケィ素化合物、式 (2)で表さ れるケィ素化合物及び式（3)で表されるケィ素化合物の合計を 100モル％としたとき 、前記加水分解物及び/又は加水分解縮合物が、式（1)で表されるケィ素化合物 6 0〜98モノレ％、式（2)で表されるケィ素化合物 1〜30モル％及び式（3)で表されるケ ィ素化合物 1〜20モル％の反応物からなる、請求項 2に記載の反射防止膜。 [4] The porous silica particles (B2) are composed of a key compound represented by the formula (1), a key compound represented by the formula (2), and a key compound represented by the formula (3). When the total is 100 mol%, the hydrolyzate and / or hydrolyzed condensate is a key compound represented by the formula (1) 60 to 98 mono%, a key represented by the formula (2). The antireflection film according to claim 2, comprising a reaction product of 1 to 30 mol% of the compound and 1 to 20 mol% of the silicon compound represented by the formula (3).
[5] 前記式（1)で表されるケィ素化合物において、 hが 0である、請求項:!〜 4のいずれ か一項に記載の反射防止膜。  [5] The antireflection film according to any one of [5] to [4], wherein h is 0 in the key compound represented by the formula (1).
[6] 前記多孔質シリカ粒子（B1)又は (B2)力 水、炭素数 1〜3のアルコール、塩基性 化合物、並びに酸アミド、ジオール及びジオールの半エーテルからなる群から選ば れる少なくとも 1種の存在下でカ卩水分解及び Z又は加水分解縮合されたものである 請求項:!〜 5のいずれか一項に記載の反射防止膜。 [6] The porous silica particles (B1) or (B2) force at least one selected from the group consisting of water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols and half ethers of diols. It has been hydrolyzed and Z or hydrolytically condensed in the presence. Claim: The antireflection film according to any one of! To 5.
[7] 前記エチレン性不飽和基含有含フッ素重合体 (A)が、 [7] The ethylenically unsaturated group-containing fluoropolymer (A) is:
1個のイソシァネート基と、少なくとも 1個のエチレン性不飽和基とを含有する化合物 と、  A compound containing one isocyanate group and at least one ethylenically unsaturated group;
水酸基含有含フッ素重合体と、  A hydroxyl group-containing fluoropolymer,
をイソシァネート基 Z水酸基のモル比が 1. 1〜： 1. 9の割合で反応させて得られる エチレン性不飽和基含有含フッ素重合体である請求項 1〜6のいずれか一項に記載 の反射防止膜。  Is an ethylenically unsaturated group-containing fluorine-containing polymer obtained by reacting an isocyanate group with a molar ratio of Z hydroxyl group of 1.1 to 1.9. Antireflection film.
[8] 前記水酸基含有含フッ素重合体が、下記構造単位 (a)、（b)及び (c)の合計 100モ ル％に対して、構造単位（a) 20〜70モノレ％、構造単位（b) 10〜70モル％及び構造 単位（c) 5〜70モル％の割合で含んでなり、かつ、  [8] The hydroxyl group-containing fluoropolymer has a structural unit (a) of 20 to 70 monolayers, a structural unit (100%) of the following structural units (a), (b) and (c). b) comprising 10 to 70 mol% and structural units (c) in a proportion of 5 to 70 mol%, and
ゲルパーミエーシヨンクロマトグラフィーで測定したポリスチレン換算数平均分子量 が 5, 000-500, 000である請求項 7に記載の反射防止膜。  8. The antireflection film according to claim 7, wherein the polystyrene-reduced number average molecular weight measured by gel permeation chromatography is 5,000-500,000.
(a)下記式 (4)で表される構造単位  (a) Structural unit represented by the following formula (4)
(b)下記式（5)で表される構造単位  (b) Structural unit represented by the following formula (5)
(c)下記式 (6)で表される構造単位  (c) Structural unit represented by the following formula (6)
[化 15]  [Chemical 15]
Figure imgf000052_0001
Figure imgf000052_0001
[式（4)中、 R4はフッ素原子、フルォロアルキル基又は— OITで表される基（R5はァ ルキル基又はフルォロアルキル基を示す）を示す] [In the formula (4), R 4 represents a fluorine atom, a fluoroalkyl group or a group represented by —OIT (R 5 represents an alkyl group or a fluoroalkyl group)]
[化 16]  [Chemical 16]
H R6 C—— C ( 5 ) HR 6 C—— C (5)
I  I
1  1
H R'  H R '
[式（5)中、 R6は水素原子又はメチル基を、 R7はアルキル基、 _ (CH )—OR8若し [In the formula (5), R 6 is a hydrogen atom or a methyl group, R 7 is an alkyl group, _ (CH 3) —OR 8 or
2 OCOR8で表される基（ はアルキル基又はグリシジル基を、 Xは 0又は 1の数 を示す）、カルボキシル基又はアルコキシ力ルポ二ル基を示す] 2 A group represented by OCOR 8 (represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxy group.
[化 17]  [Chemical 17]
Figure imgf000053_0001
Figure imgf000053_0001
[式（6)中、 R9は水素原子又はメチル基を、 R1Qは水素原子又はヒドロキシアルキル 基を、 Vは 0又は 1の数を示す] [In the formula (6), R 9 represents a hydrogen atom or a methyl group, R 1Q represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]
[9] 前記水酸基含有含フッ素重合体が、さらに、前記構造単位 (a)、 （b)及び (c)の合 計 100モル部に対して、ァゾ基含有ポリシロキサン化合物に由来する下記構造単位 (d) 0.：!〜 10モル部を含む請求項 8に記載の反射防止膜。  [9] The following structure derived from an azo group-containing polysiloxane compound, wherein the hydroxyl group-containing fluoropolymer is further added to 100 mol parts of the total of the structural units (a), (b) and (c). The antireflection film according to claim 8, comprising the unit (d) 0.:! To 10 mol parts.
(d)下記一般式 (7)で表される構造単位  (d) Structural unit represented by the following general formula (7)
[化 18]  [Chemical 18]
R11 R 11
-0- ( 7 ) -0- (7)
12  12
[一般式（7)中、 R11及び R12は、同一でも異なっていてもよぐ水素原子、アルキノレ 基、ハロゲン化アルキル基又はァリール基を示す] [In the general formula (7), R 11 and R 12 may be the same or different and each represents a hydrogen atom, an alkynole group, a halogenated alkyl group or an aryl group]
[10] さらに、導電層と低屈折率層との間に、ハードコート層を有する請求項 1〜9のいず れか一項に記載の反射防止膜。  10. The antireflection film according to any one of claims 1 to 9, further comprising a hard coat layer between the conductive layer and the low refractive index layer.
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CN102050834B (en) * 2009-11-06 2013-04-17 财团法人工业技术研究院 Reactive silica compound and optical protective film with same
CN113684469A (en) * 2021-08-06 2021-11-23 宁波摩华科技有限公司 Organic protective coating for electronic device and preparation method thereof
CN113684469B (en) * 2021-08-06 2023-08-22 宁波摩华科技有限公司 Organic protective coating for electronic device and preparation method thereof

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JP2006209050A (en) 2006-08-10
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