WO2014054542A1 - Composition de couche de revêtement - Google Patents

Composition de couche de revêtement Download PDF

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Publication number
WO2014054542A1
WO2014054542A1 PCT/JP2013/076367 JP2013076367W WO2014054542A1 WO 2014054542 A1 WO2014054542 A1 WO 2014054542A1 JP 2013076367 W JP2013076367 W JP 2013076367W WO 2014054542 A1 WO2014054542 A1 WO 2014054542A1
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meth
coating layer
sensitive adhesive
adhesive sheet
pressure
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PCT/JP2013/076367
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English (en)
Japanese (ja)
Inventor
西川　健一
中川　善夫
上杉　正紀
康徳 山本
栄一 井本
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日東電工株式会社
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Publication of WO2014054542A1 publication Critical patent/WO2014054542A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2477/00—Presence of polyamide
    • C09J2477/006—Presence of polyamide in the substrate

Definitions

  • the present invention relates to a coating layer composition, and a multilayer sheet and an adhesive sheet having a coating layer using the coating layer composition, and in particular, a coating layer composition having a specific fluoroethylene vinyl ether alternating copolymer, and
  • the present invention relates to a multilayer sheet and an adhesive sheet.
  • a transparent adhesive sheet may be affixed to prevent damage to the painted surface of bodies such as automobiles.
  • a polyurethane substrate is used as the substrate of the transparent adhesive sheet (see, for example, JP-A-59-41376 and JP-A-2005-272558).
  • This pressure-sensitive adhesive sheet can be applied directly to the painted surface by hand using a squeegee, etc., but it may be misaligned during application, dirty with hands, or especially in areas where the 3D curved surface is severe. There were problems such as being unable to paste neatly. In addition, since the squeegee does not slide on the surface of the pressure-sensitive adhesive sheet, there are problems such as wrinkles and scratches on the pressure-sensitive adhesive sheet.
  • the followability deteriorates in a severe part of the three-dimensional curved surface, and it is possible to follow and adhere to an adherend having a three-dimensional curved surface. A difficult problem occurred.
  • a pressure-sensitive adhesive sheet for coating film protection in which a coating layer made of a fluororesin is provided on a base material (for example, see JP-A-2009-299053) is also known. Insufficient and difficult to apply to complex sites.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a pressure-sensitive adhesive sheet having flexibility and excellent surface slipperiness.
  • the coat layer composition of the present invention is characterized by comprising at least a fluorine-based polymer, a polyol, and a polyfunctional isocyanate.
  • the fluoropolymer is preferably a fluoroethylene vinyl ether alternating copolymer represented by the following formula (I).
  • X represents fluorine, chlorine or bromine
  • R a represents hydrogen or a C1-C10 alkyl group
  • R b represents a C1-C16 alkyl group
  • R c represents a C1-C16 alkylene group.
  • M and n are each integers and are selected in the range where the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is 1,000 to 2,000,000.
  • the coat layer composition may include at least a fluoroethylene vinyl ether alternating copolymer represented by the above formula (I), a polyol, a hydroxyl group-containing (meth) acryl monomer, and a polyfunctional isocyanate. preferable.
  • the polyol component is preferably a diol selected from divalent alcohols or a triol selected from trivalent alcohols.
  • the coating layer composition preferably further contains at least one selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, a phosphorus compound, and a phenolic antioxidant.
  • the multilayer sheet of the present invention is a multilayer sheet having a coating layer on at least one surface of a substrate, the coating layer using any one of the above coating layer compositions, and the substrate having at least (meta ) Acrylic urethane polymer or urethane polymer is contained.
  • the base material can be a composite film containing a (meth) acrylic polymer and a urethane polymer.
  • the base material constituting the multilayer sheet preferably contains at least one selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, a phosphorus compound, and a phenolic antioxidant.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer on at least one surface of any one of the multilayer sheets.
  • the pressure-sensitive adhesive sheet is preferably used as a protective sheet for protecting the surface of the adherend.
  • the present invention it is possible to realize a pressure-sensitive adhesive sheet having excellent flexibility and surface slipperiness. Moreover, according to this invention, the adhesive sheet excellent also in the adhesiveness of a coating layer and a base material is realizable. Furthermore, a multilayer sheet and a coating layer composition suitable for these pressure-sensitive adhesive sheets can be realized.
  • the multilayer sheet of the present invention is a laminated sheet having at least a coat layer and a substrate, and the coat layer is formed using a coat layer composition.
  • the coating layer composition of the present invention comprises at least a fluorine-based polymer, a polyol, and a polyfunctional isocyanate.
  • This fluoropolymer is preferably a fluoroethylene vinyl ether alternating copolymer.
  • this fluoroethylene vinyl ether alternating copolymer is a fluoroethylene vinyl ether alternating copolymer in which fluoroethylene units and vinyl ether units are alternately arranged, and the fluoroethylene vinyl ether alternating copolymer represented by the following formula (I) It is.
  • X represents fluorine, chlorine or bromine
  • R a represents hydrogen or a C1 to C10 alkyl group
  • R b represents a C1 to C16 alkyl group
  • R c represents a C1 to C16 alkyl group.
  • m and n are each an integer, and are selected in the range where the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is 1,000 to 2,000,000.
  • the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is 1,000 to 2,000,000, preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000.
  • m and n in the above formula (I) are selected in the range where the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer is 1,000 to 2,000,000.
  • the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer can be measured by the GPC method.
  • the measuring method of GPC method is shown below. That is, the fluoroethylene vinyl ether alternating copolymer is adjusted to 2.0 g / L using a THF solution and then allowed to stand for 12 hours. Thereafter, this solution is filtered through a 0.45 ⁇ m membrane filter, and GPC measurement is performed on the filtrate under the following measurement conditions using “HLC-8120GPC” manufactured by Tosoh Corporation as an analyzer.
  • the polyol constituting the coating layer composition of the present invention is preferably a diol selected from divalent alcohols or a triol selected from trivalent alcohols.
  • examples of the divalent alcohol include carbonate diol, tetramethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and the like.
  • examples of the trivalent alcohol include caprolactone triol, Examples include glycerol, trimethylolpropane, butanetriol, hexanetriol, and the like.
  • polycarbonate diol polytetramethylene ether glycol (PTMG), bifunctional caprolactone polyol, trifunctional caprolactone polyol, polyethylene glycol, polypropylene glycol and the like are preferably used.
  • PTMG polytetramethylene ether glycol
  • bifunctional caprolactone polyol bifunctional caprolactone polyol
  • trifunctional caprolactone polyol polyethylene glycol, polypropylene glycol and the like are preferably used.
  • the polyfunctional isocyanate constituting the coating layer composition of the present invention is one having two or more isocyanate groups in the molecule.
  • Examples of the polyfunctional isocyanate used in the present invention include hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and norbornene diisocyanate.
  • Difunctional isocyanate Difunctional isocyanate, Death Module N3200 (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate L (manufactured by Nippon Polyurethane Co., Ltd.), Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.), Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) ), Takenate D-140N (manufactured by Mitsui Chemicals Polyurethanes), Takenate D-127 (manufactured by Mitsui Chemicals Polyurethanes), Takenate D-110 Such trifunctional isocyanate (manufactured by Mitsui Chemicals Polyurethane Co.) and the like. In the present invention, these polyfunctional isocyanates can be used alone or in combination of two or more.
  • the ratio ([OH] / [NCO]) of the number of moles [OH] of the hydroxyl group of the polyol and the number of moles [NCO] of the isocyanate group of the polyfunctional isocyanate is preferably 0.05 to 0.5, more preferably 0.05 to 0.4, particularly preferably 0.05 to 0.3.
  • the coat layer composition of the present invention preferably further contains a hydroxyl group-containing (meth) acrylic monomer.
  • the hydroxyl group-containing (meth) acrylic monomer constituting the coating layer composition of the present invention has one or more hydroxyl groups in the molecule and one or more (meth) acryloyl groups in the molecule.
  • the hydroxyl group-containing (meth) acrylic monomer include 2-hydroxyethyl acrylate, 2-hydroxy methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, 1,4 -Cyclohexane dimethanol monomethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol acrylate and the like.
  • these hydroxyl group-containing (meth) acrylic monomers can be used alone or in combination of two or more.
  • those having a long chain between the hydroxyl group and the (meth) acryloyl group are preferable from the viewpoint of flexibility.
  • hydroxyl group-containing (meth) acrylic monomer used in the present invention examples include trade name “4-HBA” (4-hydroxybutyl acrylate), trade name “V # 802”, trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd. “V # 300”, trade names “FM2D” and “FA2D” manufactured by Daicel Corporation can be obtained commercially.
  • the ratio ([OH] / [NCO]) of the number of moles of hydroxyl group [OH] of the hydroxyl group-containing (meth) acrylic monomer to the number of moles of isocyanate group [NCO] of the polyfunctional isocyanate is preferably 0.05 to 0. 0.5, more preferably 0.05 to 0.4, and particularly preferably 0.05 to 0.3.
  • the coating layer composition of the present invention can further contain a catalyst.
  • the catalyst used include dibutyltin dilaurate, and the trade name “OL1” manufactured by Tokyo Fine Chemical Co., Ltd. can be obtained commercially.
  • the coating layer coating solution can be formed by using a solvent or the like, for example, by dissolving the coating layer composition in the solvent.
  • the solvent used include toluene, methyl ethyl ketone, hexane and the like.
  • the coating layer composition of the present invention can further contain an ultraviolet absorber, a hindered amine light stabilizer, a phosphorus compound, a phenolic antioxidant, and the like.
  • an ultraviolet absorber used here, a hindered amine light stabilizer, a phosphorus compound, and a phenolic antioxidant can use the thing similar to what is disclosed in description of the base material mentioned later.
  • the multilayer sheet of the present invention is a laminated sheet having a substrate and a coat layer, and has a coat layer on at least one surface of the substrate.
  • the base material constituting the multilayer sheet of the present invention preferably contains at least a (meth) acryl urethane polymer or a urethane polymer.
  • film includes a sheet
  • sheet includes a film
  • a urethane homopolymer or a copolymer is preferably used, and the urethane homopolymer can be obtained, for example, by reacting a polyol and a polyisocyanate.
  • the urethane polymer preferably used in the present invention include adipate-ester thermoplastic polyurethane, polyether-based thermoplastic polyurethane, polycarbonate-based thermoplastic polyurethane, polycaprolactone-ester-based thermoplastic polyurethane, and the like.
  • products manufactured by Nippon Matai Co., Ltd. can be commercially obtained as adipate-ester thermoplastic polyurethane, polycaprolactone-ester thermoplastic polyurethane, and the like.
  • the substrate constituting the multilayer sheet of the present invention may contain a (meth) acrylic urethane polymer, for example, a composite film containing a (meth) acrylic polymer and a urethane polymer.
  • the content ratio of the (meth) acrylic polymer is less than 1/99, the viscosity of the precursor mixture is increased and workability may be deteriorated.
  • it exceeds 80/20 flexibility and strength as a film are obtained. There may not be.
  • the (meth) acrylic polymer is preferably formed using an acrylic component containing at least a (meth) acrylic acid monomer and a monofunctional (meth) acrylic monomer, and in particular, a glass transition temperature (Tg) of a homopolymer.
  • Tg glass transition temperature
  • a (meth) acrylic polymer uses the acrylic component which further contains the monofunctional (meth) acryl monomer whose glass transition temperature (Tg) of a homopolymer is less than 0 degreeC.
  • the (meth) acrylic acid monomer is a (meth) acrylic monomer having a carboxyl group, and examples thereof include acrylic acid, methacrylic acid, maleic acid, and crotonic acid. Among these, acrylic acid is particularly preferable.
  • the content of the (meth) acrylic acid monomer is 1% by weight or more and 15% by weight or less, and preferably 2% by weight or more and 10% by weight or less in the composite film precursor described later. When the content of the (meth) acrylic acid monomer is less than 1% by weight, a long time is required for the reaction, making it very difficult to form a film, and there may be a problem that the strength of the film is not sufficient.
  • the (meth) acrylic acid monomer greatly affects the compatibility with the urethane component and the acrylic component, and is an essential component having a very important function.
  • (meth) acryl when “(meth) acryl” is displayed, such as a (meth) acrylic polymer and a (meth) acrylic acid monomer, the concept is a generic term for methacrylic and acrylic. Further, even when “acrylic” is displayed, the concept includes methacrylic if there is no problem in general sense.
  • examples of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher include acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, t-butyl acrylate, cyclohexyl acrylate, lauryl acrylate, and the like. . These may be used alone or in combination of two or more.
  • acryloylmorpholine isobornyl acrylate, and dicyclopentanyl acrylate as the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher. It is more preferable to use morpholine and / or isobornyl acrylate, or acryloyl morpholine and / or dicyclopentanyl acrylate, and it is particularly preferable to use isobornyl acrylate.
  • the content of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more is preferably 20% by weight or more and 99% by weight or less, and preferably 30% by weight or more and 98% by weight or less in the acrylic component. Further preferred. If the content of this monofunctional (meth) acrylic monomer is less than 20% by weight, there may be a problem that the strength of the film is insufficient. If it exceeds 99% by weight, the rigidity of the film becomes too high and the film becomes brittle. There is.
  • monofunctional (meth) acrylic monomers having a Tg of less than 0 ° C. include, for example, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofluoro Examples include furyl acrylate, phenoxyethyl acrylate, ethoxyethyl acrylate, and 3-methoxybutyl acrylate. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use n-butyl acrylate as the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C.
  • a monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. may not be contained (content is 0% by weight), but the content when contained is more than 0% by weight in the acrylic component , Preferably 50% by weight or less, more preferably more than 0% by weight and 45% by weight or less. When the content of the monofunctional (meth) acrylic monomer exceeds 50% by weight, there may be a problem that the strength of the film is not sufficient.
  • the type, combination, amount used, etc. of the (meth) acrylic monomer are appropriately determined in consideration of compatibility with urethane, polymerizability at the time of photocuring such as radiation, and characteristics of the high molecular weight obtained.
  • N-methylolacrylamide, glycidyl acrylate, glycidyl methacrylate, N , N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylamide, 2-hydroxypropyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, imide acrylate, N-vinylpyrrolidone, oligoester acrylate, ⁇ -caprolactone acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxylated cyclododecatriene Acrylate may be copolymerized monomer such as methoxyethyl acryl
  • Polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol.
  • Examples include tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, polyester acrylate, and the like, and trimethylolpropane tri (meth) acrylate is particularly preferable.
  • the polyfunctional monomer may be contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the acrylic monomer. If the content of the polyfunctional monomer is 1 part by weight or more, the cohesive force of the composite film is sufficient, and if it is 20 parts by weight or less, the elastic modulus does not become too high, and the unevenness of the adherend surface is reduced. Can follow.
  • Urethane polymer is obtained by reacting diol with diisocyanate.
  • a catalyst is used for the reaction between the hydroxyl group of the diol and the isocyanate.
  • the reaction is promoted without using an environmental load catalyst such as dibutyltin dilaurate or tin octoate. Can be made.
  • low molecular weight diol examples include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol.
  • Examples of the high molecular weight diol include polyether polyols obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc., or the above-mentioned divalent alcohols, 1,4-butanediol, 1,6-hexanediol, etc. And polyester polyols composed of polycondensates of dihydric basic acids such as adipic acid, azelaic acid and sebacic acid, acrylic polyols, carbonate polyols, epoxy polyols and caprolactone polyols. Among these, for example, polyoxytetramethylene glycol (PTMG), polyalkylene carbonate diol (PCD) and the like are preferably used.
  • PTMG polyoxytetramethylene glycol
  • PCD polyalkylene carbonate diol
  • acrylic polyol examples include a copolymer of a hydroxyl group-containing monomer and a (meth) acryl monomer, in addition to a copolymer of a monomer having a hydroxyl group.
  • epoxy polyol examples include an amine-modified epoxy resin.
  • the urethane polymer constituting the composite film does not include a crosslinked structure.
  • the diol used for forming the urethane polymer is preferably a linear (linear) diol.
  • the diol may be a side chain diol or a diol containing a branched structure as long as the condition that the urethane polymer does not form a crosslinked structure is satisfied. That is, the urethane polymer constituting the composite film of the present invention does not contain a crosslinked structure, and therefore is completely different from the IPN structure.
  • the above diols can be used alone or in combination in consideration of solubility in acrylic monomers, reactivity with isocyanates, and the like.
  • the strength is required, it is effective to increase the amount of the urethane hard segment by the low molecular weight diol.
  • a diol having a large molecular weight is preferably used alone.
  • Polyether polyols are generally inexpensive and have good water resistance, and polyester polyols have high strength.
  • the type and amount of the polyol can be freely selected according to the use and purpose, and the viewpoints such as the properties of the base material to be applied, reactivity with isocyanate, compatibility with acrylic, etc. From the above, the type, molecular weight and amount of use of the polyol can be selected as appropriate.
  • diisocyanate examples include aromatic, aliphatic and alicyclic diisocyanates, dimers and trimers of these diisocyanates.
  • aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), phenylene diisocyanate (PPDI), m.
  • Tetramethylxylylene diisocyanate (TMXDI), methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexane diisocyanate (hydrogenated PPDI), bis (isocyanatomethyl) cyclohexane (hydrogenated XDI), norbornene Diisocyanate (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), butanedi Cyanate, 2,4-hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like. Moreover, these dimers, trimers, and polyphenylmethane diisocyanate are used. Examples of the trimer include isocyanurate type, burette type, and allophanate type, and can be used as appropriate.
  • TDI methylcyclohexane diisocyanate
  • MDI dicyclohexylmethane diisocyanate
  • PPDI cyclohexane diisocyanate
  • NBDI norbornene diisocyanate
  • Aliphatic and alicyclic diisocyanates such as isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), butane diisocyanate, 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate are preferred. used. This is because it is not preferable to use an aromatic diisocyanate containing a benzene ring because a colored substance having a conjugated structure is easily generated by a photoreaction. In the present invention, it does not contain a benzene ring, is hardly yellowed, and has no yellow color. Modified aliphatic and alicyclic diisocyanates are preferably used.
  • diisocyanates can be used alone or in combination. From the viewpoints of the characteristics of the support to which the composite film is applied (applied or the like), solubility in acrylic monomers, reactivity with hydroxyl groups, and the like, the type and combination of diisocyanates may be appropriately selected.
  • the urethane polymer contains hexamethylene diisocyanate (HDI), hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4-diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), and hydrogenated xylene diisocyanate ( It is preferably formed using at least one diisocyanate selected from the group consisting of HXDI), and hydrogenated xylene diisocyanate is particularly preferred.
  • HDI hexamethylene diisocyanate
  • HMDI hydrogenated tolylene diisocyanate
  • HMDI hydrogenated 4,4-diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • hydrogenated xylene diisocyanate It is preferably formed using at least one diisocyanate selected from the group consisting of HXDI), and hydrogenated xylene diisocyanate is particularly preferred.
  • the amount of the diol component and diisocyanate component used to form the urethane polymer is preferably NCO / OH (equivalent ratio) of 1.1 or more and 2.0 or less, preferably 1.12 or more, 1 Is more preferably 1.60 or less, and particularly preferably 1.15 or more and 1.40 or less.
  • NCO / OH (equivalent ratio) is less than 1.1, the molecular weight of the urethane polymer becomes too large, the viscosity of the composite film precursor (syrup solution) becomes large, and the work becomes difficult in the subsequent sheeting process. There is.
  • NCO / OH (equivalent ratio) exceeds 2.0, the molecular weight of a urethane polymer will become small and break strength will fall easily.
  • the ratio of the acrylic component and the urethane component forming the composite film is a weight ratio
  • the acrylic component / urethane component is 0.25 or more and 4.00 or less, preferably 0.429 or more, 2 .333 or less, particularly preferably 0.538 or more and 1.857 or less.
  • the acrylic component / urethane component is less than 0.25, the viscosity of the syrup solution becomes large, and the work may be difficult in the subsequent sheet forming step.
  • the acrylic component / urethane component exceeds 4.00, the amount of urethane polymer in the composite film becomes less than 25%, the tensile strength at break is lowered, and it may not be practically used.
  • a hydroxyl group-containing acrylic monomer may be added to the urethane polymer constituting the composite film.
  • a hydroxyl group-containing acrylic monomer By adding a hydroxyl group-containing acrylic monomer, a (meth) acryloyl group can be introduced into the molecular end of the urethane prepolymer, and a copolymerizability with the (meth) acrylic monomer is imparted. The compatibility is enhanced, and SS characteristics such as breaking strength can be improved.
  • the hydroxyl group-containing acrylic monomer used here include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and the like.
  • the amount of the hydroxyl group-containing acrylic monomer used is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the urethane polymer.
  • additives that are usually used, for example, an ultraviolet absorber, an antioxidant, etc.
  • Antiaging agents, fillers, pigments, colorants, flame retardants, antistatic agents, light stabilizers, and the like can be added within a range that does not impair the effects of the present invention.
  • These additives are used in normal amounts depending on the type. For example, when forming a composite film, these additives may be added in advance before the polymerization reaction of diisocyanate and diol, or may be added to the urethane polymer and the acrylic monomer.
  • UVA ultraviolet absorber
  • 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole for example, Ciba Japan Co., Ltd.
  • benzotriazole-based ultraviolet absorber examples include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (for example, Ciba Japan Co., Ltd.) as a benzotriazole-based ultraviolet absorber.
  • TINUVIN PS benzenepropanoic acid and 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C 7 -C 9 side chain and straight chain Ester compounds
  • octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole) -2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- 5-Chloro-2H-benzotriazol-2-yl) phenyl] propionate for example, “TINUVIN 109” manufactured by Ciba Japan
  • 2- (2H-benzotriazol-2-yl) -4,6 -Bis (1-methyl-1-phenylethyl) phenol for example, “TINUVIN 900” manufactured by Ciba
  • hydroxyphenyl triazine-based ultraviolet absorber examples include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and [ Reaction product with (C10-C16, mainly C12-C13 alkyloxy) methyl] oxirane (for example, “TINUVIN 400” manufactured by Ciba Japan), 2- (2,4-dihydroxyphenyl) -4,6 Reaction product of bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester (for example, “TINUVIN 405” manufactured by Ciba Japan), 2 , 4-Bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine (eg For example, “TINUVIN 460” manufactured by Ciba Japan Ltd.), 2- (4,6-
  • benzophenone ultraviolet absorber examples include “CHIMASORB 81” manufactured by Ciba Japan.
  • benzoate UV absorber examples include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (for example, “TINUVIN 120” manufactured by Ciba Japan Co., Ltd.). ) And the like.
  • the above ultraviolet absorber can be used alone or in combination of two or more.
  • the total amount of the ultraviolet absorber used is 0.1% by weight or more with respect to 100% by weight of the composition for forming each layer, for example, 100% by weight of the film precursor in the case of a composite film. It is preferably 0% by weight or less, more preferably 0.5% by weight or more and 2.0% by weight or less. If the content of the UV absorber is 0.1% by weight or more, absorption of UV light causing deterioration or coloring is sufficient, and if it is 4.0% by weight or less, coloring by the UV absorber itself is caused. There is no.
  • the light stabilizer used in the present invention is preferably a hindered amine light stabilizer (HALS).
  • HALS hindered amine light stabilizer
  • examples of the hindered amine light stabilizer used in the present invention include a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (for example, manufactured by Ciba Japan Co., Ltd.).
  • TINUVIN 622 a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and N, N ′, N ′′, N ′ ′′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10 -One-to-one reaction product with diamine (eg, “TINUVIN 119” manufactured by Ciba Japan), dibutylamine, 1,3-triazine, N, N′-bis (2,2,6,6- Tetra A polycondensate of til-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine (for example, “TINUVIN 2020 manufactured by Ciba Japan Co., Ltd.) )), Poly [ ⁇ 6
  • a urethane polymer has a problem of heat resistance and heat-and-moisture resistance in a dark place, and a colored substance having a conjugated structure or a nitrogen-containing colored substance is generated.
  • Japanese Patent Application Laid-Open No. 9-130706 and Japanese Patent No. 2625508 disclose that for the purpose of preventing such a phenomenon, a phenolic or phosphorus compound, a hindered amine light stabilizer, a benzotriazole ultraviolet absorber or the like is used alone. It is known that it is effective when used in combination.
  • the phosphorus compound used in the present invention is not particularly limited, but for example, a trisubstituted phosphite compound represented by the following formula is desirable.
  • R 1, R 2 and R 3 may be the same or different and are linear or branched having an aromatic or aromatic aliphatic group having 1 to 18 carbon atoms, or an ether group as required Represents an aliphatic group of the chain, or R1 and R2 together with a phosphorus atom and two oxygen atoms form a 5- or 6-membered heterocycle. However, at least one of the substituents R1, R2 and R3 represents an aromatic group having 6 to 18 carbon atoms or a linear or branched aliphatic group having 9 to 18 carbon atoms.
  • aryl phosphites such as triphenyl phosphite or tris (nonylphenyl) phosphite; diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diisodecyl phenyl phosphite, diisooctyl octyl phenyl phosphite Alkyl-aryl phosphites such as phenyl neopentyl glycol phosphite or 2,4,6-tri-t-butylphenyl- (2-butyl-2-ethyl-1,3-propanediol) phosphite; Alkyl phosphites such as decyl phosphite, trilauryl phosphite or tris (tridecyl) phosphite; diisodecyl penta
  • triisodecyl phosphite, phenyl diisodecyl phosphite, and diphenyl isodecyl phosphite are preferable from the viewpoint of the yellowing suppression effect, and it is particularly preferable to use a mixture thereof.
  • the structure of triisodecyl phosphite, the structure of phenyl diisodecyl phosphite, the structure of diphenyl isodecyl phosphite, and the structure of triphenyl phosphite are shown below.
  • the phenolic compound used in the present invention is, for example, a compound having a phenol skeleton having a bulky substituent (for example, t-butyl group, sec-butyl group, neopentyl group, etc.), and is represented by the following formula, for example.
  • the above phenolic compounds are commercially available, for example, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1325, Irganox1726, Irganox1726, Irganox1027 Irganox5057, Irganox565, Irganox565DD, Irganox295, Irganox1222, Irganox1141 (above, manufactured by Ciba Japan) and the like can be mentioned.
  • the phenol type compound represented by the said formula can obtain "Irganox1135" (made by Ciba Japan) as a commercial item, for example.
  • a small amount of solvent may be added to adjust the viscosity of the coating.
  • the solvent can be appropriately selected from commonly used solvents, and examples thereof include ethyl acetate, toluene, chloroform, dimethylformamide and the like.
  • an acrylic monomer is used as a diluent, a diol and a diisocyanate are reacted in the acrylic monomer to form a urethane polymer, and the acrylic monomer and the urethane polymer are mainly used.
  • a composite film can be formed by irradiating and curing ionizing radiation such as ultraviolet rays, visible light, and the like, and then peeling and removing the support and the like. Or it can also obtain in the form by which the composite film was laminated
  • the composite film can be obtained by curing using a low-pressure mercury lamp or the like.
  • the acrylic monomer may be added at a time during urethane synthesis, or may be added in several divided portions.
  • the diisocyanate is dissolved in the acrylic monomer, the diol may be reacted.
  • the molecular weight is not limited and a high molecular weight polyurethane can be produced, so that the molecular weight of the finally obtained urethane can be designed to an arbitrary size.
  • a release sheet (separator, etc.) may be placed on the mixture coated on the substrate sheet, etc. to block oxygen, or filled with an inert gas.
  • the oxygen concentration may be lowered by placing a substrate in the container.
  • the type of radiation and the type of lamp used for irradiation can be selected as appropriate, such as a low-pressure lamp such as a fluorescent chemical lamp, a black light and a sterilization lamp, a high-pressure such as a metal halide lamp and a high-pressure mercury lamp.
  • a low-pressure lamp such as a fluorescent chemical lamp, a black light and a sterilization lamp
  • a high-pressure such as a metal halide lamp and a high-pressure mercury lamp.
  • a lamp or the like can be used.
  • Irradiation amounts such as ultraviolet rays can be arbitrarily set according to required film characteristics.
  • the irradiation amount of ultraviolet rays is 100 to 5,000 mJ / cm 2 , preferably 1,000 to 4,000 mJ / cm 2 , more preferably 2,000 to 3,000 mJ / cm 2 .
  • the irradiation amount of ultraviolet rays is less than 100 mJ / cm 2 , a sufficient polymerization rate may not be obtained, and when it is more than 5,000 mJ / cm 2 , deterioration may be caused.
  • the temperature at the time of irradiation with ultraviolet rays or the like is not particularly limited and can be arbitrarily set. However, if the temperature is too high, a termination reaction due to polymerization heat is likely to occur, which may cause deterioration of characteristics.
  • the temperature is usually 70 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower.
  • the mixture containing a urethane polymer and an acrylic monomer as main components contains a photopolymerization initiator.
  • the photopolymerization initiator can be used without any particular limitation, and examples thereof include ketal photopolymerization initiators, ⁇ -hydroxyketone photopolymerization initiators, ⁇ -aminoketone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators.
  • Polymerization initiator bezophenone photopolymerization initiator, thioxanthone photopolymerization initiator, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator Agents, benzoin photopolymerization initiators, benzyl photopolymerization initiators, and the like can be used.
  • ketal photopolymerization initiators examples include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, “Irgacure 651” manufactured by Ciba Specialty Chemicals, Inc. Etc.).
  • Examples of the ⁇ -hydroxyketone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone (such as “Irgacure 184” manufactured by Ciba Japan Co., Ltd.), 2-hydroxy-2- Methyl-1-phenylpropan-1-one (commercially available products such as “Darocur 1173” manufactured by Ciba Japan), 1- [4- (2-hydroxyethoxy) -phenyl] -2 -Hydroxy-2-methyl-1-propan-1-one (commercially available products such as “Irgacure 2959” manufactured by Ciba Japan) and the like.
  • 1-hydroxycyclohexyl phenyl ketone such as “Irgacure 184” manufactured by Ciba Japan Co., Ltd.
  • 2-hydroxy-2- Methyl-1-phenylpropan-1-one commercially available products such as “Darocur 1173” manufactured by Ciba Japan
  • ⁇ -aminoketone photopolymerization initiator for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (commercially available is Ciba “Irgacure 907” manufactured by Japan, Inc.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (commercially available products manufactured by Ciba Japan Co., Ltd.) "Irgacure 369" etc.).
  • acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, “Lucirin TPO” manufactured by BASF Corporation).
  • benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, and anisole. And methyl ether.
  • acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone.
  • aromatic sulfonyl chloride photopolymerization initiator examples include 2-naphthalenesulfonyl chloride, and examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (O-ethoxycarbonyl) -oxime and the like.
  • benzoin photopolymerization initiator examples include benzoin, and examples of the benzyl photopolymerization initiator include benzyl.
  • benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
  • thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
  • a small amount of solvent may be added to adjust the viscosity of the coating.
  • the solvent can be appropriately selected from commonly used solvents, and examples thereof include ethyl acetate, toluene, chloroform, dimethylformamide and the like.
  • the thickness of the coating layer constituting the multilayer sheet of the present invention is preferably 2 to 50 ⁇ m, more preferably 5 to 40 ⁇ m, still more preferably 8 to 30 ⁇ m.
  • the thickness of the coat layer is less than 2 ⁇ m, a defect site where the coat layer is not formed, such as pinholes, is likely to occur, and the characteristics of the coat layer may not be sufficiently exhibited.
  • it exceeds 50 ⁇ m the physical properties of the coating layer may deteriorate the physical properties of the multilayer sheet.
  • the thickness of the base material constituting the multilayer sheet of the present invention can be appropriately selected according to the purpose and the like, for example, according to the type and location of the object to be covered and protected, and is not particularly limited, but is 100 ⁇ m or more. It is preferably 150 ⁇ m or more, more preferably 200 ⁇ m or more. Moreover, it is preferable that the upper limit of thickness is about 1 mm.
  • the thickness of the film constituting the substrate is preferably about 50 to 800 ⁇ m, and more preferably about 100 to 600 ⁇ m, for example, in the case of chipping used for protecting the body of an automobile. Is preferred. In the case of aircraft use, it is about 50 to 1,000 ⁇ m, more preferably about 200 to 800 ⁇ m. In the case of a motorcycle, it is preferably about 50 to 800 ⁇ m, more preferably about 100 to 600 ⁇ m.
  • thermosetting it is preferable to form a coating by thermosetting in a state where the coating liquid for forming the coating layer is applied on the surface of the substrate. Since excellent adhesion can be realized by thermosetting in such a state, the coat layer can keep excellent adhesion to the substrate for a long period of time. Therefore, even if the application sheet is stuck on the coating film surface for positioning the adhesive sheet, the coat layer is not peeled off when the application sheet is peeled off.
  • the coating layer may be crosslinked with the base material by bonding the component constituting the coating layer and the component constituting the base material to form a crosslinking point, and may have a structure having a crosslinking point.
  • the substrate is a urethane-acrylic composite film
  • this residual isocyanate group reacts with the hydroxyl group of the urethane polymer-acrylic monomer mixture.
  • a crosslinking point can be formed.
  • the hydroxyl group of the fluoroethylene vinyl ether alternating copolymer used for forming the coating layer remains, it can react with the isocyanate group present in the coating solution for composite film to form a crosslinking point. it can. Therefore, in this case, when the composite film coating solution is applied, it is preferable that the residual isocyanate group or the residual hydroxyl group exists in the coat layer in a state where it can react. Moreover, it is preferable to apply the composite film coating solution before the crosslinking reaction of the coating layer is completely completed.
  • the coat layer composition used for forming the coat layer further contains a hydroxyl group-containing (meth) acrylic monomer. is required.
  • the coat layer and the base material form a cross-linked structure, excellent adhesion can be exerted, so that the coat layer keeps excellent adhesion to the base material for a long time. Can do. Therefore, even in this case, even when the application sheet is stuck on the coating film surface for positioning the adhesive sheet, the coating layer is not peeled off when the application sheet is peeled off.
  • the coating layer surface is semi-cured and then the composite film coating solution is applied to form a crosslinking point, or the surface is completely cured even when the surface is completely cured.
  • a coating solution for composite film can be applied thereon to form a crosslinking point. It is preferable to design appropriately considering the types and amounts of components used for forming the coat layer and the composite film. For example, in a state in which the remaining isocyanate group can react, a crosslinked structure can be formed by applying a composite film coating solution within 24 hours and causing a photocuring reaction.
  • a crosslinked structure can be formed by applying a composite film coating solution within 5 days and allowing it to undergo photocuring reaction. it can. If a hydroxyl group-containing monomer is reacted with the isocyanate crosslinking agent in advance, the residual isocyanate group can be reacted even after being stored at 50 ° C. for one week or longer.
  • coating is performed by dissolving a fluoroethylene vinyl ether alternating copolymer and a polyol in a solvent as required in a reaction liquid obtained by reacting a polyfunctional isocyanate and a hydroxyl group-containing (meth) acrylic monomer.
  • a layer coating solution can be formed, and a coating layer can be formed using this solution.
  • this solution is applied onto a polyethylene terephthalate film that has been subjected to a release treatment, and dried to form a coat layer.
  • a laminate (multilayer sheet) having a structure in which the film is crosslinked to the coat layer can be obtained.
  • the multilayer sheet can be laminated with another film on one side of the substrate (the side on which the coating layer is not provided) within a range that does not impair the effects of the present invention.
  • film forming materials include polyester resins such as polyethylene terephthalate (PET), polyolefin resins such as polyethylene (PE) and polypropylene (PP), polyimide (PI), polyetheretherketone (PEEK), and poly
  • PET polyethylene terephthalate
  • PP polypropylene
  • PI polyimide
  • PEEK polyetheretherketone
  • thermoplastic resins such as vinyl chloride (PVC), polyvinylidene chloride resin, polyamide resin, polyurethane resin, polystyrene resin, acrylic resin, fluororesin, cellulose resin, polycarbonate resin, thermosetting resin and the like can be given.
  • the pressure-sensitive adhesive sheet of the present invention preferably has a structure having a coating layer on one side of the substrate and a pressure-sensitive adhesive layer on the other side.
  • the pressure-sensitive adhesive that forms this pressure-sensitive adhesive layer is not particularly limited, and general materials such as acrylic, rubber-based, silicon-based, etc. can be used, but adhesion at low temperatures and retention at high temperatures, In view of cost and the like, an acrylic adhesive is preferable.
  • an acrylic adhesive an acrylic copolymer obtained by copolymerizing a monomer component mainly composed of an acrylate ester and a monomer component having a functional group such as a carboxyl group or a hydroxyl group (may be two or more types)
  • An acrylic pressure-sensitive adhesive containing can be used.
  • acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec- Butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth)
  • the following monomer components can be copolymerized with the above alkyl (meth) acrylate.
  • copolymerizable monomer components include monomers containing carboxyl groups such as (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like.
  • the pressure-sensitive adhesive used in the present invention comprises at least one selected from the group consisting of 2-ethylhexyl acrylate and isononyl acrylate, and at least one carboxyl group-containing monomer selected from the group consisting of acrylic acid and methacrylic acid. It is preferable to include. That is, the pressure-sensitive adhesive used in the present invention may be a copolymer obtained by copolymerizing 2-ethylhexyl acrylate, isononyl acrylate, etc. as a main monomer and a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, etc. .
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited and can be arbitrarily set, but is usually preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and particularly preferably 40 ⁇ m or more. However, the upper limit is usually preferably about 100 ⁇ m.
  • the pressure-sensitive adhesive layer is formed by, for example, applying a solvent-based or emulsion-based pressure-sensitive adhesive directly to a substrate and drying it, and applying these pressure-sensitive adhesives to release paper to form a pressure-sensitive adhesive layer in advance.
  • a method of attaching the pressure-sensitive adhesive layer to a substrate or the like can be applied. It is also possible to apply a method in which a radiation curable pressure-sensitive adhesive is applied to a base material, and both the pressure-sensitive adhesive layer and the film are irradiated with radiation to simultaneously cure the base material and the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention has excellent surface slipperiness.
  • the surface slipperiness can be evaluated by, for example, a numerical value of a static friction coefficient.
  • the static friction coefficient is determined by measuring the static friction coefficient of the outermost surface layer according to JISK7125. That is, an adhesive sheet of a predetermined size is fixed on a standard test plate, a sliding piece is placed on the adhesive sheet, the sliding piece is pulled while applying normal force (uniform pressure distribution), and the maximum load is measured.
  • the static friction coefficient is obtained using the following calculation formula.
  • ⁇ Fs / Fp ( ⁇ : static friction coefficient, Fs: static friction force (N), Fp: normal force)
  • the static friction coefficient is preferably 1.50 or less, and more preferably 1.00 or less.
  • the pressure-sensitive adhesive sheet of the present invention has a breaking elongation of 150% or more, preferably 200% or more and 1,000% or less, more preferably 250% or more and 800% or less, and particularly preferably 300% or more. 600% or less. If the elongation at break is 200% or more, the pressure-sensitive adhesive sheet is sufficiently stretched at the time of sticking, so that the sticking work is not reduced. Further, if the elongation at break is 1,000% or less, the pressure-sensitive adhesive sheet will not grow too much at the time of sticking, and the sticking work will not be reduced.
  • the elongation at break means that the pressure-sensitive adhesive sheet (width 1 cm, length 13 cm) is subjected to a tensile test at a tensile speed of 200 mm / min, a distance between chucks of 50 mm, and room temperature (23 ° C.). The value divided by the distance (50 mm).
  • the pressure-sensitive adhesive sheet of the present invention is required to be transparent in order to reflect the color and the like of the painted surface of the adherend in the appearance as it is, but is colored with the same color as the color of the painted surface using a pigment or the like. Or may be colored in a different color and used as a paint substitute adhesive sheet.
  • an application sheet can be used, for example, for positioning and sticking, in order to improve the work of attaching the pressure-sensitive adhesive sheet.
  • a multilayer sheet is formed by thermosetting in a state where a coating layer coating solution is applied on a substrate, and then an adhesive layer is formed on the surface of the substrate to create an adhesive sheet, or After forming the pressure-sensitive adhesive layer on the temporary support, the pressure-sensitive adhesive layer formed on the substrate surface of the obtained multilayer sheet is laminated and bonded to form a pressure-sensitive adhesive sheet.
  • a coating layer is first formed by applying a coating liquid for a coating layer on the release-treated surface of a polyethylene terephthalate film (temporary support 1) that has been subjected to a release treatment. Then, a coating solution for the composite film is applied thereon, a transparent separator or the like is placed thereon, and a crosslinking point is also formed while forming a substrate by irradiating ultraviolet rays or the like from the separator. Remove. Separately, a pressure-sensitive adhesive layer coating solution is applied to the release-treated surface of the release-treated polyester film (temporary support 2) to form a pressure-sensitive adhesive layer.
  • this pressure-sensitive adhesive layer can be stacked on the substrate surface to obtain a pressure-sensitive adhesive sheet.
  • this pressure-sensitive adhesive layer can be stacked on the substrate surface to obtain a pressure-sensitive adhesive sheet.
  • the layer structure of the polyethylene terephthalate film (temporary support body 1) / coating layer / base material / adhesive layer / peeling process polyester film (temporary support body 2) by which peeling processing was carried out here Since the temporary support 1 and the temporary support 2 and the temporary support are peeled and removed at the time of use, that is, when the pressure-sensitive adhesive sheet is applied and applied, they are particularly included in the structure of the pressure-sensitive adhesive sheet of the present invention. Not. However, the temporary support 1, the temporary support 2, the temporary support, and the like can be appropriately provided as necessary, and these configurations belong to the technical scope of the present invention.
  • the pressure-sensitive adhesive sheet of the present invention is excellent in flexibility with respect to a curved surface, it can be neatly adhered even to a portion where a three-dimensional curved surface is severe. Moreover, since the pressure sensitive adhesive sheet of the present invention has excellent slipperiness on the outermost surface, the squeegee slides well during the sticking operation, and the pressure sensitive adhesive sheet is not wrinkled or damaged. In addition, according to the present invention, it is possible to realize a pressure-sensitive adhesive sheet in which the coat layer is firmly adhered to the base material. If such a pressure-sensitive adhesive sheet is used, for example, the coat layer does not peel off during a sticking operation.
  • protective multilayers for protecting painted surfaces of transport machines for example, motorcycles, bicycles, rail cars, ships, snowmobiles, gondola, lifts, escalators, automobiles, aircraft, etc., especially automobiles, aircraft, motorcycles etc.
  • Suitable for applications such as sheets, light guide films for mobile phones, sealing materials for electrode substrates, decorative films for handrails of escalators, and transparent films used in combination with transparent glass.
  • the cellophane tape was peeled off at a 30 m angle from the back of the cellophane tape at a tensile speed of 70 m / min, and the peeled state of the coating layer was evaluated. That is, powder such as flour is attached to the entire adhesive surface of the peeled cellophane tape, and the number of squares on which the powder adheres in an area exceeding 50% of the area of one glance is counted according to the following evaluation criteria. The adhesion was evaluated. Evaluation criteria 3 points (excellent) Powder adheres to all 100cm. 2 points (good) The powder adheres with the number in the range of 1 to 99 mm. 1 point (poor) No adhesion of powder.
  • the value of the static friction coefficient was calculated
  • the method for measuring the static friction coefficient is shown below.
  • the pressure-sensitive adhesive sheet is cut into a size of 80 mm in width and 100 mm in length, and this pressure-sensitive adhesive sheet is stuck on a standard test plate (JISG 3141: manufactured by Nippon Test Panel Co., Ltd.), and a sliding piece is placed on the pressure-sensitive adhesive sheet.
  • the static friction coefficient of the outermost surface layer was measured according to JISK7125.
  • the contact area of the sliding piece is 63 mm ⁇ 63 mm, the total mass of the sliding piece is 200 g (1.96 N), and a squeegee cloth is attached to the contact surface of the sliding piece with the adhesive sheet surface, and the sliding speed is 100 mm / min. Measurement was performed by pulling the sliding piece under the conditions. The static friction coefficient was calculated
  • FIG. 1 (A) and (b) in FIG. 1 are schematic diagrams for explaining a method for measuring a static friction coefficient.
  • the sample 1 is fixed to the counterpart material 2 so that the measurement surface of the sample 1 (ex. Adhesive sheet) faces upward, that is, for example, the adhesive layer of the adhesive sheet is opposed to the counterpart.
  • material 2 ex. Standard test plate
  • a sliding piece contact area 63 mm ⁇ 63 mm
  • the sliding piece is pulled at a test speed of 100 mm / min.
  • the bottom surface of the sliding piece is covered with an elastic material (felt or the like) in order to apply a uniform pressure distribution.
  • sample 1 may be fixed directly to the counterpart material 1, it may be fixed by being attached to an auxiliary plate such as a support.
  • the sliding piece may be connected to the load cell via a spring.
  • the force increases linearly to give friction and reach a maximum load. This peak represents the static friction force (Fs).
  • the modulus value is larger than the modulus value of the reference pressure-sensitive adhesive sheet +0.3 MPa, but Comparative Example 2, Comparative Example 4, Comparative Example 6, Comparative Example 8, Comparative Example 10, and Comparative Example corresponding to each Example
  • the case where the modulus value was smaller than that of Example 12 and the coefficient of static friction was 1.50 or less was indicated as “good”, and the other cases were indicated as “poor”.
  • Example 1 ⁇ Preparation of coating layer coating liquid >> 11. 100 parts of a 50% concentration solution of fluoroethylene vinyl ether in xylene and toluene ("Lumiflon LF600” manufactured by Asahi Glass Co., Ltd.) and an isocyanate-based crosslinking agent ("Coronate HX” manufactured by Nippon Polyurethane Co., Ltd.) 10 parts, 10.25 parts of "PTMG2000” (polytetramethylene glycol, average molecular weight 2000) manufactured by Mitsubishi Chemical Corporation as a polyol, and 0.35 parts of dibutyltin lauric acid (manufactured by Tokyo Fine Chemical Co., Ltd.) as a catalyst "OL1”) xylene dilution (solids concentration 0.1% by weight) and 25.85 parts toluene, 25.85 parts hexane and 51.70 parts methyl ethyl ketone as diluent solvents, A coating layer coating solution was prepared.
  • PTMG2000
  • adipate film a 150- ⁇ m thick adipate-ester thermoplastic polyurethane film (manufactured by Nippon Matai Co., Ltd., hardness 85A (hereinafter referred to as “adipate film”)) was used as the substrate. On this adipate film, the coating layer coating solution obtained above was applied so that the thickness after curing was 10 ⁇ m, and dried and cured at a temperature of 140 ° C. for 3 minutes. A multilayer sheet having a coating layer on one surface was formed.
  • the pressure-sensitive adhesive composition was applied as a temporary support to a release-treated surface of a polyethylene terephthalate film having a thickness of 50 ⁇ m so that the final product had a thickness of 50 ⁇ m.
  • a peel-treated PET film as a separator is overlaid and coated, and then the surface of the PET film is cured by irradiating with ultraviolet rays (illuminance 290 mW / cm 2 , light amount 4,600 mJ / cm 2 ) using a metal halide lamp. Then, an adhesive layer was formed on the temporary support. Then, it was made to dry at 140 degreeC for 3 minute (s), the unreacted residual acrylic monomer was dried, and the adhesive layer was produced.
  • ultraviolet rays illumination 290 mW / cm 2 , light amount 4,600 mJ / cm 2
  • Examples 2-7, Comparative Examples 1-2 A coating layer, a multilayer sheet, and an adhesive sheet were prepared in the same manner as in Example 1 except that the coating layer coating solution having the composition shown in Table 1 was used in the preparation of the coating layer coating solution.
  • the comparative example 1 is a thing in which the coating layer is not provided, and an adhesive sheet consists of a base material and an adhesive layer. This pressure-sensitive adhesive sheet was used as a standard pressure-sensitive adhesive sheet in the evaluation. About the obtained adhesive sheet, the same measurement and evaluation as Example 1 were performed. The results are shown in Table 3.
  • Example 8 Comparative Examples 3 and 4
  • adipate film As the base material, an adipate film having a thickness of 290 ⁇ m (manufactured by Nippon Matai Co., Ltd., hardness 87A (hereinafter referred to as “adipate film”)) is used, and the coating layer coating liquid shown in Table 2 is used.
  • a coat layer, a multilayer sheet and an adhesive sheet were produced in the same manner as in Example 1 except that they were used.
  • the comparative example 3 is a thing in which the coating layer is not provided, and an adhesive sheet consists of a base material and an adhesive layer. This pressure-sensitive adhesive sheet was used as a standard pressure-sensitive adhesive sheet in the evaluation. About the obtained adhesive sheet, the same measurement and evaluation as Example 1 were performed. The results are shown in Table 4.
  • Example 9 Comparative Examples 5 and 6
  • a caprolactone film having a thickness of 150 ⁇ m manufactured by Nippon Matai Co., Ltd., hardness 87A (hereinafter referred to as “caprolactone film”)
  • the coating layer coating liquid shown in Table 2 is used.
  • a coat layer, a multilayer sheet and an adhesive sheet were produced in the same manner as in Example 1 except that they were used.
  • the comparative example 5 is a thing in which the coating layer is not provided, and an adhesive sheet consists of a base material and an adhesive layer.
  • This pressure-sensitive adhesive sheet was used as a standard pressure-sensitive adhesive sheet in the evaluation. About the obtained adhesive sheet, the same measurement and evaluation as Example 1 were performed. The results are shown in Table 4.
  • Example 10 As a base material, a caprolactone film having a thickness of 290 ⁇ m (manufactured by Nippon Matai Co., Ltd., hardness 87A (hereinafter referred to as “caprolactone film”)) is used, and the coating liquid coating composition shown in Table 2 is used. A coat layer, a multilayer sheet and an adhesive sheet were produced in the same manner as in Example 1 except that they were used.
  • the comparative example 3 is a thing in which the coating layer is not provided, and an adhesive sheet consists of a base material and an adhesive layer. This pressure-sensitive adhesive sheet was used as a standard pressure-sensitive adhesive sheet in the evaluation. About the obtained adhesive sheet, the same measurement and evaluation as Example 1 were performed. The results are shown in Table 4.
  • Example 6 In the same manner as in Example 1 except that the type and amount of coating liquid for coating layer were changed to those shown in Table 5 and the coating liquid for coating layer was applied on the UA-A substrate, An adhesive sheet was prepared. About the obtained adhesive sheet, the same measurement and evaluation as Example 1 were performed. The results are shown in Table 6.
  • Example 6 In the same manner as in Example 1 except that the type and amount of coating liquid for coating layer were changed to those shown in Table 5 and the coating liquid for coating layer was applied on the UA-B base material, An adhesive sheet was prepared. About the obtained adhesive sheet, the same measurement and evaluation as Example 1 were performed. The results are shown in Table 6.
  • A Fluoroethylene vinyl ether alternating copolymer “LF600” (Asahi Glass Co., Ltd.)
  • B-1 Isocyanate-based crosslinking agent “Coronate HX” (manufactured by Nippon Polyurethane Industry Co., Ltd.) “C / HX”
  • B-2 Isocyanate-based crosslinking agent “Coronate HL” (manufactured by Nippon Polyurethane Industry Co., Ltd.) “ C / HL ”Polyol: ⁇ "PTMG2000” (polytetramethylene glycol (average molecular weight 2000), manufactured by Mitsubishi Chemical Corporation) ⁇ "PTMG1000” (polytetramethylene glycol (average molecular weight 1000), manufactured by Mitsubishi Chemical Corporation) ⁇ "T5650E” (polycarbonate diol (average molecular weight 500), manufactured by Asahi Kasei Chemicals Corporation) "PLACCEL 305" (trifunctional
  • Examples 1 to 7 which are the pressure-sensitive adhesive sheets of the present invention, showed a value of 5% modulus equivalent to that of the pressure-sensitive adhesive sheet (reference) of Comparative Example 1, and 5% modulus of Comparative Example 2 It was found to be smaller than the value. This indicates that the pressure-sensitive adhesive sheet in which a coating layer is formed using a coating layer composition containing a polyol maintains the excellent flexibility of the substrate itself. This is probably because the molecular weight between crosslinking points in the coating layer increased due to the addition of the polyol.
  • the molecular weight of the polyol is preferably 300 or more, more preferably 500 or more, and particularly preferably 1,000 or more.
  • the molecular weight of the polyol is preferably 10,000 or less, more preferably 8,000 or less, and particularly preferably 5,000 or less, from the viewpoint of the appearance turbidity.
  • the molar ratio of the polyol to the main agent is preferably 0.2 or more, more preferably 0.25 or more, and particularly preferably 0.5 or more. I understood.
  • the molar ratio of the polyol is preferably 0.7 or less.
  • the adhesive sheet was produced using the coating layer composition which mix
  • the pressure-sensitive adhesive sheets of Examples 1 to 7 of the present invention are superior in surface slipperiness compared to Comparative Example 2, and in particular, the pressure-sensitive adhesives of Examples 1 to 4 and Example 6 are used. It has been found that the sheet exhibits very good slipperiness.
  • Example 8 which is the pressure-sensitive adhesive sheet of the present invention shows a value of 5% modulus equivalent to that of the pressure-sensitive adhesive sheet (reference) of Comparative Example 3, and the value of 5% modulus of Comparative Example 4 is 5% modulus. It was found that the pressure-sensitive adhesive sheet of Example 9 of the present invention had a value of 5% modulus equivalent to that of the pressure-sensitive adhesive sheet (reference) of Comparative Example 5, and 5% of Comparative Example 6 It was found that the modulus was smaller than the value of the modulus, and Example 10 which is the pressure-sensitive adhesive sheet of the present invention showed a value of 5% modulus equivalent to that of the pressure-sensitive adhesive sheet of Comparative Example 7 (reference).
  • Example 11 which is the pressure-sensitive adhesive sheet of the present invention shows a value of 5% modulus equivalent to that of the pressure-sensitive adhesive sheet (reference) of Comparative Example 9, and 5% modulus of Comparative Example 10 It was found that the pressure-sensitive adhesive sheet of Example 12 of the present invention was smaller than the value, and the value of 5% modulus equivalent to that of the pressure-sensitive adhesive sheet (reference) of Comparative Example 11 was 5%. It was found to be smaller than the modulus value. This indicates that the pressure-sensitive adhesive sheet in which a coating layer is formed using a coating layer composition containing a polyol maintains the excellent flexibility of the base material itself. No. 12 was found to be excellent in terms of surface slipperiness. That is, the same effect as in Table 3 was also observed here.
  • the pressure-sensitive adhesive sheet of the present invention has a coating layer using at least a fluorine-based polymer, a polyol, and a polyfunctional isocyanate using a composite film, and has excellent flexibility and excellent slipperiness at the same time. It turns out that it can be achieved.
  • O1 dibutyltin lauric acid
  • the prepared coating solution for composite film was applied so that the thickness after curing was 290 ⁇ m (300 ⁇ m including the thickness of the coating layer), and then the polyethylene terephthalate was subjected to release treatment as a separator.
  • PET films were stacked. A multilayer having a coat layer and a composite film on the temporary support 1 by irradiating the PET film surface with ultraviolet rays (illuminance 210 mW / cm 2 , light amount 4,000 mJ / cm 2 ) using a metal halide lamp. A sheet (having a separator) was formed.
  • the pressure-sensitive adhesive composition was applied as a temporary support 2 to a release-treated surface of a polyethylene terephthalate film having a thickness of 50 ⁇ m so that the final product had a thickness of 50 ⁇ m.
  • a peel-treated PET film as a separator is overlaid and coated, and then the surface of the PET film is cured by irradiating with ultraviolet rays (illuminance 290 mW / cm 2 , light amount 4,600 mJ / cm 2 ) using a metal halide lamp.
  • ultraviolet rays illumination 290 mW / cm 2 , light amount 4,600 mJ / cm 2
  • an adhesive layer was formed on the temporary support 2. Then, it was made to dry at 140 degreeC for 3 minute (s), the unreacted residual acrylic monomer was dried, and the adhesive layer was produced.
  • Example 14 to 23 A coat layer, a multilayer sheet, and an adhesive sheet were produced in the same manner as in Example 13 except that the type and blending amount of the coating layer coating liquid were changed to those shown in Table 7.
  • the obtained adhesive sheet it carried out similarly to Example 13, and evaluated the softness
  • Example 24 A coating layer, a multilayer sheet, and an adhesive sheet were produced in the same manner as in Example 13 except that the type and blending amount of the coating layer coating solution were changed to those shown in Table 8. About the obtained adhesive sheet, it carried out similarly to Example 13, and evaluated the softness
  • PLACCEL 305" trifunctional caprolactone polyol (average molecular weight 550), Daicel Chemical Industries, Ltd.) “305”-“PTMG1000” (polytetramethylene glycol (average molecular weight 1000), manufactured by Mitsubishi Chemical Corporation) Catalyst: Dibutyltin dilaurate (DBTDL) ("OL1", manufactured by Tokyo Fine Chemical Co., Ltd.), but using xylene dilution (concentration of dibutyltin laurate: 0.01% by weight)
  • the molecular weight of a polyol is 300 or more, More preferably, it is 500 or more, Most preferably, it is 1,000 or more.
  • the molecular weight of the polyol is preferably 10,000 or less, more preferably 8,000 or less, and particularly preferably 5,000 or less, from the viewpoint of the appearance turbidity.
  • the molar ratio of the polyol to the main agent is preferably 0.2 or more, more preferably 0.25 or more, and particularly preferably 0.5 or more. I understood. However, from the viewpoint of appearance turbidity, the molar ratio of the polyol is preferably 0.7 or less.
  • the adhesive sheets of Examples 13 to 22 and 24 to 28 of the present invention are superior in adhesion between the coating layer and the substrate as compared with Comparative Example 13, and in particular, Examples 13 to 15 , 26 to 28 were found to exhibit extremely good adhesion.
  • the reason for this is that in the preparation of a coating liquid for a coating layer having a specific composition, a composite is formed on the coating layer using a coating liquid for a coating layer obtained by reacting a hydroxyl group-containing (meth) acrylic monomer in advance with an isocyanate-based crosslinking agent. This is because a coating solution for film is applied to crosslink the coat layer and the composite film layer.
  • the molar ratio of the hydroxyl group-containing (meth) acrylic monomer for exhibiting adhesion is preferably 0.1 or more, more preferably 0.2 or more, particularly preferably 0.8, relative to the main agent. 3 or more.
  • the molar ratio of the (meth) acrylic monomer is preferably 0.5 or less from the viewpoint of elongation characteristics (breaking elongation).
  • V # 802 which is a polyfunctional monomer, has high skeletal rigidity and a short distance between acryloyl groups, so that the number of reactive points did not increase and adhesion was not improved. . Rather, it is speculated that V # 802 is less reactive due to steric hindrance than 4HBA. In order to improve the adhesion, it is considered that it is more preferable that the distance between the acrylic groups and the hydroxyl groups is separated to some extent (the degree is unknown), and the skeleton is long and flexible.
  • a pressure-sensitive adhesive sheet having a coating layer formed using at least a fluorine-based polymer, a polyol, a hydroxyl group-containing (meth) acrylic monomer, and a polyfunctional isocyanate. It has been found that excellent flexibility and excellent adhesion can be achieved at the same time.
  • Examples 13 to 22, 24 to 28 and Comparative Examples 13 to 14 were also comprehensively evaluated based on the evaluation results of flexibility and adhesion. That is, the value of the flexibility of Comparative Example 13 is taken as a reference value, the case where the flexibility is smaller than this reference value (2.02 MPa) and the evaluation point of adhesion is 2 is “good”, and the flexibility is the reference. When the evaluation score is smaller than the value and the adhesion evaluation score is 3, “excellent” is displayed. Otherwise, “impossible” is displayed. Examples 13 to 15 and 26 to 28 are “excellent”. 16 to 22, 24 to 25 and 29 were “good”, and comparative example 14 was “impossible”.
  • the adhesive sheet of Example 23 is inferior in adhesiveness, in order to form a crosslinking point by applying the composite film coating liquid on the coating layer formed using the coating layer coating liquid. It is necessary to add a hydroxyl group-containing (meth) acrylic monomer to the coating layer coating solution.
  • a coating solution for a composite film is formed on a coating layer using a coating solution for a coating layer obtained by reacting a hydroxyl group-containing (meth) acrylic monomer with an isocyanate-based crosslinking agent in advance. This is because the coating layer and the composite film layer are crosslinked.
  • the molar ratio of the hydroxyl group-containing (meth) acrylic monomer for exhibiting adhesion is preferably 0.1 or more, more preferably 0.2 or more, particularly preferably 0.8, relative to the main agent. 3 or more.
  • the molar ratio of the (meth) acrylic monomer is preferably 0.5 or less from the viewpoint of elongation characteristics (breaking elongation).
  • V # 802 which is a polyfunctional monomer, has high skeletal rigidity and a short distance between acryloyl groups, so that the number of reactive points did not increase and adhesion was not improved. . Rather, it is speculated that V # 802 is less reactive due to steric hindrance than 4HBA. In order to improve the adhesion, it is considered that it is more preferable that the distance between the acrylic groups and the hydroxyl groups is separated to some extent (the degree is unknown), and the skeleton is long and flexible.
  • At least a pressure-sensitive adhesive sheet having a coating layer using a fluorine-based polymer, a polyol, a hydroxyl group-containing (meth) acrylic monomer and a polyfunctional isocyanate can simultaneously achieve excellent flexibility and excellent adhesion. I found out.
  • the pressure-sensitive adhesive sheet of the present invention can be suitably used as a pressure-sensitive adhesive sheet that requires flexibility for complex parts or curved surfaces. Moreover, since the pressure-sensitive adhesive sheet of the present invention has a coat layer formed by using a coat layer composition made of a fluororesin, it is excellent in slipperiness and workability at the time of sticking is good. Furthermore, according to this invention, the adhesive sheet excellent in the adhesiveness of a coating layer and a base material is realizable.
  • the coating layer composition of the present invention is also excellent in antifouling properties, for example, an adhesive for protecting the coating film surface exposed to harmful environments including outdoor weather, solvents, dust, fats and oils, and marine environments. It can be used as a sheet, a decorative adhesive sheet or a multilayer sheet. Further, it is also suitable as a chipping tape for protecting a coating film of an automobile body or the like, an adhesive sheet for a body protection film, or a multilayer sheet.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

Le but de l'invention est de fournir une feuille adhésive qui possède une bonne flexibilité et un bon lissé de surface. Cette feuille adhésive comprend une couche de revêtement, une base et une couche adhésive. La couche de revêtement est obtenue en utilisant au moins un polymère à base de fluor, un polyol, et un isocyanate polyfonctionnel. Il est préférable que le polymère à base de fluor soit un copolymère alternant de fluoroéthylène éther de vinyle possédant une structure spécifique. Il est également préférable que la base contienne un polymère d'uréthanne (méth)acrylique ou un polymère d'uréthanne. Il est en outre préférable que la couche de revêtement comprenne en outre un monomère (méth)acrylique contenant un groupe hydroxyle.
PCT/JP2013/076367 2012-10-01 2013-09-27 Composition de couche de revêtement WO2014054542A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135394A1 (fr) * 2017-01-19 2018-07-26 パナソニックＩｐマネジメント株式会社 Composition de revêtement, élément optique et illuminateur

Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
JP6718226B2 (ja) * 2015-12-11 2020-07-08 旭化成株式会社 フッ素塗料組成物
WO2018150502A1 (fr) * 2017-02-15 2018-08-23 リンテック株式会社 Rouleau
US20200062999A1 (en) * 2017-05-23 2020-02-27 Lintec Corporation Roll and method for producing roll
JP7259855B2 (ja) * 2018-06-13 2023-04-18 Ａｇｃ株式会社 加飾フィルム、組成物、加飾フィルムの製造方法、加飾フィルム付き３次元成形品の製造方法
JP7365777B2 (ja) * 2019-03-20 2023-10-20 リンテック株式会社 粘着フィルムの作製方法

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6135243A (ja) * 1984-07-27 1986-02-19 大成化工株式会社 フツ素含有ポリマ−を含む塗料で被覆されたプラスチツク物品及びその製造方法
JPS61157384A (ja) * 1984-12-28 1986-07-17 Dainippon Toryo Co Ltd 自動車車体の塗装方法
JPS62212471A (ja) * 1986-03-13 1987-09-18 Dainippon Ink & Chem Inc 塗料用樹脂組成物
JPH04106117A (ja) * 1990-08-28 1992-04-08 Dainippon Ink & Chem Inc 含ふっ素ビニル重合体組成物
JPH04292677A (ja) * 1991-03-22 1992-10-16 Tonen Corp 塗料用組成物
JPH08295840A (ja) * 1995-04-27 1996-11-12 Asahi Glass Co Ltd 塗料用樹脂組成物
JPH08319455A (ja) * 1995-05-26 1996-12-03 Asahi Glass Co Ltd 塗料用組成物
JPH10147746A (ja) * 1996-11-20 1998-06-02 Daikin Ind Ltd 耐汚染性被膜形成組成物及び塗装品
JPH10211681A (ja) * 1997-01-30 1998-08-11 Bridgestone Corp Ｏａ機器用部材
JP2002317142A (ja) * 2001-04-23 2002-10-31 Daido Toryo Kk 低汚染性塗料および低汚染性塗膜の形成方法
WO2007063698A1 (fr) * 2005-11-30 2007-06-07 Daikin Industries, Ltd. Composition de revêtement pour des doublages de protection de piles solaires
JP2008144178A (ja) * 2007-12-28 2008-06-26 Kaneka Corp 上塗り塗料用硬化性樹脂組成物およびそれを塗布してなる塗装物
JP2009155500A (ja) * 2007-12-27 2009-07-16 Sakai Silk Screen:Kk 防汚用塗料組成物及び付着防止体
JP2009155487A (ja) * 2007-12-27 2009-07-16 Creative Products Tashiro:Kk 含フッ素コーティング剤、コーティング体及びコーティング体の製造方法
JP2010260937A (ja) * 2009-05-01 2010-11-18 Tohpe Corp クリヤーコーティング組成物およびそれからなる塗装品

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6135243A (ja) * 1984-07-27 1986-02-19 大成化工株式会社 フツ素含有ポリマ−を含む塗料で被覆されたプラスチツク物品及びその製造方法
JPS61157384A (ja) * 1984-12-28 1986-07-17 Dainippon Toryo Co Ltd 自動車車体の塗装方法
JPS62212471A (ja) * 1986-03-13 1987-09-18 Dainippon Ink & Chem Inc 塗料用樹脂組成物
JPH04106117A (ja) * 1990-08-28 1992-04-08 Dainippon Ink & Chem Inc 含ふっ素ビニル重合体組成物
JPH04292677A (ja) * 1991-03-22 1992-10-16 Tonen Corp 塗料用組成物
JPH08295840A (ja) * 1995-04-27 1996-11-12 Asahi Glass Co Ltd 塗料用樹脂組成物
JPH08319455A (ja) * 1995-05-26 1996-12-03 Asahi Glass Co Ltd 塗料用組成物
JPH10147746A (ja) * 1996-11-20 1998-06-02 Daikin Ind Ltd 耐汚染性被膜形成組成物及び塗装品
JPH10211681A (ja) * 1997-01-30 1998-08-11 Bridgestone Corp Ｏａ機器用部材
JP2002317142A (ja) * 2001-04-23 2002-10-31 Daido Toryo Kk 低汚染性塗料および低汚染性塗膜の形成方法
WO2007063698A1 (fr) * 2005-11-30 2007-06-07 Daikin Industries, Ltd. Composition de revêtement pour des doublages de protection de piles solaires
JP2009155500A (ja) * 2007-12-27 2009-07-16 Sakai Silk Screen:Kk 防汚用塗料組成物及び付着防止体
JP2009155487A (ja) * 2007-12-27 2009-07-16 Creative Products Tashiro:Kk 含フッ素コーティング剤、コーティング体及びコーティング体の製造方法
JP2008144178A (ja) * 2007-12-28 2008-06-26 Kaneka Corp 上塗り塗料用硬化性樹脂組成物およびそれを塗布してなる塗装物
JP2010260937A (ja) * 2009-05-01 2010-11-18 Tohpe Corp クリヤーコーティング組成物およびそれからなる塗装品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135394A1 (fr) * 2017-01-19 2018-07-26 パナソニックＩｐマネジメント株式会社 Composition de revêtement, élément optique et illuminateur
JPWO2018135394A1 (ja) * 2017-01-19 2019-12-19 パナソニックＩｐマネジメント株式会社 塗料組成物、光学部材及び照明装置
JP7241298B2 (ja) 2017-01-19 2023-03-17 パナソニックＩｐマネジメント株式会社 塗料組成物、光学部材及び照明装置

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