WO2011099505A1 - Dispositif pour l'extérieur et couche antireflet destinée à un dispositif pour l'extérieur - Google Patents

Dispositif pour l'extérieur et couche antireflet destinée à un dispositif pour l'extérieur Download PDF

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Publication number
WO2011099505A1
WO2011099505A1 PCT/JP2011/052716 JP2011052716W WO2011099505A1 WO 2011099505 A1 WO2011099505 A1 WO 2011099505A1 JP 2011052716 W JP2011052716 W JP 2011052716W WO 2011099505 A1 WO2011099505 A1 WO 2011099505A1
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group
layer
composition
organosilane
acid
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PCT/JP2011/052716
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English (en)
Japanese (ja)
Inventor
吉井　公彦
昌泰 藤岡
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Jsr株式会社
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Priority to KR1020127018169A priority Critical patent/KR20120126068A/ko
Priority to JP2011553857A priority patent/JPWO2011099505A1/ja
Publication of WO2011099505A1 publication Critical patent/WO2011099505A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to an outdoor installation device having an antireflection layer and an antireflection layer for an outdoor installation device. More specifically, the present invention relates to an outdoor installation device having an antireflection layer that can be formed by a simple method and exhibits excellent weather resistance in outdoor use, and the antireflection layer.
  • an antireflection film composed of a low refractive index material on the surface of the article, or an antireflection film composed of a multilayer structure of a low refractive index layer and a high refractive index layer Has been made to form.
  • conversion efficiency can be improved by performing the antireflection process on the surface.
  • Patent Documents 1 to 3 As a method of forming these antireflection films, for example, a method using an organic ultraviolet / radiation curable material or a method of forming an inorganic material by vapor deposition or the like is known (Patent Documents 1 to 3). ).
  • the top layer contains a large amount of high-refractive-index metal oxides such as titanium oxide and zinc oxide, the difference in refractive index from air becomes large, and instead of preventing surface reflection, the reflectance is reversed. Is incompatible with anti-reflection applications.
  • polydimethylsiloxane silicone
  • the coating film has low hardness. There are problems such as inferior adhesiveness, difficulty in increasing the refractive index, and difficulty in designing a laminate, and use as an antireflection layer has been difficult.
  • an object of the present invention is to provide an outdoor installation device having an antireflection layer that exhibits excellent weather resistance in outdoor use and that can be formed on a substrate by a simple method.
  • Another object of the present invention is to provide an antireflection layer for a device for outdoor installation, which exhibits excellent weather resistance in outdoor use and can be formed on a substrate by a simple method.
  • the outdoor installation device of the present invention mainly comprises a layer (I) containing polyorganosiloxane (A) and metal oxide particles (B), polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm. It has an antireflection layer comprising a laminate with a layer (II) containing hollow or porous particles (D) as a component.
  • the layer (I) has the following formula (1) R 1 n Si (OR 2 ) 4-n (1) (Wherein, R 1 represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, optionally .R 2 be different be the same as each other if there are two or more are each independently Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3.) At least one silane compound (a1) selected from the group consisting of at least one organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane represented by the formula: Obtained from a cured product of the composition (I) containing,
  • the layer (II) is represented by the following formula (2) R 3 m Si (OR 4 ) 4-m (2) (Wherein, R 3 represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, optionally .R 4 be
  • the silane compound (a1) of the composition (I) preferably contains a silane compound in which at least one of R 1 in the formula (1) is a phenyl group.
  • R 1 in the formula (1) is a phenyl group.
  • 5 to 80 mol% of all R 1 in the formula (1) is preferably a phenyl group.
  • Typical examples of the outdoor installation device on which the antireflection layer is formed include an outdoor installation display and a solar cell.
  • the antireflection layer for a device for outdoor installation of the present invention comprises a layer (I) containing a polyorganosiloxane (A) and metal oxide particles (B), a polyorganosiloxane (C) and a number average particle diameter of 1 to 100 nm. It consists of a laminated body with the layer (II) containing the hollow or porous particle
  • the present invention it is possible to obtain a device for outdoor installation having an antireflection layer that can be easily formed by means such as coating and has excellent weather resistance in outdoor use.
  • the device for outdoor installation of the present invention comprises a layer (I) containing polyorganosiloxane (A) and metal oxide particles (B) on the surface of the surface member of the device for outdoor installation as a base material, and polyorganosiloxane. It has an antireflection layer comprising a laminate of (C) and a layer (II) containing hollow or porous particles (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm. .
  • polyorganosiloxane refers to a polymer having a Si—O bond as a skeleton.
  • the device for outdoor installation of the present invention is not particularly limited as long as antireflection properties are required on the surface thereof, for example, a display for outdoor installation, a solar cell, and the like. Can be mentioned.
  • a surface forming member that forms such a surface in a device for outdoor installation is used as a base material, and an antireflection layer is formed thereon.
  • the material of this base material is not particularly limited, and examples thereof include metals, ceramics, glass, resin, wood, slate and the like.
  • the resin examples include polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin (TAC), diallyl carbonate of diethylene glycol (CR-39), ABS resin, and AS resin. , Polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene resin), and the like. By forming an antireflection layer on the surface of these substrates, an excellent antireflection effect can be obtained.
  • Layer (I) contains polyorganosiloxane (A) and metal oxide particles (B).
  • the layer (I) has a refractive index of 1.50 or more and less than 1.85, depending on the type of device for outdoor installation, and has a film thickness in the range of 0.01 ⁇ m to 10 ⁇ m.
  • composition (I) Such a layer (I) has, for example, the following formula (1): R 1 n Si (OR 2 ) 4-n (1) (Wherein, R 1 represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, optionally .R 2 be different be the same as each other if there are two or more are each independently Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3.) And selected from the group consisting of hydrolyzate of organosilane (1) and condensate of organosilane (1). It can be obtained from a cured product of a composition comprising at least one silane compound (a1) and metal oxide particles (B) (hereinafter also referred to as “composition (I)”).
  • silane compound (a1) The silane compound (a1) used in the present invention is selected from the group consisting of organosilane (1) represented by the above formula (1), hydrolyzate of organosilane (1) and condensate of organosilane (1). At least one silane compound, and among these three silane compounds, only one silane compound may be used, or any two silane compounds may be used in combination, or You may mix and use all three types of silane compounds. Moreover, when using organosilane (1) as a silane compound (a1), organosilane (1) may be used individually by 1 type, or may use 2 or more types together.
  • the hydrolyzate and condensate of the organosilane (1) may be formed from one kind of organosilane (1) or may be formed by using two or more kinds of organosilane (1) in combination. Good.
  • the hydrolyzate of the organosilane (1) is sufficient if at least one of the OR 2 groups contained in 1 to 4 of the organosilane (1) is hydrolyzed, for example, one OR 2 group. In which two or more OR 2 groups are hydrolyzed, or a mixture thereof.
  • the organosilane (1) condensate is a product in which silanol groups in the hydrolyzate produced by hydrolysis of organosilane (1) are condensed to form Si—O—Si bonds.
  • the condensate is a product obtained by condensing a small part of silanol groups, a product obtained by condensing most (including all) silanol groups, Includes a mixture thereof.
  • R 1 is a non-hydrolyzable organic group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group.
  • Alkyl groups such as heptyl group, octyl group, decyl group, 2-ethylhexyl group; Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group; Vinyl group, allyl group, cyclohexyl group, phenyl group, epoxycycloalkyl group, 3,4-epoxycyclohexylethyl group, glycidyl group, 3-glycidyloxypropyl group, (meth) acryloxy group, 3- (meth) acryloxy Examples thereof include a propyl group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.
  • examples of R 1 include substituted derivatives of the above organic groups.
  • examples of the substituent of the substituted derivative of R 1 include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, Examples thereof include a ureido group and an ammonium base.
  • a plurality of R 1 are present in formula (1), they may be the same or different.
  • R 2 that is an alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and R 2 that is an acyl group having 1 to 6 carbon atoms.
  • R 2 include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.
  • silane compounds substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, etc.
  • a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-oc
  • silane compounds substituted with two non-hydrolyzable groups and two hydrolyzable groups dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane , Di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxy Silane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyl
  • At least one of R 1 contains a silane compound which is a phenyl group, and in formula (1), the phenyl group is 5 to 80 mol% with respect to all R 1 . What is contained is preferable.
  • the organosilane having a phenyl group is a mole of the organosilane having a phenyl group in the formula (1) from the viewpoint of the storage stability of the composition (I) according to the present invention and the crack resistance of the layer (I) to be formed.
  • the concentration is preferably 5 to 80% with respect to all R 1 , more preferably 5 to 60%.
  • the composition (I) When the content of the organosilane having a phenyl group is too much more than the above range, the composition (I) When the content of the organosilane having a phenyl group is too smaller than the above range, the storage stability of the composition (I) and the crack resistance of the layer (I) to be formed may be inferior. is there.
  • one type of organosilane (1) may be used alone as the silane compound (a1), but two or more types of organosilane (1) may be used in combination.
  • the averaged n (hereinafter also referred to as “average value of n”) is.
  • it is 0.5 to 2.0, more preferably 0.6 to 1.8, and particularly preferably 0.7 to 1.6.
  • the average value of n is less than the lower limit, the storage stability of the composition (I) and the crack resistance of the layer (I) may be inferior, and when the upper limit is exceeded, the curability of the composition (I) is inferior.
  • the average value of n can be adjusted to the above range by appropriately using a monofunctional to tetrafunctional organosilane (1) and appropriately adjusting the blending ratio.
  • organosilane (1) may be used as it is as silane compound (a1), but hydrolyzate and / or condensate of organosilane (1) can be used.
  • organosilane (1) is used as a hydrolyzate and / or condensate
  • a product prepared by previously hydrolyzing and condensing the organosilane (1) may be used, but the composition (I) is prepared.
  • the hydrolyzate and / or condensate of organosilane (1) can also be prepared by hydrolyzing and condensing organosilane (1).
  • the conditions for hydrolyzing and condensing the silane compound (a1) represented by the above formula (1) are hydrolyzable by hydrolyzing at least a part of the organosilane (1) represented by the above formula (1). Although it does not specifically limit as long as it converts a group into a silanol group or causes a condensation reaction, it can be carried out as follows as an example.
  • the water used for hydrolysis of the organosilane (1) represented by the above formula (1) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.
  • the amount of water used is preferably from 0.1 to 3 mol, more preferably from 1 mol of the total amount of hydrolyzable groups (—OR 2 ) of the organosilane (1) represented by the above formula (1). Is in an amount of 0.3 to 2 mol, more preferably 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of hydrolysis can be optimized.
  • Organic solvent Although it does not specifically limit as a solvent which can be used for hydrolysis and condensation of the organosilane (1) represented by the said Formula (1), Usually, for manufacture of the polymer (A1) mentioned later. The thing similar to the solvent used can be used.
  • a solvent include propyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. .
  • propyl alcohol methyl isobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate are preferable.
  • catalyst Although it does not specifically limit as a catalyst which can be used for the hydrolysis and condensation reaction of organosilane (1) represented by the said Formula (1), Usually, manufacture of the polymer (A1) mentioned later The same catalyst as used in the above can be used.
  • Such catalysts include acid catalysts (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids), Basic catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate Carboxylates such as sodium acetate; various Lewis bases] or alkoxides (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide) and the like.
  • acid catalysts for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulf
  • tetra-i-propoxyaluminum can be used as the aluminum alkoxide.
  • the amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis reaction. It is.
  • the reaction temperature and reaction time in hydrolysis / condensation of the organosilane (1) represented by the above formula (1) are appropriately set.
  • the reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
  • the reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis reaction can be performed most efficiently.
  • the hydrolyzable silane compound, water and catalyst may be added to the reaction system at a time to carry out the reaction in one step, or the hydrolyzable silane compound, water and catalyst may be added,
  • the hydrolysis and condensation reaction may be performed in multiple stages by adding them into the reaction system in several times.
  • the condensate of the organosilane (1) has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC method), preferably 300 to 100,000. More preferably, it is 500 to 50,000.
  • Mw polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography
  • organosilane (1) condensate When used as the silane compound (a1) in the present invention, it may be prepared from the organosilane (1) or a commercially available organosilane condensate.
  • organosilane condensates include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resins and silicone oligomers manufactured by Toray Dow Corning Silicone Co., Momentive Performance Examples include silicone resins and silicone oligomers manufactured by Materials Co., Ltd., silicone resins and silicone oligomers manufactured by Shin-Etsu Chemical Co., Ltd., and hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd. These condensates of commercially available organosilanes may be used as they are or may be further condensed.
  • the above silane compound (a1) and the vinyl polymer (a2) containing a specific silyl group are hydrolyzed / condensed for the purpose of improving the adhesion to the substrate.
  • the polymer (A1) comprises a catalyst containing water and a catalyst that promotes hydrolysis / condensation reaction in a mixture containing the silane compound (a1) and a vinyl polymer (a2) containing a silyl group. And added.
  • the vinyl polymer (a2) containing a specific silyl group used in the present invention (hereinafter also referred to as “specific silyl group-containing vinyl polymer (a2)”) is composed of a hydrolyzable group and / or a hydroxyl group. It contains a silyl group having a bonded silicon atom (hereinafter referred to as “specific silyl group”).
  • the specific silyl group-containing vinyl polymer (a2) preferably has a specific silyl group at the terminal and / or side chain of the polymer molecular chain.
  • the hydrolyzable group and / or hydroxyl group in the specific silyl group co-condenses with the silane compound (a1) to form the polymer (A1).
  • the composition containing this polymer (A1) and metal oxide particles (B) acts as a high refractive index layer, and further layer (II) described later is further coated An antireflection layer can be formed.
  • the specific silyl group has the following formula (3): (Wherein X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group, or a hydroxyl group, and R 5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or Represents an aralkyl group having 1 to 10 carbon atoms, and i is an integer of 1 to 3.) It is preferable that it is group represented by these.
  • Such a specific silyl group-containing vinyl polymer (a2) can be produced, for example, by the following methods (I) and (II).
  • hydrosilane compound (I) A hydrosilane compound having a specific silyl group represented by the above formula (3) (hereinafter also simply referred to as “hydrosilane compound (I)”) is converted into a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “hydrosilane compound (I)”). , “Unsaturated vinyl polymer”)) in which the carbon-carbon double bond is subjected to an addition reaction.
  • hydrosilane compound (I) used in the above method (I) examples include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldimethoxysilane, methyldiethoxysilane, and phenyldimethoxy.
  • Alkoxysilanes such as silane, trimethoxysilane, triethoxysilane; Acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane; Methyldiaminoxysilane, triaminoxysilane, dimethylaminoxysilane And aminoxysilanes.
  • These hydrosilane compounds (I) can be used alone or in admixture of two or more.
  • the unsaturated vinyl polymer used in the method (I) is not particularly limited as long as it is a polymer having a hydroxyl group. For example, the following methods (I-1) and (I-2) Or it can manufacture by these combinations.
  • (I-2) Radical polymerization initiator having functional group ( ⁇ ) (for example, 4,4′-azobis-4-cyanovaleric acid Or a compound having a functional group ( ⁇ ) in both radical polymerization initiator and chain transfer agent (for example, 4,4′-azobis-4-cyanovaleric acid and dithioglycolic acid)
  • the vinyl monomer is (co) polymerized and one end of the polymer molecular chain or After synthesizing a (co) polymer having a functional group ( ⁇ ) derived from a radical polymerization initiator or chain transfer agent at the terminal, a functional group ( ⁇ ) is added to the functional group ( ⁇ ) in the (co) polymer.
  • a functional group ( ⁇ ) is added to the functional group ( ⁇ ) in the (co) polymer.
  • Examples of the reaction between the functional group ( ⁇ ) and the functional group ( ⁇ ) in the methods (I-1) and (I-2) include an esterification reaction between a carboxyl group and a hydroxyl group, and a carboxylic anhydride group and a hydroxyl group.
  • Vinyl monomer having a functional group ( ⁇ ) examples include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and the like.
  • unsaturated carboxylic acids include unsaturated carboxylic acids; Unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; Hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether; Amino group-containing vinyl monomers such as 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-aminoethyl vinyl ether; 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1 -Dimethyl-1
  • vinyl monomers that can be copolymerized with a vinyl monomer having a functional group ( ⁇ ) include, for example, styrene, ⁇ -methylstyrene, 4-methylstyrene.
  • UV-absorbing monomers such as 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone and 2-hydroxy-4- (acryloyloxyethoxy) benzophenone; Examples include dicaprolactone and allyl (meth) acrylate. These can be used alone or in combination of two or more.
  • an unsaturated compound having a functional group ( ⁇ ) and a carbon / carbon double bond for example, a vinyl monomer similar to the vinyl monomer having a functional group ( ⁇ ), or the above hydroxyl group-containing vinyl type
  • An isocyanate group-containing unsaturated compound obtained by reacting a monomer and a diisocyanate compound in an equimolar amount can be exemplified.
  • Examples of other vinyl monomers copolymerized with the unsaturated silane compound include, for example, vinyl monomers having the functional group ( ⁇ ) exemplified in the method (I-1) and other vinyl monomers. A monomer etc. can be mentioned.
  • Examples of the method for producing the specific silyl group-containing vinyl polymer (a2) include, for example, a method in which each monomer is added at once and polymerized. For example, a method in which polymerization is carried out by adding them intermittently or a method in which a monomer is continuously added from the start of polymerization. These polymerization methods may be combined.
  • a preferred polymerization method includes solution polymerization.
  • the solvent used in the solution polymerization is not particularly limited as long as it can produce the specific silyl group-containing vinyl polymer (a2).
  • alcohols diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene Examples include glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ethers, ketones and esters.
  • Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-octyl alcohol, and ethylene glycol.
  • Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
  • Ethylene glycol alcohol examples include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.
  • Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether and propylene glycol monoethyl ether. Propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like.
  • propylene glycol monoalkyl ether acetates for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol
  • propylene glycol monoalkyl ether propionate propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol mono Examples include butyl ether propionate.
  • Aromatic hydrocarbons include benzene, toluene, xylene, etc.
  • ethers include tetrahydrofuran, dioxane, etc.
  • ketones include acetone, cyclohexanone, 2-heptanone, 4-hydroxy- 4-methyl-2-pentanone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like.
  • esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate Butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate
  • the specific silyl group-containing vinyl polymer (a2) in addition to the specific silyl group-containing vinyl polymer polymerized as described above, the specific silyl group-containing epoxy resin and the specific silyl group-containing polyester resin are used.
  • Other specific silyl group-containing vinyl polymers such as can also be used.
  • the specific silyl group-containing epoxy resin include epoxy groups in epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, aliphatic polyglycidyl ethers, and aliphatic polyglycidyl esters.
  • the specific silyl group-containing polyester resin is produced, for example, by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with an aminosilane having a specific silyl group, a carboxysilane, or a glycidylsilane. Can do.
  • the polystyrene-equivalent Mw of the specific silyl group-containing vinyl polymer (a2) measured by the GPC method is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.
  • the specific silyl group-containing vinyl polymer (a2) can be used alone or in admixture of two or more.
  • the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) may be co-condensed.
  • it can be prepared by adding a hydrolysis / condensation reaction catalyst and water to a mixture of the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) and co-condensing it.
  • Wa1 is a complete hydrolysis condensate conversion value of the silane compound (a1)
  • Wa2 is a solid content conversion value of the specific silyl group-containing vinyl polymer (a2).
  • the completely hydrolyzed condensate means a product in which the —OR group of a silane compound is hydrolyzed to 100% to become a Si—OH group, and further completely condensed to a siloxane structure.
  • the polymer (A1) is preferably prepared by the following methods (1) to (2).
  • the polymer (A1) is prepared by co-condensing the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) in ⁇ 12 hours. Thereafter, if necessary, other additives such as a stability improver may be added.
  • the weight average molecular weight of the polymer (A1) obtained by the above method is usually 2,500 to 200,000, preferably 3,000 to 150,000, more preferably in terms of polystyrene measured by gel permeation chromatography. 3,500 to 100,000.
  • the silane compound (a1) or the specific silyl group-containing vinyl polymer (a2) is promoted by hydrolysis / condensation reaction. And a specific silyl group-containing vinyl polymer (a2).
  • a catalyst By adding a catalyst, the degree of cross-linking of the resulting polymer (A1) can be increased, and the molecular weight of the polysiloxane produced by the polycondensation reaction of the organosilane (1) is increased.
  • a layer (I) excellent in durability and the like can be obtained.
  • the addition of the catalyst promotes the reaction between the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2), and sufficient reaction sites (alkoxy groups) are formed in the polymer (A1).
  • the catalyst used for promoting such hydrolysis / condensation reaction include basic compounds, acidic compounds, salt compounds, and organometallic compounds.
  • Basic compound examples include ammonia (including ammonia aqueous solution), organic amine compounds, alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals, alkalis such as sodium methoxide and sodium ethoxide. Examples thereof include metal alkoxides. Of these, ammonia and organic amine compounds are preferred.
  • Examples of the organic amine include alkylamine, alkoxyamine, alkanolamine, and arylamine.
  • Alkylamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine
  • alkylamines having an alkyl group having 1 to 4 carbon atoms such as triethylamine, tripropylamine, and tributylamine.
  • Alkoxyamines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine , Alkoxyamines having an alkoxy group having 1 to 4 carbon atoms, such as butoxyethylamine, butoxypropylamine, and butoxybutylamine.
  • Alkanolamines include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, min, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N -Methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N -Dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N- Ethylethanolamine, N, N-dipropylethanolamine, N, N-dibutyl
  • tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; tetramethylethylenediamine, tetraethylethylenediamine Tetraalkylethylenediamine such as tetrapropylethylenediamine and tetrabutylethylenediamine; methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, Propylaminomethylamine, propylamino Alkylaminoalkylamines such as ethyl
  • Such basic compounds may be used singly or in combination of two or more. Of these, triethylamine, tetramethylammonium hydroxide, and pyridine are preferable.
  • Examples of the acidic compound include organic acids and inorganic acids.
  • Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, methylmalonic acid, adipic acid, Sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfone Examples include acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid
  • Such acidic compounds may be used singly or in combination of two or more. Of these, maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are particularly preferred.
  • salt compound examples include naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and alkali metal salts such as carbonic acid.
  • organometallic compounds examples include organometallic compounds and / or partial hydrolysates thereof (hereinafter, organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organometallic compounds”).
  • organometallic compounds include the following formula (b): M (OR 7 ) r (R 8 COCHCOR 9 ) s (b) (Wherein M represents at least one metal atom selected from the group consisting of zirconium, titanium and aluminum, and R 7 and 8 each independently represent a methyl group, an ethyl group, an n-propyl group, Monovalent hydrocarbon groups having 1 to 6 carbon atoms such as i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group and phenyl group
  • R 9 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, represents an alkoxy group having 1 to 16 carbon atoms
  • organometallic compounds such as tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-butoxy titanium; methyl trimethoxy titanium, ethyl triethoxy titanium, n-propyl tri Methoxytitanium, i-propyltriethoxytitanium, n-hexyltrimethoxytitanium, cyclohexyltriethoxytitanium, phenyltrimethoxytitanium, 3-chloropropyltriethoxytitanium, 3-aminopropyltrimethoxytitanium, 3-aminopropyltriethoxytitanium 3- (2-aminoethyl) -aminopropyltrimethoxytitanium, 3- (2-aminoethyl) -aminopropyltriethoxytitanium, 3- (2-aminoethyl
  • organometallic compound (b) examples include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate).
  • Organic zirconium compounds such as acetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, di-n-butoxybis (acetylacetonato) zirconium;
  • Organic titanium compounds such as tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium ; Tri-i-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetyl acetonato aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetonate) And organoa
  • organic tin compound for example, Carboxylic acid-type organotin compounds such as
  • Mercaptide-type organotin compounds such as
  • Sulfide-type organotin compounds such as;
  • Chloride-type organotin compounds such as; Reaction of organotin oxides such as (C 4 H 9 ) 2 SnO, (C 8 H 17 ) 2 SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate, and dioctyl phthalate Products; and the like.
  • Such organometallic compounds may be used singly or in combination of two or more.
  • di-n-butoxy bis (acetylacetonato) zirconium, dioctyltin dioctyl maleate, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxyethylacetoacetate aluminum, Tris (ethyl acetoacetate) aluminum or a partial hydrolyzate thereof is preferred.
  • the said catalyst can also be used in mixture with another reaction retarder.
  • the amount of the catalyst used is usually 0.001 with respect to 100 parts by weight of the silane compound (a1) (in terms of a completely hydrolyzed condensate of organosilane (1)) when the catalyst is other than organometallic compounds.
  • To 100 parts by weight preferably 0.01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight.
  • the catalyst is an organometallic compound, it is usually 100 parts by weight or less, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the silane compound (a1) (in terms of complete hydrolysis condensate of organosilane (1)). 80 parts by weight, more preferably 0.5 to 50 parts by weight. If the amount of the catalyst used exceeds the upper limit, gelation may occur due to a decrease in the storage stability of the polymer (A1), or cracks may occur due to the degree of crosslinking of the layer (1) being too high.
  • Stability improver In the present invention, in order to improve the storage stability of the polymer (A1), it is preferable to add a stability improver as necessary after preparing the polymer (A1).
  • the stability improver used in the present invention is represented by the following formula (5).
  • R 10 COCH 2 COR 11 (5)
  • R 10 represents methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group
  • R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a phenyl group
  • R 11 is a monovalent hydrocarbon group having 1 to 6 carbon atoms similar to R 10 , or a methoxy group
  • And represents an alkoxyl group having 1 to 16 carbon atoms such as ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, stearyloxy group).
  • organometallic compounds When organometallic compounds are used as the catalyst, it is preferable to add a stability improver represented by the above formula (5).
  • the stability improver By using the stability improver, the stability improver is coordinated to the metal atom of the organometallic compound, and this coordination is obtained between the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2). It is considered that excessive cocondensation reaction can be suppressed and the storage stability of the resulting polymer (A1) can be further improved.
  • stability improvers include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, Acetoacetic acid-t-butyl, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl Hexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline, Diethylenetriamine, 2-ethanol
  • the amount of the stability improver used in the present invention is usually 2 moles or more, preferably 3 to 20 moles per mole of the organometallic compound of the organometallic compounds. If the amount of the stability improver is less than the above lower limit, the effect of improving the storage stability of the resulting composition may be insufficient.
  • water is added to a mixture of the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2), and the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) Can be co-condensed to prepare the polymer (A1).
  • the amount of water added at this time is usually 0.1 to 1.0 mol, preferably 0.2 to 0.8 mol, based on 1 mol of all OR 2 groups in the silane compound (a1). More preferably, it is 0.25 to 0.6 mol.
  • the amount of water added is in the above range, gelation hardly occurs and the composition exhibits good storage stability. Further, when the amount of water is in the above range, a sufficiently crosslinked polymer (A1) is obtained, and by using such a composition containing the polymer (A1) and the metal oxide particles (B), Layer (I) can be obtained.
  • the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) may be hydrolyzed and condensed in an organic solvent.
  • the organic solvent used at the time of preparation of the silyl group-containing vinyl polymer (a2) can be used as it is.
  • an organic solvent can also be added as needed.
  • the organic solvent used in the preparation of the silyl group-containing vinyl polymer (a2) may be removed and an organic solvent may be newly added.
  • the organic solvent is added in such an amount that the solid content concentration in the preparation of the polymer (A1) is preferably in the range of 10 to 80% by weight, more preferably 15 to 60% by weight, and particularly preferably 20 to 50% by weight. can do.
  • an organic solvent is added. However, it may not be added.
  • the reactivity of the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) can be controlled by adjusting the solid content concentration during the preparation of the polymer (A1).
  • the reactivity between the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) may be lowered. If the solid content concentration at the time of preparing the polymer (A1) exceeds the above upper limit, it may be gelled.
  • the amount of solid content in solid content concentration said here is the usage-amount (Wa1) of the complete hydrolysis-condensation product conversion of a silane compound (a1), and the usage-amount of solid content conversion of a specific silyl group containing vinyl polymer (a2). This is the total amount of (Wa2).
  • the organic solvent is not particularly limited as long as the above components can be mixed uniformly.
  • Alcohols and diethylene glycol alkyl exemplified as the organic solvent used in the production of the specific silyl group-containing vinyl polymer (a2).
  • Ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ethers, ketones, esters, etc. Can be mentioned.
  • these organic solvents may be used individually by 1 type, or may mix and use 2 or more types.
  • Metal oxide particles (B) The composition (I) of the present invention further contains metal oxide particles (B).
  • the metal oxide particles are not particularly limited as long as they are metal element oxide particles. For example, antimony oxide, zirconium oxide, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide.
  • Tantalum oxide indium oxide, hafnium oxide, tin oxide, niobium oxide, aluminum oxide, cerium oxide, scandium oxide, yttrium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, oxide Dysprosium, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, barium oxide, magnesium oxide Neshiumu, and these complexes, as well as indium - metal oxides such as oxides of the metal 2 or more complex such as tin composite oxides.
  • metal oxide particles (B) composite oxide particles of silicon oxide and metal oxide or oxide particles in which the surface of the metal oxide is coated with silicon oxide can also be used.
  • a metal oxide particle (B) individually by 1 type or in mixture of 2 or more types.
  • the metal oxide particles (B) can be appropriately selected according to the function to be imparted.
  • anatase-type titanium oxide, rutile-type titanium oxide, zirconium oxide, aluminum oxide, and zinc oxide can be preferably used.
  • a powder or a solvent-based sol or colloid dispersed in a polar solvent such as isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, or a nonpolar solvent such as toluene It can also be used in the form.
  • the metal oxide particles (B) before addition may be aggregated to form secondary particles.
  • the primary particle diameter of these metal oxide particles (B) is usually 0.0001 to 1 ⁇ m, more preferably 0.001 to 0.5 ⁇ m, and particularly preferably 0.002 to 0.2 ⁇ m.
  • its solid content concentration is usually more than 0% by weight and 50% by weight or less, preferably 0.01% by weight or more and 40% by weight or less.
  • the metal oxide particles (B) are used in the form of sol or colloid, they can be dispersed in the solution by a stirring blade or the like.
  • dispersion in the case of using powder in the metal oxide particles (B) is ball mill, sand mill (bead mill, high shear bead mill), homogenizer, ultrasonic homogenizer, nanomizer, propeller mixer, high shear mixer, paint shaker, planetary
  • Known dispersing machines such as a mixer, a two-roll, a three-roll, a kneader roll and the like can be used.
  • a highly dispersed fine particle dispersion ball mill, a sand mill (bead mill, a high shear bead mill), and a paint shaker are preferably used. .
  • the amount of the metal oxide particles (B) used is generally more than 10% by weight and 90% by weight or less, preferably 20% by weight or more and 80% by weight based on the total solid weight in the composition (I). % Or less.
  • the amount of the metal oxide particles (B) used is larger than the above weight, the storage stability of the composition (I) may be inferior.
  • the layer (II) is formed on the layer (I). ) May not be sufficiently reduced, and the crack resistance of the layer (I) may be inferior.
  • a curing catalyst can also be added to the composition (I) used in the present invention.
  • a curing catalyst include the basic compound, acidic compound, salt compound, and organometallic compound used in preparing the polymer (A1).
  • a basic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, and triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferable.
  • An acidic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, Maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are especially preferable.
  • the organometallic compounds may be used singly or in combination of two or more, such as di-n-butoxy bis (acetylacetonate) zirconium, dioctyltin dioctyl maleate, di-i- Propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or partial hydrolysates thereof are preferred.
  • Organic solvent, water An organic solvent and water may be further added to the composition (I) used in the present invention to adjust the solid content concentration.
  • organic solvent what was illustrated by the term of the said polymer (A1) preparation can be used.
  • a leveling agent In the composition (I) used in the present invention, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, ( Inorganic fillers other than the component B) can be added.
  • composition (I) used in the present invention comprises a powder of metal oxide particles (B) on the silane compound (a1) and / or the polymer (A1). It is obtained by adding a body and performing a dispersion
  • a solvent-based sol or colloid is used as the metal oxide particles (B), and a stirring blade or the like is used.
  • a ball mill, a bead mill, or a paint shaker is used when powder particles are used. Etc. can be used.
  • composition (I) may contain the above-mentioned organic solvent, water, stability improver, curing catalyst, and optional additive components as necessary, and these may be added before the dispersion step. It may be added after the dispersion step.
  • the metal oxide particle (B) works also as a curing catalyst of composition (I)
  • composition (I) used in the present invention is applied to a substrate which is a surface member of a device for outdoor installation, and is heated and dried.
  • the application method is not particularly limited, but brush coating, brush coating, bar coater, knife coater, doctor blade, screen printing, spray coating, spin coater, applicator, roll coater, flow coater, centrifugal coater, ultrasonic coater , (Micro) gravure coater, dip coating, flexographic printing, potting, and the like can be used, and they may be transferred onto another substrate (transfer substrate) and transferred.
  • Heat drying is preferably performed at a temperature in the range of 50 to 250 ° C. for 0.5 to 180 minutes.
  • a normal oven is used for heat drying, but a hot air type, a convection type, an infrared type, or the like can be used.
  • the condensation reaction proceeds in the layer, and a stronger layer can be obtained. It is desirable that the heating temperature is high, the heating time is long, the residual solvent is small, and the condensation reaction further proceeds.
  • the heating process may be performed through a plurality of stages, or may be performed in one stage. Depending on the content and boiling point of the solvent to be used and the heating conditions, the surface of the obtained layer may be rough.
  • the layer (II) includes a polyorganosiloxane (C) and hollow or porous particles (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm.
  • the layer (II) has a refractive index of 1.25 or more and less than 1.50 depending on the type of device for outdoor installation, and has a film thickness in the range of 0.01 ⁇ m to 10 ⁇ m.
  • composition (II) Such a layer (II) has, for example, the following formula (2): R 3 m Si (OR 4 ) 4-m (2) (Wherein, R 3 represents a monovalent organic group having 1 to 12 carbon atoms, optionally different from one another the same if there are two or more .R 4 each independently And represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, m is an integer of 0 to 3.) At least one organosilane (hereinafter also referred to as “organosilane (2)”), a hydrolyzate of organosilane (2), and a condensate of organosilane (2). It can be obtained from a cured product of a composition containing at least one silane compound (c1) (hereinafter referred to as “composition (II)”).
  • the silane compound (c1) used in the present invention is at least one silane compound selected from the group consisting of the organosilane (2), the hydrolyzate of organosilane (2), and the condensate of organosilane (2). Of these three silane compounds, only one silane compound may be used, any two silane compounds may be mixed, or all three silane compounds may be mixed. May be used. Moreover, when using organosilane (2) as a silane compound (c1), organosilane (2) may be used individually by 1 type, or may use 2 or more types together. The hydrolyzate and condensate of the organosilane (2) may be formed from one type of organosilane (2) or may be formed by using two or more types of organosilane (2) in combination. Good.
  • the hydrolyzate of the organosilane (2) is sufficient if at least one of the OR 2 groups contained in 1 to 4 of the organosilane (2) is hydrolyzed, for example, one OR 2 group. In which two or more OR 2 groups are hydrolyzed, or a mixture thereof.
  • the organosilane (2) condensate is a product in which a silanol group in a hydrolyzate produced by hydrolysis of organosilane (2) is condensed to form a Si—O—Si bond.
  • the condensate may be one obtained by condensing a small part of silanol groups, one containing most (including all) silanol groups, These mixtures are also included.
  • R 3 is a non-hydrolyzable organic group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group.
  • Alkyl groups such as heptyl group, octyl group, decyl group, 2-ethylhexyl group; Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group; Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxycycloalkyl group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.
  • examples of R 3 include substituted derivatives of the above organic groups.
  • examples of the substituent of the substituted derivative of R 3 include a substituted or unsubstituted amino group, hydroxyl group, mercapto group, isocyanate group, glycidoxy group, 3-glycidyloxypropyl group, 3,4-epoxycyclohexyl group, 3,4 -Epoxycyclohexylethyl group, (meth) acryloxy group, 3- (meth) acryloyloxypropyl group, ureido group, ammonium base and the like.
  • R 3 When a plurality of R 3 are present in the formula (2), they may be the same or different.
  • R 4 that is an alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and the like, and R that is an acyl group having 1 to 6 carbon atoms.
  • Examples of 2 include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.
  • silane compounds substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, etc. ;
  • silane compounds substituted with two non-hydrolyzable groups and two hydrolyzable groups dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane , Di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxy Silane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyl
  • silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane Etc., respectively.
  • R 3 is preferably an organic group containing no fluorine.
  • fluorine for the purpose of the present invention for reducing the reflectance as a laminate, it is advantageous to introduce fluorine into the layer (II) to lower the refractive index and increase the refractive index difference from the layer (I).
  • a functional group containing fluorine acts in a direction to reduce the interaction between molecules. Accordingly, when fluorine is introduced into the polymer, there is a problem that the coating film becomes soft and the hardness decreases.
  • one type of organosilane (2) may be used alone as the silane compound (c1), but two or more types of organosilane (2) may be used in combination.
  • the averaged n (hereinafter also referred to as “average value of n”) is.
  • it is 0.5 to 2.0, more preferably 0.6 to 1.8, and particularly preferably 0.7 to 1.6.
  • the storage stability of the composition (II) may be inferior, and when it exceeds the above upper limit, the curability of the layer (II) may be inferior.
  • the average value of n can be adjusted to the above range by appropriately using a monofunctional to tetrafunctional organosilane (2) and appropriately adjusting the blending ratio thereof.
  • organosilane (2) may be used as it is as silane compound (c1), but hydrolyzate and / or condensate of organosilane (2) can be used.
  • organosilane (2) is used as a hydrolyzate and / or a condensate
  • a product prepared by previously hydrolyzing and condensing the organosilane (2) may be used, but the composition (II) is prepared.
  • the hydrolyzate and / or condensate of organosilane (2) can also be prepared by hydrolyzing and condensing organosilane (2).
  • the conditions for hydrolyzing and condensing the silane compound (c1) represented by the above formula (2) are hydrolyzable by hydrolyzing at least a part of the organosilane (2) represented by the above formula (2). Although it does not specifically limit as long as it converts a group into a silanol group or causes a condensation reaction, it can be carried out as an example as follows.
  • the water used for hydrolysis of the organosilane (2) represented by the above formula (2) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.
  • the amount of water used is preferably from 0.1 to 3 mol, more preferably from 1 mol of the total amount of hydrolyzable groups (—OR 2 ) of the organosilane (2) represented by the above formula (2). Is in an amount of 0.3 to 2 mol, more preferably 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of hydrolysis can be optimized.
  • Organic solvent Although it does not specifically limit as a solvent which can be used for hydrolysis and condensation of the organosilane (2) represented by the said Formula (2), Usually, in manufacture of the polymer (A1) mentioned above. The thing similar to the solvent used can be used.
  • a solvent include propyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. .
  • propyl alcohol methyl isobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate are preferable.
  • catalyst Although it does not specifically limit as a catalyst which can be used for the hydrolysis and condensation reaction of organosilane (2) represented by the said Formula (2), Usually, manufacture of the polymer (A1) mentioned above The same catalyst as that used in the above can be used.
  • Such catalysts include acid catalysts (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids), Basic catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate Carboxylates such as sodium acetate; various Lewis bases] or alkoxides (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide) and the like.
  • acid catalysts for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulf
  • tetra-i-propoxyaluminum can be used as the aluminum alkoxide.
  • the amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis reaction. It is.
  • the reaction temperature and reaction time in hydrolysis / condensation of the organosilane (2) represented by the above formula (2) are appropriately set.
  • the reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
  • the reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis reaction can be performed most efficiently.
  • the hydrolyzable silane compound, water and catalyst may be added to the reaction system at a time to carry out the reaction in one step, or the hydrolyzable silane compound, water and catalyst may be added,
  • the hydrolysis and condensation reaction may be performed in multiple stages by adding them into the reaction system in several times.
  • the condensate of the organosilane (2) has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) measured by a gel permeation chromatography method (GPC method), preferably 300 to 100,000. More preferably, it is 500 to 50,000.
  • Mw polystyrene-equivalent weight average molecular weight
  • organosilane (2) condensate When used as the silane compound (c1) in the present invention, it may be prepared from the organosilane (2) or a commercially available organosilane condensate.
  • organosilane condensates include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resins and silicone oligomers manufactured by Toray Dow Corning Silicone Co., Momentive Performance Examples include silicone resins and silicone oligomers manufactured by Materials Co., Ltd., silicone resins and silicone oligomers manufactured by Shin-Etsu Chemical Co., Ltd., and hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd. These condensates of commercially available organosilanes may be used as they are or may be further condensed.
  • the composition (II) of the present invention contains hollow or porous particles (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm.
  • the particle size is measured with a transmission electron microscope.
  • a cured product obtained by curing the composition of the present invention can exhibit a low refractive index and scratch resistance.
  • D As a particle, a well-known thing can be used, Moreover, the shape is not restricted spherical and may be indefinite. Colloidal silica having a solid content of 5 to 40% by weight is preferred.
  • the dispersion medium is preferably water or an organic solvent.
  • organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane.
  • the amount of component (D) is usually 10 to 80% by weight, preferably 20 to 80% by weight, more preferably 30 to 80% by weight based on the total amount of the composition other than the organic solvent.
  • the amount of particles means solid content, and when the particles are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of solvent.
  • the amount of the metal oxide particles (D) used is less than the above weight, the reflectance, luminous reflectance, and scratch resistance of the resulting antireflection layer may be inferior.
  • the particles (D) containing silica as a main component can be obtained by subjecting the particle surface to surface treatment such as chemical modification, for example, hydrolyzable silicon compounds having one or more alkyl groups in the molecule. Or what contains the hydrolyzate etc. can be made to react.
  • hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1.
  • Hydrolyzable silicon compounds having one or more reactive groups in the molecule include, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethylsilane having NH 2 groups as reactive groups.
  • a preferred compound is 3-mercaptopropyltrimethoxysilane.
  • the surface treatment of the particles (D) containing silica as a main component can be performed with an organic compound containing a polymerizable unsaturated group such as an acryloyl group.
  • composition (II) is laminated on the previously formed layer (I) and cured to form a layer (II), whereby a low refractive index layer is formed, and this laminate forms an antireflection layer.
  • Compound (E) having a polydimethylsiloxane skeleton In the composition (II) of the present invention, a compound (E) having a polydimethylsiloxane skeleton can be blended as necessary.
  • the compound (E) having a polydimethylsiloxane skeleton can improve surface slipperiness, improve the scratch resistance of the cured coating film, and can impart antifouling properties.
  • the compound (E) having these polydimethylsiloxanes preferably has a high molecular weight, and further preferably has a reactive group such as a (meth) acryloyl group, a hydroxyl group, an epoxy group, a carboxyl group, or an amino group.
  • Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-DA11, FM -DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso Corp.), UV3500, UV3510, UV3530 (manufactured by Big Chemie Japan Corp.), YF3800, XF3905, YF3057 YF3807, YF3802, YF3897, XC96-723 (made by Momentive Performance Materials Japan), BY16-004, SF8428 (made by Toray Dow Corning Silicone Co., Ltd.), VPS-1001 (made by Wako Pure Chemical Industries, Ltd.) Rad 2500, 2600 (manufactured by TEGO), KF-101, X-22-2046, X-22-16
  • the amount of component (E) added is usually 0.01 to 20% by weight based on the total amount of the composition excluding the organic solvent. The reason for this is that when the addition amount is less than 0.01% by weight, the effect of improving the slipperiness cannot be sufficiently obtained. On the other hand, when the addition amount exceeds 20% by weight, the coating strength decreases due to an excessive amount of components. This is because the coatability deteriorates. For this reason, the amount of component (E) added is more preferably 0.1 to 15% by weight, and even more preferably 0.5 to 10% by weight.
  • a curing catalyst can also be added to the composition (II) used in the present invention.
  • a curing catalyst include the basic compound, acidic compound, salt compound, and organometallic compound used in preparing the polymer (A1).
  • a basic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, and triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferable.
  • An acidic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, Maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are especially preferable.
  • the organometallic compounds may be used singly or in combination of two or more, such as di-n-butoxy bis (acetylacetonate) zirconium, dioctyltin dioctyl maleate, di-i- Propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or partial hydrolysates thereof are preferred.
  • Organic solvent water
  • An organic solvent or water may be further added to the composition (II) used in the present invention to adjust the solid content concentration.
  • the organic solvent is not particularly limited.
  • alcohols diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate.
  • Aromatic hydrocarbons, ethers, ketones, esters and the like are examples of the organic solvent.
  • Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-octyl alcohol, and ethylene glycol.
  • Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
  • Ethylene glycol alcohol examples include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.
  • Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether and propylene glycol monoethyl. Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.
  • propylene glycol monoalkyl ether acetates examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene group
  • propylene glycol monoalkyl ether propionate propylene glycol monomethyl ether propionate
  • propylene glycol monoethyl ether propionate propylene glycol monopropyl ether propionate
  • propylene glycol mono Examples include butyl ether propionate.
  • Aromatic hydrocarbons include benzene, toluene, xylene, etc.
  • ethers include tetrahydrofuran, dioxane, etc.
  • ketones include acetone, cyclohexanone, 2-heptanone, 4-hydroxy- 4-methyl-2-pentanone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like.
  • esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, normal propyl lactate, isoprolactide Pill, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy
  • composition (II) used in the present invention a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic, if necessary Fillers can be added.
  • composition (II) used in the present invention is a silane compound (c1) that is hollow or mainly composed of silica having a silica number average particle diameter of 1 to 100 nm. It is obtained by adding porous particles (D) and performing a mixing and / or dispersion step.
  • a method such as a stirring blade is used when (i) a solvent-based sol or colloid is used as the hollow or porous particle (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm.
  • a technique such as a ball mill, a bead mill, or a paint shaker can be used.
  • the composition (II) may contain the organic solvent, water, stability improver, curing catalyst, and optional additive components, which are added before the dispersion step. It may be added after the dispersion step.
  • composition (II) used in the present invention is applied onto the layer (I) formed on the base material and dried by heating.
  • the layer (II) has a lower refractive index than the layer (I), and antireflection ability can be imparted by forming such a laminate.
  • the coating method of the composition (II) is not particularly limited, but brush coating, brush coating, bar coater, knife coater, doctor blade, screen printing, spray coating, spin coater, applicator, roll coater, flow coater, Techniques such as centrifugal coater, ultrasonic coater, (micro) gravure coater, dip coating, flexographic printing, and potting can be used, and they may be used after being applied on another substrate (transfer substrate). . Heat drying is preferably performed at a temperature in the range of 50 to 250 ° C. for 0.5 to 180 minutes.
  • a normal oven is used for heat drying, but a hot air type, a convection type, an infrared type, or the like can be used. While removing the solvent by heating, the condensation reaction proceeds in the layer, and a stronger layer can be obtained. It is desirable that the heating temperature is high, the heating time is long, the residual solvent is small, and the condensation reaction further proceeds.
  • the heating process may be performed through a plurality of stages, or may be performed in one stage. Depending on the content and boiling point of the solvent to be used and the heating conditions, the surface of the obtained layer may be rough. Therefore, it is desirable to examine an appropriate heating step in advance.
  • the antireflection layer formed by the present invention has a siloxane structure as a main skeleton, and is excellent in heat resistance, light resistance, and weather resistance as compared with a normal organic polymer. Moreover, since it can manufacture by application
  • the antireflection layer obtained in the present invention is useful as an antireflection film, and can be used indoors, but is particularly used for large screen display devices used outdoors, car navigation systems, mobile phones, video monitors, Various displays such as cathode ray tube display, liquid crystal display, plasma display, organic EL display, rear projection display, crystalline silicon type, amorphous silicon type, organic thin film type, dye sensitized type, compound semiconductor type, polymer type, quantum dot type It can be suitably used as an antireflection film for the glue of various solar cells. In particular, it is useful for devices for outdoor installation, especially for devices for outdoor installation such as digital signage.
  • composition kit comprising the above composition (I) and composition (II) is constructed, and the kit is made anti-reflective on the surface using the surface member of the device for outdoor installation as a base material. Can be used to form a layer.
  • composition to be measured was applied on a silicon wafer by spin coating so that the coating film thickness was 1 ⁇ m, and baked and dried in an oven as a sample.
  • a prism coupler apparatus Metal The refractive index at 633 nm was measured by a company manufactured 2010).
  • Initial luminous reflectance (Y value) measurement Assuming the use of an outdoor display, the initial luminous reflectance (Y value) is measured using a spectrophotometer (manufactured by JASCO Corporation, V-670). Analysis was performed in the wavelength range of ⁇ 780 nm. ⁇ : Y value is less than 1% ⁇ : Y value is 1% or more and less than 1.5% ⁇ : Y value is 1.5% or more
  • Anti-reflection layer standard ⁇ : No change in appearance (crack, whitening, etc.) up to 2000 hours, reflectance is less than 2% ⁇ : No change in appearance (crack, whitening, etc.) up to 1000 hours, reflectance is less than 2% ⁇ : Change in appearance (cracks) No whitening, etc.), but Y value is 2% or more and less than 4%.
  • Pencil Hardness (Surface Hardness) Test Pencil hardness (surface hardness) was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990 for the sample to be measured.
  • a solution prepared by dissolving 3 parts of azobisisobutyronitrile in 8 parts of butyl acetate was added dropwise to this mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours. After cooling, 40 parts of methyl ethyl ketone was added to obtain a polymer (2) solution having a solid content concentration of 40% and Mw of 15000.
  • Preparation Example 5 To 17 parts of the polymer (3) solution of the present invention, 8 parts of zirconium oxide powder having a primary particle diameter of 10 nm, 25 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-5) having a partial concentration of 25% by weight was obtained. The storage stability was A.
  • Preparation Example 7 To 15 parts of the polymer (4) solution of the present invention, 8 parts of zirconium oxide powder having a primary particle diameter of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed in a paint shaker for 4 hours. A composition (X-7) having a partial concentration of 25% by weight was obtained. The storage stability was A.
  • Preparation Example 8 To 15 parts of the polymer (5) solution of the present invention, 8 parts of titanium oxide powder having a primary particle diameter of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-8) having a partial concentration of 25% by weight was obtained. The storage stability was A.
  • Preparation Example 10 To 15 parts of the polymer (8) solution of the present invention, 8 parts of zirconium oxide powder having a primary particle size of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-10) having a partial concentration of 25% by weight was obtained. The storage stability was A.
  • Example 1 The composition (X-1) was applied onto a glass substrate using a spin coater so that the film thickness after drying was 1.5 ⁇ m, and dried at 200 ° C. for 30 minutes (first stage drying).
  • the composition (Y-1) was applied from above the obtained (X-1) layer using a spin coater so that the film thickness after drying was 100 nm, and dried at 200 ° C. for 30 minutes (second stage)
  • the sample was prepared. A plurality of samples were prepared, and luminous reflectance, pencil hardness, scratch resistance, and crack resistance were measured as initial evaluation. One of the samples was subjected to an accelerated weathering test, and the appearance observation and luminous reflectance measurement after the test were performed. The results are shown in Table 1.
  • Example 2> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-2) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 3> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-3) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 4> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Y-2) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 5> A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (X-2) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 6> A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (X-3) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 7> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-4) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 8> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-5) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 9> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-6) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 10> A sample having an antireflection layer was prepared in the same manner as in Example 7 except that the composition (Y-2) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 11> A sample having an antireflection layer was prepared in the same manner as in Example 10 except that the composition (X-5) was used instead of the composition (X-4), and the same evaluation was performed. The results are shown in Table 1.
  • Example 12> A sample having an antireflection layer was prepared in the same manner as in Example 10 except that the composition (X-6) was used instead of the composition (X-4), and the same evaluation was performed. The results are shown in Table 1.
  • Example 13> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-7) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 14> A sample having an antireflection layer was prepared in the same manner as in Example 13 except that the composition (Y-2) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 15> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-8) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 16> A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (X-9) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • Example 17> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-10) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
  • ⁇ Comparative Example 1> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Z-1) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 2.
  • ⁇ Comparative Example 2> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Y-3) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 2.
  • ⁇ Comparative Example 3> A sample having an antireflection layer was prepared in the same manner as in Example 7 except that the composition ( ⁇ -1) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 2.
  • ⁇ Comparative Example 4> A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (Z-2) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 2.
  • ⁇ Comparative Example 5> A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Y-4) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 2.
  • Examples 18 to 34 and Comparative Examples 7 to 12 were carried out as evaluation of the antireflection layer assuming a crystalline silicon type solar cell application. The results are shown in Tables 3 and 4.
  • Example 18 The composition (X-1) was applied onto a glass substrate using a spin coater so that the film thickness after drying was 1.0 ⁇ m, and dried at 200 ° C. for 30 minutes (first stage drying).
  • the composition (Y-1) was applied from above the obtained (X-1) layer using a spin coater so that the film thickness after drying was 200 nm, and dried at 200 ° C. for 30 minutes (second stage)
  • the sample was prepared. A plurality of samples were prepared, and reflectance, pencil hardness, scratch resistance, and crack resistance were measured as initial evaluation. One of the samples was subjected to an accelerated weathering test, and an appearance observation and a reflectance measurement were performed after the test. The results are shown in Table 3.

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Abstract

La présente invention a trait à un dispositif pour l'extérieur qui est pourvu d'une couche antireflet possédant une excellente résistance à la lumière, pouvant être formée de manière simple, et présentant une activité antireflet, ainsi qu'à une couche antireflet destinée à être utilisée dans un dispositif pour l'extérieur. La présente invention concerne en particulier une couche antireflet qui comprend un stratifié composé d'une couche (I) comportant un polyorganosiloxane (A) et des particules d'oxyde métallique (B), et d'une couche (II) comportant un polyorganosiloxane (C) ainsi que des particules creuses ou poreuses (D) composées essentiellement de silice et présentant un diamètre particulaire moyen en nombre compris entre 1 et 100 nm. La couche antireflet est formée sur un élément de surface (qui sert de matériau de base à la couche antireflet) d'un dispositif pour l'extérieur.
PCT/JP2011/052716 2010-02-15 2011-02-09 Dispositif pour l'extérieur et couche antireflet destinée à un dispositif pour l'extérieur WO2011099505A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2015161791A (ja) * 2014-02-27 2015-09-07 旭硝子株式会社 反射防止膜付き基材および物品
JP2022506660A (ja) * 2018-12-07 2022-01-17 コーロン インダストリーズ インク 防眩性コーティング用樹脂組成物及びこれを含んで製造された防眩性コーティングフィルム
EP3892695A4 (fr) * 2018-12-07 2022-08-31 Kolon Industries, Inc. Composition de résine destinée à un revêtement antireflet et film de revêtement antireflet ainsi préparé

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JP2003201443A (ja) * 2001-10-25 2003-07-18 Matsushita Electric Works Ltd コーティング材組成物及びそれにより形成された被膜を有する物品
JP2007011033A (ja) * 2005-06-30 2007-01-18 Fujifilm Holdings Corp 反射防止フィルム、それを用いた偏光板及びディスプレイ装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003201443A (ja) * 2001-10-25 2003-07-18 Matsushita Electric Works Ltd コーティング材組成物及びそれにより形成された被膜を有する物品
JP2007011033A (ja) * 2005-06-30 2007-01-18 Fujifilm Holdings Corp 反射防止フィルム、それを用いた偏光板及びディスプレイ装置

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015161791A (ja) * 2014-02-27 2015-09-07 旭硝子株式会社 反射防止膜付き基材および物品
JP2022506660A (ja) * 2018-12-07 2022-01-17 コーロン インダストリーズ インク 防眩性コーティング用樹脂組成物及びこれを含んで製造された防眩性コーティングフィルム
EP3892695A4 (fr) * 2018-12-07 2022-08-31 Kolon Industries, Inc. Composition de résine destinée à un revêtement antireflet et film de revêtement antireflet ainsi préparé

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