WO2016175054A1 - Composition de résine durcissable par un rayonnement d'énergie active, stratifié anti-salissure et anti-condensation, article, procédé pour sa production, et procédé anti-salissure - Google Patents

Composition de résine durcissable par un rayonnement d'énergie active, stratifié anti-salissure et anti-condensation, article, procédé pour sa production, et procédé anti-salissure Download PDF

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Publication number
WO2016175054A1
WO2016175054A1 PCT/JP2016/062118 JP2016062118W WO2016175054A1 WO 2016175054 A1 WO2016175054 A1 WO 2016175054A1 JP 2016062118 W JP2016062118 W JP 2016062118W WO 2016175054 A1 WO2016175054 A1 WO 2016175054A1
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WIPO (PCT)
Prior art keywords
antifouling
antifogging
active energy
energy ray
resin composition
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PCT/JP2016/062118
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English (en)
Japanese (ja)
Inventor
祥吾 坂本
亮介 遠藤
水野　幹久
忍 原
Original Assignee
デクセリアルズ株式会社
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Priority claimed from JP2016075819A external-priority patent/JP2017030347A/ja
Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to US15/569,276 priority Critical patent/US10875977B2/en
Priority to KR1020177033951A priority patent/KR20170141749A/ko
Priority to CN201680024107.7A priority patent/CN107531029B/zh
Priority to EP16786331.5A priority patent/EP3290203B1/fr
Publication of WO2016175054A1 publication Critical patent/WO2016175054A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • C08F20/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/054—Forming anti-misting or drip-proofing coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings

Definitions

  • the present invention has an antifogging and antifouling property, and can be used in a wide range of building applications, industrial applications, automotive applications, optical applications, solar battery panels, etc.
  • Articles using anti-fogging and antifouling laminate, method for producing the same, antifouling method using antifogging and antifouling laminate, and active energy ray curable that can be used for producing antifogging and antifouling laminate The present invention relates to a resin composition.
  • a resin film, glass, or the like is attached to the surface.
  • the visibility and aesthetics of the article may deteriorate due to fogging and soiling of resin films, glass, etc. that decorate and protect the surface of the article. Therefore, in order to prevent the visibility and aesthetic deterioration of such articles, the resin film and glass are subjected to an antifogging treatment.
  • an antifogging film-forming base material in which a silane coupling layer as a base layer, an organic-inorganic composite film as a water-absorbing layer, and a water-repellent layer as a protective layer are sequentially laminated on the surface of the base material.
  • a silane coupling layer as a base layer
  • an organic-inorganic composite film as a water-absorbing layer
  • a water-repellent layer as a protective layer
  • the present invention has an antifogging and antifouling laminate having excellent antifogging and antifouling properties and excellent production efficiency, an article using the antifogging and antifouling laminate, and a method for producing the same, It is an object of the present invention to provide an antifouling method using an antifogging and antifouling laminate and an active energy ray-curable resin composition that can be used in the production of the antifogging and antifouling laminate.
  • the antifogging and antifouling layer is a cured product obtained by curing the active energy ray-curable resin composition with active energy rays
  • the active energy ray-curable resin composition contains a hydrophilic monomer having a radical polymerizable unsaturated group, and a photopolymerization initiator,
  • the content of the hydrophilic monomer having the radical polymerizable unsaturated group in the active energy ray-curable resin composition is 60% by mass or more
  • the antifogging and antifouling laminate is characterized in that a pure water contact angle on the surface of the antifogging and antifouling layer is 90 ° or more.
  • ⁇ 2> The antifogging and antifouling laminate according to ⁇ 1>, wherein the active energy ray-curable resin composition further contains a water-repellent monomer having a radical polymerizable unsaturated group.
  • the active energy ray-curable resin composition further contains a water-repellent monomer having a radical polymerizable unsaturated group.
  • ⁇ 3> The anti-fogging and antifouling laminate according to ⁇ 2>, wherein the content of the water-repellent monomer having the radical polymerizable unsaturated group in the active energy ray-curable resin composition is more than 0.018% by mass. Is the body.
  • ⁇ 4> The antifogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the base material is any one of a resin base material and an inorganic base material.
  • ⁇ 5> An article having the antifogging and antifouling laminate according to any one of ⁇ 1> to ⁇ 4> on a surface thereof.
  • ⁇ 6> The method for producing an article according to ⁇ 5>, A heating step of heating the antifogging and antifouling laminate, An anti-fogging and antifouling laminate forming step for forming the heated antifogging and antifouling laminate into a desired shape.
  • ⁇ 7> The method for manufacturing an article according to ⁇ 5>, wherein the heating in the heating step is performed by infrared heating.
  • An active energy ray-curable resin composition comprising a hydrophilic monomer having a radical polymerizable unsaturated group, a water repellent monomer having a radical polymerizable unsaturated group, and a photopolymerization initiator, The active energy ray-curable resin composition is characterized in that a pure water contact angle of the surface of the anti-fogging and antifouling layer obtained by curing the active energy ray-curable resin composition with active energy rays is 90 ° or more. .
  • the hydrophilic monomer having a radical polymerizable unsaturated group is a (meth) acrylate having a polyoxyalkylene chain
  • the conventional problems can be solved, the object can be achieved, the antifogging and antifouling laminate has excellent antifogging and antifouling properties, and is excellent in production efficiency.
  • Articles using the antifogging and antifouling laminate, a method for producing the same, an antifouling method using the antifogging and antifouling laminate, and active energy ray curing that can be used for producing the antifogging and antifouling laminate A functional resin composition can be provided.
  • FIG. 1A is a process diagram for explaining an example of producing an article of the present invention by in-mold molding.
  • FIG. 1B is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 1C is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 1D is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 1E is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 1F is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 2 is a schematic sectional view of an example of the article of the present invention (No.
  • FIG. 3 is a schematic sectional drawing of an example of the articles
  • FIG. 4 is a schematic sectional view of an example of the article of the present invention (No. 3).
  • FIG. 5 is a schematic sectional drawing of an example of the articles
  • the anti-fogging and antifouling laminate of the present invention has at least a base material and an antifogging and antifouling layer, and further includes other members as necessary.
  • Base material> There is no restriction
  • a triacetyl cellulose TAC
  • polyester TPE
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PE polyacrylate
  • PMMA acrylic resin
  • PC Polycarbonate
  • epoxy resin epoxy resin, urea resin, urethane resin, melamine resin, phenol resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer (C C), PC / PMMA laminate, such as rubber additives PMMA and the like.
  • Examples of the material for the inorganic base material include metal oxides (eg, quartz, sapphire, glass, etc.), metals (eg, iron, chromium, nickel, molybdenum, niobium, copper, titanium, aluminum, zinc, silicon, magnesium). , Manganese, etc.), alloys (for example, combinations of the above metals), and the like.
  • the substrate has transparency.
  • the average thickness of the resin substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 ⁇ m to 1,000 ⁇ m, and preferably 50 ⁇ m to 500 ⁇ m. Is more preferable.
  • the average thickness of the inorganic substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 mm to 100 mm.
  • a character, pattern, image or the like may be printed on the surface of the substrate.
  • a binder layer may be provided.
  • various adhesives can be used in addition to various binders such as acrylic, urethane, polyester, polyamide, ethylene butyl alcohol, and ethylene vinyl acetate copolymer systems.
  • Two or more binder layers may be provided.
  • the binder to be used one having heat sensitivity and pressure sensitivity suitable for the molding material can be selected.
  • the pure water contact angle on the surface of the anti-fogging and antifouling layer is 90 ° or more.
  • the antifogging and antifouling layer is a cured product obtained by curing the active energy ray-curable resin composition with active energy rays.
  • the antifogging and antifouling layer is disposed on the substrate.
  • the antifogging and antifouling layer has a smooth surface.
  • that the surface is smooth means that there are no intentionally formed convex portions or concave portions on the surface.
  • the anti-fogging and antifouling laminate when the antifogging and antifouling layer is formed (when the cured product is formed), fine convex portions or concave portions by physical processing are formed on the surface. Absent.
  • the anti-fogging and antifouling layer does not have fine convex portions or concave portions on the surface, so that water-based stains and / or oily stains such as magic ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.) are difficult to adhere. .
  • water-based stains and / or oily stains such as magic ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.
  • the surface of the anti-fogging and antifouling layer itself has water repellency, it is more resistant to abrasion as compared with the case where two layers of a water absorbing layer and a protective layer are laminated as in the technique described in JP-A-2001-233638. An anti-fogging and antifouling laminate having excellent properties can be obtained.
  • the pure water contact angle on the surface of the anti-fogging and antifouling layer is 90 ° or more, preferably 100 ° or more, more preferably 110 ° or more, and particularly preferably 115 ° or more.
  • the pure water contact angle can be measured by, for example, an ellipse fitting method using DM-701 (manufactured by Kyowa Interface Chemical Co., Ltd.) under the following conditions.
  • the hexadecane contact angle on the surface of the anti-fogging and antifouling layer is preferably 30 ° or more, more preferably 60 ° or more, still more preferably 70 ° or more, and particularly preferably 80 ° or more.
  • the hexadecane contact angle is within the preferred range, even when fingerprints, sebum, sweat, tears, cosmetics, etc. adhere to the surface, it can be easily wiped away, and excellent antifogging properties can be maintained. It is advantageous.
  • the hexadecane contact angle can be measured by, for example, an ellipse fitting method using DM-701 (manufactured by Kyowa Interface Chemical Co., Ltd.) under the following conditions.
  • -Put hexadecane in a plastic syringe attach a Teflon-coated stainless steel needle to the tip, and drop it onto the evaluation surface.
  • ⁇ Drop amount of hexadecane 2 ⁇ L
  • Measurement temperature 25 °C Hexadecane is dropped and the contact angle after 4 seconds is measured at any 10 locations on the surface of the anti-fogging and antifouling layer, and the average value is taken as the hexadecane contact angle.
  • the pure water contact angle is within the above range and the hexadecane contact angle is within the above range, water-based stains such as magic ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.) and / or oily stains are adhered. Even so, those soils are prevented from penetrating the bulk underlayer. Therefore, the dirt can be easily wiped off by wiping with a tissue or the like, and the antifogging property returns to the state before the dirt is adhered.
  • water-based stains such as magic ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.) and / or oily stains are adhered. Even so, those soils are prevented from penetrating the bulk underlayer. Therefore, the dirt can be easily wiped off by wiping with a tissue or the like, and the antifogging property returns to the state before the dirt is adhered.
  • the active energy ray-curable resin composition contains at least a hydrophilic monomer having a radical polymerizable unsaturated group (hereinafter sometimes referred to as “hydrophilic monomer”) and a photopolymerization initiator, preferably It contains a water-repellent monomer having a radically polymerizable unsaturated group (hereinafter sometimes referred to as “water-repellent monomer”), and further contains other components as necessary.
  • hydrophilic monomer having a radical polymerizable unsaturated group
  • water-repellent monomer a water-repellent monomer having a radically polymerizable unsaturated group
  • Water repellent monomer- examples include a monomer having a radical polymerizable unsaturated group and at least one of fluorine and silicon.
  • water-repellent monomers include (meth) acrylates having at least one of fluorine and silicon, and further examples include fluorinated (meth) acrylates, silicone (meth) acrylates, and the like. More specifically, (meth) acrylate having a fluoroalkyl group, (meth) acrylate having a fluoroalkyl ether group, (meth) acrylate having a dimethylsiloxane group, and the like can be given.
  • the water repellent monomer is preferably compatible with the hydrophilic monomer.
  • (meth) acrylate means acrylate or methacrylate. The same applies to (meth) acryloyl and (meth) acryl.
  • the water repellent monomer may be a commercially available product.
  • commercially available products of the fluorinated (meth) acrylate include KY-1200 series manufactured by Shin-Etsu Chemical Co., Ltd., MegaFac RS series manufactured by DIC Corporation, and OPTOOL DAC manufactured by Daikin Industries, Ltd.
  • Examples of commercially available silicone (meth) acrylates include X-22-164 series manufactured by Shin-Etsu Chemical Co., Ltd., and TEGO Rad series manufactured by Evonik.
  • 0.018 mass% is preferable, 0.018 mass % To less than 5.0% by mass, more preferably 0.075% by mass to 3.0% by mass, and particularly preferably 0.18% by mass to 1.5% by mass.
  • content is 5.0% by mass or more, although the water repellency of the cured product is excellent, the glass transition temperature becomes low, so that it becomes too soft and wear resistance may be lowered.
  • the breath antifogging property may be lowered.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition part.
  • hydrophilic monomer-- examples include (meth) acrylate having a polyoxyalkylene chain, quaternary ammonium salt-containing (meth) acrylate, tertiary amino group-containing (meth) acrylate, and sulfonic acid. Examples thereof include a group-containing monomer, a carboxylic acid group-containing monomer, a phosphoric acid group-containing monomer, and a phosphonic acid group-containing monomer. These may be monofunctional monomers or polyfunctional monomers.
  • the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. Among these, a polyoxyethylene chain is preferable in terms of excellent hydrophilicity.
  • hydrophilic monomer examples include mono- or polyacrylates obtained by a reaction between a polyhydric alcohol (polyol or polyhydroxy-containing compound) and a compound selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof, Alternatively, mono or polymethacrylate can be used.
  • polyhydric alcohol examples include divalent alcohol, trivalent alcohol, and tetravalent or higher alcohol.
  • divalent alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a number average molecular weight of 300 to 1,000, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2′-thiodiethanol, 1,4-cyclohexanedi For example, methanol.
  • trivalent alcohol examples include trimethylolethane, trimethylolpropane, pentaglycerol, glycerol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like.
  • tetravalent or higher alcohol examples include pentaerythritol, diglycerol, and dipentaerythritol.
  • Examples of the (meth) acrylate having a polyoxyalkylene chain include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, ethoxylated glycerin (meth) acrylate, and ethoxylated pentaerythritol tetra (meth) acrylate. It is done.
  • Examples of the polyethylene glycol (meth) acrylate include methoxypolyethylene glycol (meth) acrylate.
  • a commercial item can be used as said methoxypolyethyleneglycol (meth) acrylate.
  • the commercially available product include MEPM-1000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • MEPM-1000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • ethoxylated glycerin (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate are preferable from the viewpoint that both moderate hardness and hydrophilicity of the antifogging and antifouling layer can be achieved.
  • Examples of the quaternary ammonium salt-containing (meth) acrylate include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethyldimethylglycidylammonium chloride, (meth) Acryloyloxyethyltrimethylammonium methylsulfate, (meth) acryloyloxydimethylethylammonium ethylsulfate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidopropyldimethyl Benzyl ammonium chloride, (meth) acrylamide Pills dimethyl glycidyl chloride, (meth
  • Examples of the tertiary amino group-containing (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, 1,2, Examples include 2,6,6-pentamethylpiperidyl (meth) acrylate and 2,2,6,6-tetramethylpiperidyl (meth) acrylate.
  • Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, and sulfonic acid group-containing (meth) acrylate.
  • Examples of the sulfonic acid group-containing (meth) acrylate include, for example, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and terminal sulfonic acid-modified polyethylene glycol mono (meth) Examples include chlorate. These may form a salt. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like.
  • Examples of the carboxylic acid group-containing monomer include acrylic acid and methacrylic acid.
  • Examples of the phosphate group-containing monomer include (meth) acrylate having a phosphate ester.
  • the hydrophilic monomer is preferably a polyfunctional hydrophilic monomer.
  • the molecular weight of the hydrophilic monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 200 or more.
  • the content of the hydrophilic monomer in the active energy ray-curable resin composition is 60% by mass or more, preferably 60% by mass to 99.9% by mass, more preferably 63% by mass to 95% by mass, and 65% by mass. A mass% to 90 mass% is particularly preferred.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition part.
  • photopolymerization initiator examples include a photoradical polymerization initiator, a photoacid generator, a bisazide compound, hexamethoxymethylmelamine, and tetramethoxyglycolyl.
  • the radical photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,6-dimethylbenzoyl).
  • the content of the photopolymerization initiator in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 10% by mass, 0.5% by mass to 8% by mass is more preferable, and 1% by mass to 5% by mass is particularly preferable.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition part.
  • urethane (meth) acrylate isocyanuric acid group containing (meth) acrylate, a filler, etc. are mentioned. These may be used to adjust the elongation rate, hardness, etc. of the anti-fogging and anti-fouling layer.
  • the urethane (meth) acrylate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate. Among these, aliphatic urethane (meth) acrylate is preferable.
  • the content of the urethane (meth) acrylate in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass to 45% by mass, More preferred is 40% by weight, and especially preferred is 20% to 35% by weight.
  • the said active energy ray curable resin composition contains a volatile matter (for example, organic solvent)
  • the said content is content with respect to the non volatile matter of the said active energy ray curable resin composition part.
  • the filler is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include silica, zirconia, titania, tin oxide, indium tin oxide, antimony-doped tin oxide, and antimony pentoxide.
  • examples of the silica include solid silica and hollow silica.
  • the active energy ray-curable resin composition can be diluted with an organic solvent when used.
  • organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethyl
  • organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethyl
  • formamide dimethyl sulfoxide, dimethylacetamide, and the like.
  • the active energy ray-curable resin composition is cured when irradiated with active energy rays.
  • active energy ray There is no restriction
  • the Bokumoribo The Martens hardness of the fouling layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5N / mm 2 ⁇ 300N / mm 2, 10N / mm 2 ⁇ 290N / mm 2 Is more preferable, and 15 N / mm 2 to 280 N / mm 2 is particularly preferable.
  • the anti-fogging and antifouling laminate for example, at the time of injection molding of polycarbonate, the antifogging and antifouling laminate is heated and pressurized at 290 ° C. and 200 MPa.
  • the anti-fogging and antifouling layer is usually used for surface cleaning during normal use, such as handling and surface cleaning when producing or molding the antifogging and antifouling laminate. May be easily scratched.
  • the Martens hardness exceeds 300 N / mm 2 , cracks may occur in the anti-fogging and antifouling layer or the antifogging and antifouling layer may be peeled off during molding.
  • the antifogging and antifouling laminate is variously produced without deteriorating the antifogging performance and without causing defects such as scratches, cracks and peeling.
  • the Martens hardness of the antifogging and antifouling layer is increased as compared with that before the molding.
  • the Martens hardness can be measured by using, for example, PICODETOR HM500 (trade name; manufactured by Fisher Instruments).
  • the load is 1 mN / 20 s, a diamond cone is used as the needle, and the surface angle is 136 °.
  • the pencil hardness of the anti-fogging and antifouling layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably B to 4H, more preferably HB to 4H, and particularly preferably F to 4H.
  • B softer than B
  • the antifogging and anti-fogging treatment is carried out by surface cleaning during normal use such as handling and surface cleaning when manufacturing or molding the anti-fogging and antifouling laminate. Soil is easily damaged. If the pencil hardness exceeds 4H (harder than 4H), cracks may occur in the anti-fogging and antifouling layer or the antifogging and antifouling layer may be peeled off during molding.
  • the antifogging and antifouling laminate is variously produced without deteriorating the antifogging performance and without causing defects such as scratches, cracks, and peeling. This is advantageous in that it can be easily molded into a three-dimensional shape.
  • the pencil hardness of the antifogging and antifouling layer is increased than before the molding. There is.
  • the pencil hardness is measured according to JIS K 5600-5-4.
  • the average thickness of the antifogging and antifouling layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 4 ⁇ m to 50 ⁇ m, and particularly preferably 10 ⁇ m to 30 ⁇ m.
  • the average thickness is within a preferable range, it is advantageous in that the antifogging property is excellent, the interference unevenness is reduced, and the productivity is excellent.
  • interference unevenness can be further reduced.
  • the anchor layer is a layer disposed between the base material and the anti-fogging and antifouling layer. By disposing the anchor layer, it is possible to improve the adhesion between the base material and the anti-fogging and antifouling layer.
  • the anchor layer preferably has a refractive index close to that of the antifogging and antifouling layer in order to prevent interference unevenness. Therefore, the refractive index of the anchor layer is preferably within ⁇ 0.10 of the refractive index of the anti-fogging and antifouling layer, and more preferably within ⁇ 0.05. Or it is preferable that the refractive index of the said anchor layer is between the refractive index of the said anti-fogging antifouling layer and the refractive index of the said base material.
  • the anchor layer can be formed, for example, by applying an active energy ray-curable resin composition. That is, the anchor layer is, for example, a cured product obtained by curing an active energy ray-curable resin composition with active energy rays.
  • the active energy ray-curable resin composition for example, an active energy ray-curable resin composition containing at least urethane (meth) acrylate and a photopolymerization initiator, and further containing other components as necessary.
  • the urethane (meth) acrylate and the photopolymerization initiator include the urethane (meth) acrylate and the photopolymerization initiator exemplified in the description of the anti-fogging and antifouling layer.
  • coating method there is no restriction
  • coating method For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.
  • examples of the material of the anchor layer include a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. These preferably have a radically polymerizable unsaturated group.
  • a method for forming the anchor layer when the substrate is an inorganic substrate for example, a solution in which the material is dissolved is applied onto the inorganic substrate, the solvent is dried, and then heat treatment is performed for a predetermined time. The method etc. are mentioned.
  • a solvent used for the solution a solvent that dissolves the material is selected.
  • water for example, water, alcohol (eg, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, etc.), anone (eg, cyclohexanone, cyclopentanone), amide
  • At least one selected from for example, N, N-dimethylformamide: DMF), sulfide (for example, dimethylsulfoxide: DMSO) and the like is used.
  • the coating method is not particularly limited, and a known coating method can be used.
  • Known coating methods include, for example, micro gravure coating method, wire bar coating method, direct gravure coating method, die coating method, dip method, spray coating method, reverse roll coating method, curtain coating method, comma coating method, knife coating method. , Spin coating, letterpress printing, offset printing, gravure printing, intaglio printing, rubber printing, screen printing, ink jet printing, and the like.
  • heating temperature it is 80 to 200 degreeC, for example.
  • the heating time is, for example, from 1 minute to 12 hours.
  • the average thickness of the anchor layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 nm to 100 ⁇ m, more preferably 0.01 ⁇ m to 10 ⁇ m, still more preferably 0.1 ⁇ m to 5 ⁇ m. 0.3 ⁇ m to 3 ⁇ m is particularly preferable.
  • the anchor layer may be provided with a function of reducing reflectivity or preventing charging.
  • the protective layer is a layer that protects the surface of the antifogging and antifouling layer (the surface having a pure water contact angle of 90 ° or more).
  • the said protective layer protects the said surface, when manufacturing the article
  • the protective layer is disposed on the surface of the antifogging and antifouling resin layer.
  • Examples of the material of the protective layer include the same material as that of the anchor layer.
  • the elongation percentage of the antifogging and antifouling laminate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% or more, more preferably 10% to 200%, and more preferably 40% to 150%. Is particularly preferred. If the elongation is less than 10%, molding may be difficult. When the elongation percentage is within the particularly preferable range, it is advantageous in that the moldability is excellent.
  • the said elongation rate can be calculated
  • the anti-fogging and antifouling laminate is formed into a strip having a length of 10.5 cm and a width of 2.5 cm to be a measurement sample.
  • the measurement temperature varies depending on the type of the resin base material, and the elongation percentage is measured at a temperature near or above the softening point of the resin base material. Specifically, it is between 10 ° C and 250 ° C.
  • the resin substrate is a polycarbonate or PC / PMMA laminate, it is preferable to measure at 150 ° C.
  • the antifogging and antifouling laminate preferably has a smaller difference in heat shrinkage between the X direction and the Y direction in the plane of the antifogging and antifouling laminate.
  • the X direction and the Y direction of the anti-fogging and antifouling laminate correspond to, for example, the longitudinal direction and the width direction of the roll when the antifogging and antifouling laminate is a roll.
  • the difference between the heat shrinkage rate in the X direction and the heat shrinkage rate in the Y direction in the anti-fogging and antifouling laminate is preferably within 5% at the heating temperature used in the heating step during molding.
  • the antifogging and antifouling layer may be peeled or cracked during molding, or the characters, patterns, images, etc. printed on the surface of the resin substrate may be deformed or misaligned. This may cause the molding process to be difficult.
  • the anti-fogging and antifouling laminate is particularly suitable for a thermal bending film, an in-mold molding film, an insert molding film, and an overlay molding film.
  • the method for producing the anti-fogging and antifouling laminate is not particularly limited and may be appropriately selected depending on the intended purpose, but the method for producing the antifogging and antifouling laminate described below is preferred.
  • the method for producing the anti-fogging and antifouling laminate includes at least an uncured resin layer forming step and an antifogging and antifouling layer forming step, and further includes other steps as necessary.
  • the method for producing the anti-fogging and antifouling laminate is a method for producing the antifogging and antifouling laminate of the present invention.
  • Uncured resin layer forming process is not particularly limited as long as it is a step of forming an uncured resin layer by applying an active energy ray-curable resin composition on a substrate, and is appropriately selected according to the purpose. be able to.
  • the active energy ray curable resin composition is not particularly limited and may be appropriately selected depending on the purpose.
  • the antifogging and antifouling layer of the antifogging and antifouling layer of the present invention examples thereof include the active energy ray-curable resin composition described above.
  • the uncured resin layer is formed by applying the active energy ray-curable resin composition on the substrate and drying it as necessary.
  • the uncured resin layer may be a solid film or a film having fluidity due to a low molecular weight curable component contained in the active energy ray curable resin composition.
  • coating method there is no restriction
  • coating method For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.
  • the uncured resin layer is not cured because it is not irradiated with active energy rays.
  • the uncured resin layer may be formed by applying the active energy ray-curable resin composition onto the anchor layer of the base material on which the anchor layer is formed.
  • the anchor layer There is no restriction
  • the antifogging and antifouling layer forming step is not particularly limited as long as it is a step of forming an antifogging and antifouling layer by irradiating the uncured resin layer with active energy rays to cure the uncured resin layer. It can be appropriately selected according to the purpose.
  • the anti-fogging and antifouling layer physical processing for forming fine convex portions or concave portions on the surface is not performed.
  • a hydrophilic component water-absorbing component
  • water droplets are made water repellent on the surface of the anti-fogging and antifouling layer, and water vapor is easily trapped in the antifogging and antifouling layer.
  • better antifogging properties can be obtained.
  • the active energy ray is not particularly limited as long as it is an active energy ray that cures the uncured resin layer, and can be appropriately selected according to the purpose.
  • the antifogging and antifouling laminate of the invention Examples of the active energy ray exemplified in the description of.
  • the active energy ray-curable resin composition of the present invention contains at least a hydrophilic monomer having a radical polymerizable unsaturated group, a water repellent monomer having a radical polymerizable unsaturated group, and a photopolymerization initiator, If necessary, other components are contained.
  • the pure water contact angle of the surface of the anti-fogging and antifouling layer obtained by curing the active energy ray-curable resin composition with active energy rays is 90 ° or more.
  • the pure water contact angle on the surface of the antifogging and antifouling layer is measured, for example, by preparing the antifogging and antifouling layer having an average thickness of 4 ⁇ m and measuring the above.
  • the properties of the anti-fogging and antifouling layer include the properties exemplified in the description of the antifogging and antifouling laminate, and preferred embodiments include the embodiments exemplified in the description of the antifogging and antifouling laminate.
  • Examples of the components of the active energy ray-curable resin composition include the components of the active energy ray-curable resin composition exemplified in the description of the antifogging and antifouling laminate.
  • a preferable aspect also includes the aspect exemplified in the description of the anti-fogging and antifouling laminate. That is, examples of the hydrophilic monomer having a radical polymerizable unsaturated group include the hydrophilic monomer having the radical polymerizable unsaturated group exemplified in the description of the antifogging and antifouling laminate.
  • Examples of preferred embodiments such as the content include the embodiments exemplified in the description of the anti-fogging and antifouling laminate.
  • Examples of the water repellent monomer having a radical polymerizable unsaturated group include the water repellent monomer having the radical polymerizable unsaturated group exemplified in the description of the anti-fogging and antifouling laminate.
  • Examples of preferred embodiments such as the content include the embodiments exemplified in the description of the anti-fogging and antifouling laminate.
  • the article of the present invention has the anti-fogging and antifouling laminate of the present invention on the surface, and further includes other members as necessary.
  • the article is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include glass windows, refrigerated / frozen showcases, window materials such as automobile windows, bathroom mirrors, automobile side mirrors, and the like. Mirrors, bathroom floors and walls, solar panels, security surveillance cameras, etc.
  • the article may be glasses, goggles, a helmet, a lens, a microlens array, an automobile headlight cover, a front panel, a side panel, a rear panel, and the like. These are preferably formed by in-mold molding, insert molding, or overlay molding.
  • the antifogging and antifouling laminate may be formed on a part of the surface of the article, or may be formed on the entire surface.
  • the method for manufacturing the article is not particularly limited and may be appropriately selected depending on the intended purpose. However, the method for manufacturing the article of the present invention described later is preferable.
  • the method for producing an article of the present invention includes at least a heating step and an anti-fogging and antifouling laminate molding step, and further includes other steps such as an injection molding step and a cast molding step as necessary.
  • the manufacturing method of the article is the manufacturing method of the article of the present invention.
  • the heating step is not particularly limited as long as it is a step for heating the anti-fogging and antifouling laminate, and can be appropriately selected according to the purpose.
  • the antifogging and antifouling laminate is the antifogging and antifouling laminate of the present invention.
  • heating there is no restriction
  • the anti-fogging and antifouling laminate forming step is not particularly limited as long as it is a step for forming the heated antifogging and antifouling laminate into a desired shape, and can be appropriately selected according to the purpose. For example, the process etc. which make it closely_contact
  • an injection molding step may be performed as necessary.
  • the injection molding step is not particularly limited as long as it is a step of injecting a molding material onto the resin substrate side of the anti-fogging and antifouling laminate molded into a desired shape and molding the molding material, It can be appropriately selected according to the purpose.
  • Examples of the molding material include resin.
  • Examples of the resin include olefin resins, styrene resins, ABS resins (acrylonitrile-butadiene-styrene copolymers), AS resins (acrylonitrile-styrene copolymers), acrylic resins, urethane resins, unsaturated polyesters.
  • Resin epoxy resin, polyphenylene oxide / polystyrene resin, polycarbonate, polycarbonate-modified polyphenylene ether, polyethylene terephthalate, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherimide, polyimide, polyamide, liquid crystal polyester, polyallyl heat-resistant resin, various composite resins, Various modified resins are exemplified.
  • the injection method is not particularly limited and can be appropriately selected depending on the purpose.
  • the injection method is melted on the resin base material side of the anti-fogging and anti-stain laminate adhered to a predetermined mold.
  • examples thereof include a method of pouring the molding material.
  • a cast forming step may be performed as necessary.
  • a resin material dissolved in a solution is poured into the resin base side of the antifogging and antifouling laminate molded into a desired shape, and the resin material is solidified and molded. If there is, there is no restriction
  • the manufacturing method of the article is preferably performed using an in-mold molding apparatus, an insert molding apparatus, and an overlay molding apparatus.
  • This manufacturing method is a manufacturing method using an in-mold molding apparatus.
  • the anti-fogging and antifouling laminate 500 is heated.
  • the heating is preferably infrared heating or exposure to a high temperature atmosphere.
  • the heated anti-fogging and antifouling laminate 500 is disposed at a predetermined position between the first mold 501 and the second mold 502.
  • the first mold 501 is a fixed mold
  • the second mold 502 is a movable mold.
  • the first mold 501 and the second mold 502 are clamped. Subsequently, the antifogging / antifouling laminate 500 is sucked into the cavity surface of the second mold 502 by sucking the antifogging / antifouling laminate 500 through the suction hole 504 opened in the cavity surface of the second mold 502. To do. By doing so, the cavity surface is shaped by the anti-fogging and antifouling laminate 500. At this time, the outer periphery of the anti-fogging / anti-stain laminate 500 may be fixed and positioned by a film pressing mechanism (not shown).
  • the molten molding material 506 is injected from the gate 505 of the first mold 501 toward the resin base material of the anti-fogging and antifouling laminate 500, and the first mold 501 and the second mold 502 are molded. Injection into the cavity formed by tightening (FIG. 1C). Thereby, the molten molding material 506 is filled in the cavity (FIG. 1D). Further, after the filling of the molten molding material 506 is completed, the molten molding material 506 is cooled to a predetermined temperature and solidified.
  • the second mold 502 is moved to open the first mold 501 and the second mold 502 (FIG. 1E).
  • an anti-fogging and antifouling laminate 500 is formed on the surface of the molding material 506, and an article 507 in-mold molded into a desired shape is obtained.
  • the protruding pin 508 is pushed out from the first mold 501 and the obtained article 507 is taken out.
  • a manufacturing method in the case of using the overlay molding apparatus is as follows. This is a step of directly decorating the surface of the molding material with the anti-fogging and anti-stain laminate, and an example thereof is a TOM (Threee Dimension Over Method) method.
  • TOM Three Dimension Over Method
  • An example of a method for producing the article of the present invention using the TOM method will be described below.
  • air is sucked by a vacuum pump or the like in both spaces in the apparatus divided by the anti-fogging and antifouling laminate fixed to the fixed frame, and the two spaces are evacuated.
  • a molding material that has been injection molded in advance is placed in a space on one side.
  • the anti-fogging / anti-fouling laminate is firmly attached to the three-dimensional shape of the molding material in a vacuum atmosphere by sending air to the side of the equipment space where there is no molding material. Adhere closely. If necessary, compressed air pressing from the side where the atmosphere is sent may be used in combination. After the anti-fogging and antifouling laminate is in close contact with the molded body, the obtained decorative molded product is removed from the fixed frame. Vacuum forming is usually performed at 80 ° C to 200 ° C, preferably about 110 ° C to 160 ° C.
  • an adhesive layer is provided on the surface opposite to the antifogging and antifouling layer surface of the antifogging and antifouling laminate in order to bond the antifogging and antifouling laminate and the molding material. Also good.
  • an acrylic adhesive, a hot-melt-adhesive etc. are mentioned.
  • the said adhesion layer there is no restriction
  • FIG. 2 to 5 are schematic cross-sectional views of an example of the article of the present invention.
  • the article in FIG. 2 includes a molding material 506, a resin base material 211, and an anti-fogging and antifouling layer 212.
  • the resin base material 211 and the antifogging and antifouling layer 212 are provided. They are stacked in this order.
  • This article can be manufactured, for example, by insert molding.
  • a molding material 506 includes a molding material 506, a resin base material 211, an anti-fogging and antifouling layer 212, and a hard coat layer 600.
  • the resin base material 211 and the anti-fogging layer are provided.
  • the antifouling layer 212 is laminated in this order.
  • a hard coat layer 600 is formed on the side of the molding material 506 opposite to the resin substrate 211 side. For example, after the article shown in FIG. 2 is manufactured, a protective layer is formed on the anti-fogging and antifouling layer 212, the hard coat layer 600 is formed on the surface of the molding material 506, and the molding material 506 is used as the hard coating liquid.
  • the anti-fogging and antifouling layer can be produced by dipping, then drying, curing, etc., and further by peeling off the protective layer.
  • the anti-fogging and antifouling layer is a smooth surface, the pure water contact angle is within the above range, and the hexadecane contact angle is within the above range, the antifogging and antifouling layer repels the hard coat liquid. Even without forming a protective layer, no hard coat is formed on the anti-fogging and antifouling layer, and the hard coat layer 600 is formed only on the side opposite to the resin base material 211 side of the molding material 506. Excellent in properties.
  • the article of FIG. 4 has a molding material 506, a resin base material 211, and an anti-fogging and antifouling layer 212. On both sides of the molding material 506, a resin base material 211 and an antifogging and antifouling layer 212 are provided. Are stacked in this order.
  • the article in FIG. 5 includes a molding material 506, a resin base material 211, an antifogging and antifouling layer 212, and an optical film 601.
  • the dirty layer 212 is laminated in this order.
  • An optical film 601 is formed on the side of the molding material 506 opposite to the resin substrate 211 side. Examples of the optical film 601 include a hard coat film, an antireflection film, an antiglare film, and a polarizing film.
  • the article shown in FIG. 4 or 5 can be manufactured by, for example, double insert molding. Double insert molding is a method of molding a double-sided laminated film integrated product, and can be performed using, for example, the method described in JP-A-03-114718.
  • the antifouling method of the present invention is a method for preventing contamination of the article by laminating the antifogging and antifouling laminate of the present invention on the surface of the article.
  • the article is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include glass windows, refrigerated / frozen showcases, window materials such as automobile windows, bathroom mirrors, automobile side mirrors, and the like. Mirrors, bathroom floors and walls, solar panels, security surveillance cameras, etc.
  • the article may be glasses, goggles, a helmet, a lens, a microlens array, an automobile headlight cover, a front panel, a side panel, a rear panel, and the like. These are preferably formed by in-mold molding or insert molding.
  • the method for laminating the anti-fogging and antifouling laminate on the surface of the article is not particularly limited and may be appropriately selected depending on the purpose.
  • the antifogging and antifouling laminate is provided on the surface of the article. Examples include a method of pasting. Further, the antifogging and antifouling laminate can be laminated on the surface of the article also by the article manufacturing method of the present invention.
  • ⁇ Pure water contact angle> The pure water contact angle was measured by an ellipse fitting method using DM-701 (Kyowa Interface Chemical Co., Ltd.) which is a contact angle meter under the following conditions. -Distilled water was put into a plastic syringe, and a stainless steel needle was attached to the tip thereof and dropped onto the evaluation surface. ⁇ Drip amount of water: 2 ⁇ L ⁇ Measurement temperature: 25 °C The contact angle after 4 seconds from dropping water was measured at any 10 locations on the surface of the anti-fogging and antifouling layer, and the average value was defined as the pure water contact angle.
  • ⁇ Hexadecane contact angle> The hexadecane contact angle was measured by an ellipse fitting method using DM-701 (Kyowa Interface Chemical Co., Ltd.), which is a contact angle meter, under the following conditions. -Hexadecane was put in a plastic syringe, and a Teflon-coated stainless steel needle was attached to the tip thereof and dropped onto the evaluation surface.
  • ⁇ Exhalation anti-fogging property> In the environment of 25 ° C. and 37% RH, the surface of the antifogging and antifouling layer was visually observed immediately after exhaling once from a distance of 5 cm in the normal direction from the surface. Evaluation was performed according to the following evaluation criteria. ⁇ Evaluation criteria ⁇ ⁇ : No change in appearance on the surface of the antifogging and antifouling layer. X: Appearance changes such as white cloudiness and water film formation were confirmed on the surface of the antifogging and antifouling layer.
  • ⁇ Anti-fouling test> A commercially available oil-based pen (oil-based pen: Mackey, manufactured by ZEBRA) was brought into contact with the surface of the anti-fogging and anti-stain layer. Then, the state (repel) of the ink on the surface of the anti-fogging and antifouling layer was visually confirmed and evaluated according to the following evaluation criteria. ⁇ Evaluation criteria ⁇ ⁇ : Ink is repelled. X: Ink adheres.
  • ⁇ Wiping test> A commercially available oil-based pen (oil-based pen: Mackey, manufactured by ZEBRA) was brought into contact with the surface of the anti-fogging and anti-stain layer. And, after wiping the ink on the surface of the anti-fogging and antifouling layer with a tissue (Daiou Paper Co., Ltd., Erière) three times to draw a circle, visually check the state, and then perform the breath antifogging test went. Evaluation was made according to the following evaluation criteria. ⁇ Evaluation criteria ⁇ ⁇ : The ink was wiped off, and after the breath test, there was no change in appearance on the antifogging and antifouling surface. X: Ink could not be wiped off and / or appearance change such as white cloudiness and water film formation was confirmed on the surface of the antifogging and antifouling layer.
  • Example 1 ⁇ Preparation of anti-fogging and antifouling laminate>
  • FE-2000 PC base material, average thickness 180 ⁇ m
  • Mitsubishi Gas Chemical Co., Ltd. was used as a resin base material.
  • an active energy ray-curable resin composition having the following composition was applied onto the resin substrate so that the coating thickness was 4 ⁇ m.
  • ultraviolet rays were irradiated at a dose of 1,800 mJ / cm 2 in a nitrogen atmosphere to cure the antifogging and antifouling layer to obtain an antifogging and antifouling laminate.
  • Example 2 to 8 and Comparative Examples 1 to 4 Example 1
  • the coating thickness and the formulation of the active energy ray curable resin composition were changed to the coating thickness and the formulation of the active energy ray curable resin composition described in Table 1-1 and Table 1-2. Except that, a laminate (antifogging and antifouling) was obtained in the same manner as in Example 1.
  • the unit of the blending amount in Table 1-1 and Table 1-2 is mass%.
  • NK ester A-GLY-20E Shin-Nakamura Chemical Co., Ltd. ethoxylated glycerin triacrylate (total number of repeating units of polyethylene oxide chain contained in the structure: 20)
  • NK ester A-TM-35E ethoxylated pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd. (total number of repeating units of polyethylene oxide chain contained in the structure: 35)
  • NK ester A-600 Shin-Nakamura Chemical Co., Ltd. polyethylene glycol diacrylate (total number of repeating units of polyethylene oxide chain contained in the structure: 14)
  • PETIA manufactured by Daicel Ornex Co., Ltd.
  • a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate polyethylene oxide chain contained in the structure: none
  • EBECRYL 40 Pentaerythritol ethoxytetraacrylate manufactured by Daicel Ornex Co., Ltd. (polyethylene oxide chain contained in the structure: none)
  • Aronix M313 isocyanuric acid group-containing acrylate manufactured by Toa Gosei Co., Ltd.
  • the antifogging and antifouling layer contains a hydrophilic molecular structure
  • the pure water contact angle on the surface of the antifogging and antifouling layer is 90 ° or more, and contains a hydrophilic molecular structure.
  • Comparative Example 1 since a water-repellent monomer was not contained, the pure water contact angle was less than 90 °, and a laminate having poor antifouling properties and wiping properties was obtained. Comparative Examples 2 to 3 were laminates having poor breath antifogging properties due to a low hydrophilic monomer content. Since Comparative Example 4 had a pure water contact angle on the surface of less than 90 °, it was a laminate having poor antifouling properties and wiping properties. Comparative Example 5 contained a predetermined amount of a hydrophilic monomer and had a pure water contact angle of 90 ° or more on the surface. However, since it had an uneven structure, it became a laminate having poor antifouling properties and wiping properties.
  • Example 9 In Example 5, an antifogging and antifouling laminate was obtained in the same manner as in Example 5 except that the coating thickness was 10 ⁇ m. About the obtained anti-fogging antifouling laminated body, evaluation similar to Example 5 was performed. Further, interference unevenness was evaluated. The results are shown in Table 2. In Example 5, the interference unevenness evaluation result was ⁇ , whereas in Example 9, it was ⁇ .
  • Double-sided adhesive sheet manufactured by Nitto Denko Corporation
  • a black acrylic plate Mitsubishi Rayon Co., Ltd., trade name: Acrylite
  • the evaluation surface anti-fog antifouling layer surface
  • a product name: LUCIACS CS9621T LUCIACS CS9621T
  • Example 10 The anti-fogging and antifouling laminate produced in Example 9 was exposed to an atmosphere of 400 ° C. for 13 seconds, and was molded into an 8-curve lens of 80 mm diameter by vacuum forming so that the concave surface became an antifogging and antifouling layer. There were no appearance defects such as scratches, cracks and peeling on the anti-fogging and antifouling layer. Thereafter, an 8-curve lens antifogging and antifouling laminate having a diameter of 80 mm was punched out with a Thomson blade. This was set in an insert mold, filled with molten polycarbonate, and then cooled until the polycarbonate solidified.
  • the mold was opened to obtain an 8-curve lens having a concave surface with an antifogging and antifouling layer.
  • the obtained 8-curve lens as it is to the hard coat layer forming step (lens cleaning ⁇ dipping in hard coat solution ⁇ drying ⁇ curing)
  • no hard coat layer is formed on the surface of the anti-fogging and antifouling layer, and the convex side Only a hard coat layer could be formed.
  • an antifouling test, and a wiping test on the antifogging and antifouling layer side all were ⁇ .
  • Example 11 The anti-fogging and antifouling laminate produced in Example 9 was exposed to an atmosphere of 500 ° C. for 7 seconds, and formed into an 8-curve lens shape of ⁇ 80 mm by vacuum forming so that the concave surface became an antifogging and antifouling layer. There were no appearance defects such as scratches, cracks and peeling on the anti-fogging and antifouling layer. Thereafter, an 8-curve lens antifogging and antifouling laminate having a diameter of 80 mm was punched out with a Thomson blade. Next, another 8-curve lens-shaped antifogging and antifouling laminate having a diameter of 80 mm was prepared in the same manner.
  • Example 12 Preparation of anti-fogging and antifouling laminate> S9213 (Glass substrate, thickness 1.2 mm to 1.5 mm) manufactured by Matsunami Glass Industrial Co., Ltd. was used as the inorganic substrate.
  • a solution having the following composition was coated on an inorganic substrate so that the coating thickness was 100 nm.
  • An anchor layer was formed by heat treatment at 110 ° C. for 30 minutes.
  • Example 2 the active energy ray-curable resin composition used in Example 1 was applied on the anchor layer so that the application thickness was 30 ⁇ m.
  • ultraviolet rays were irradiated at a dose of 1,800 mJ / cm 2 in a nitrogen atmosphere to cure the antifogging and antifouling layer to obtain an antifogging and antifouling laminate.
  • the anti-fogging and antifouling laminate of the present invention includes glass windows, refrigerated / frozen showcases, window materials such as automobile windows, mirrors in bathrooms, mirrors such as automobile side mirrors, bathroom floors and walls, solar panel surfaces It can be attached to a security surveillance camera.
  • window materials such as automobile windows, mirrors in bathrooms, mirrors such as automobile side mirrors, bathroom floors and walls, solar panel surfaces It can be attached to a security surveillance camera.
  • one aspect of the anti-fogging and antifouling laminate of the present invention is easy to mold, glasses, goggles, helmets, lenses, microlens arrays, automobiles are used by using in-mold molding and insert molding. It can be used for headlight covers, front panels, side panels, rear panels and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un stratifié antisalissure et anti-condensation, lequel stratifié comprend une base et une couche anti-salissure et anti-condensation qui est disposée sur la base et qui présente une surface lisse. La couche anti-salissure et anti-condensation est un produit durci qui est obtenu par durcissement d'une composition de résine durcissable par un rayonnement d'énergie active à l'aide d'un rayonnement d'énergie active. La composition de résine durcissable par un rayonnement d'énergie active contient un monomère hydrophile ayant un groupe insaturé polymérisable par des radicaux et un amorceur de photopolymérisation. La teneur en monomère hydrophile ayant un groupe insaturé polymérisable par des radicaux dans la composition de résine durcissable par un rayonnement d'énergie active est de 60 % en masse ou plus. La surface de la couche anti-salissure et anti-condensation a un angle de contact avec l'eau pure de 90° ou plus.
PCT/JP2016/062118 2015-04-28 2016-04-15 Composition de résine durcissable par un rayonnement d'énergie active, stratifié anti-salissure et anti-condensation, article, procédé pour sa production, et procédé anti-salissure WO2016175054A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/569,276 US10875977B2 (en) 2015-04-28 2016-04-15 Active energy ray-curable resin composition, antifogging antifouling laminate, article, method for producing same, and antifouling method
KR1020177033951A KR20170141749A (ko) 2015-04-28 2016-04-15 활성 에너지선 경화성 수지 조성물, 방담 방오 적층체, 물품, 및 그 제조 방법, 그리고 방오 방법
CN201680024107.7A CN107531029B (zh) 2015-04-28 2016-04-15 活性能量线固化性树脂组合物、防雾防污层叠体、物品及其制造方法、以及防污方法
EP16786331.5A EP3290203B1 (fr) 2015-04-28 2016-04-15 Composition de résine durcissable par un rayonnement d'énergie active, stratifié anti-salissure et anti-condensation, article, procédé pour sa production, et procédé anti-salissure

Applications Claiming Priority (6)

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JP2015091287 2015-04-28
JP2015-091287 2015-04-28
JP2015-158291 2015-08-10
JP2015158291 2015-08-10
JP2016-075819 2016-04-05
JP2016075819A JP2017030347A (ja) 2015-04-28 2016-04-05 活性エネルギー線硬化性樹脂組成物、防曇防汚積層体、物品、及びその製造方法、並びに防汚方法

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WO2018123916A1 (fr) * 2016-12-28 2018-07-05 日本板硝子株式会社 Procédé de production de plaque de verre et plaque de verre d'automobile
CN110582402A (zh) * 2017-04-26 2019-12-17 迪睿合株式会社 活性能量线固化性树脂组合物、防雾防污层叠体及其制造方法、物品以及防雾方法
JP2020066158A (ja) * 2018-10-24 2020-04-30 デクセリアルズ株式会社 活性エネルギー線硬化性樹脂組成物、防曇防汚積層体、及びその製造方法、物品、並びに防曇方法
CN114716625A (zh) * 2022-03-11 2022-07-08 箭牌家居集团股份有限公司 一种高耐污亚克力板及其制备方法与应用

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JP2018108677A (ja) * 2016-12-28 2018-07-12 日本板硝子株式会社 ガラス板の製造方法及び自動車用ガラス板
CN110582402A (zh) * 2017-04-26 2019-12-17 迪睿合株式会社 活性能量线固化性树脂组合物、防雾防污层叠体及其制造方法、物品以及防雾方法
JP2020066158A (ja) * 2018-10-24 2020-04-30 デクセリアルズ株式会社 活性エネルギー線硬化性樹脂組成物、防曇防汚積層体、及びその製造方法、物品、並びに防曇方法
WO2020085218A1 (fr) * 2018-10-24 2020-04-30 デクセリアルズ株式会社 Composition de résine durcissable par rayonnement d'énergie active, stratifié anti-buée/anti-salissure, son procédé de production, article et procédé anti-buée
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CN114716625A (zh) * 2022-03-11 2022-07-08 箭牌家居集团股份有限公司 一种高耐污亚克力板及其制备方法与应用

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