WO2014054542A1 - Coating layer composition - Google Patents

Coating layer composition Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
meth
coating layer
sensitive adhesive
adhesive sheet
pressure
Prior art date
Application number
PCT/JP2013/076367
Other languages
French (fr)
Japanese (ja)
Inventor
西川　健一
中川　善夫
上杉　正紀
康徳 山本
栄一 井本
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2014054542A1 publication Critical patent/WO2014054542A1/en

Links

Images

Classifications

    • 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.

Abstract

[Problem] To provide an adhesive sheet which has good flexibility and good surface smoothness. [Solution] This adhesive sheet comprises a coating layer, a base and an adhesive layer; and the coating layer is obtained using at least a fluorine-based polymer, a polyol and a polyfunctional isocyanate. It is preferable that the fluorine-based polymer is a fluoroethylene vinyl ether alternating copolymer having a specific structure. It is also preferable that the base contains at least a (meth)acrylic urethane polymer or a urethane polymer. It is further preferable that the coating layer additionally contains a hydroxyl group-containing (meth)acrylic monomer.

Description

コート層組成物Coat layer composition
　本発明はコート層組成物、及び、該コート層組成物を用いてなるコート層を有する多層シートと粘着シートに関し、特に、特定のフルオロエチレンビニルエーテル交互共重合体を有するコート層組成物、及び、多層シートと粘着シートに関する。 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.
　例えば、自動車、航空機業界においては、自動車等のボディーの塗装面の損傷防止のために透明粘着シートが貼り付けられることがある。この透明粘着シートの基材としてポリウレタン基材が使用されている（例えば、特開昭５９－４１３７６号公報、特開２００５－２７２５５８号公報参照）。この粘着シートは、スキージ等を用いて手作業で塗装面に直接貼り付けられるが、貼付作業時に位置ズレが生じたり、手の汚れが付着したり、または、特に三次元曲面が厳しい部位においてはきれいに貼りつけることができない等の問題があった。また、粘着シートの表面をスキージが滑らないため粘着シートにシワやキズが発生する等の問題もあった。さらにまた、表面の滑り性が良好なコーティング層を有する保護用粘着シートでは、三次元曲面の厳しい部位において追従性が悪化し、三次元曲面を持った被着体に追従させて貼りつけることが困難となる不具合が生じた。 For example, in the automobile and aircraft industries, 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. Furthermore, in the protective adhesive sheet having a coating layer with a good surface slipperiness, 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.
　また、耐候性などの観点から、基材にフッ素系樹脂からなるコート層を設けた塗膜保護用粘着シート（例えば、特開２００９－２９９０５３号公報参照）も知られているが、柔軟性が不十分であり、複雑な部位への適用が困難であった。 From the viewpoint of weather resistance and the like, 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.
特開昭５９－４１３７６号公報JP 59-41376 特開２００５－２７２５５８号公報JP 2005-272558 A 特開２００９－２９９０５３号公報JP 2009-299053 A
　　　本発明は上記問題点を解決するためになされたものであり、本発明は柔軟性を有し、かつ、表面滑り性に優れた粘着シートを提供することを目的とする。 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.
　本発明のコート層組成物は、少なくとも、フッ素系ポリマーと、ポリオールと、多官能イソシアネートとを用いてなることを特徴とする。
　ここで、フッ素系ポリマーは、下記式（Ｉ）で表されるフルオロエチレンビニルエーテル交互共重合体であることが好ましい。 The coat layer composition of the present invention is characterized by comprising at least a fluorine-based polymer, a polyol, and a polyfunctional isocyanate.
Here, the fluoropolymer is preferably a fluoroethylene vinyl ether alternating copolymer represented by the following formula (I).
Figure JPOXMLDOC01-appb-C000002
  
 
Figure JPOXMLDOC01-appb-C000002
  
 
（式中、Ｘはフッ素、塩素または臭素を表し、Ｒａは水素またはＣ１～Ｃ１０のアルキル基を表し、ＲｂはＣ１～Ｃ１６のアルキル基を表し、ＲｃはＣ１～Ｃ１６のアルキレン基を表し、ｍおよびｎは、それぞれ整数であり、フルオロエチレンビニルエーテル交互共重合体の重量平均分子量が１，０００～２，０００，０００となる範囲で選択される。） (In the formula, X represents fluorine, chlorine or bromine, R a represents hydrogen or a C1-C10 alkyl group, R b represents a C1-C16 alkyl group, and 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.)
　また、前記コート層組成物は、少なくとも上記式（Ｉ）で表されるフルオロエチレンビニルエーテル交互共重合体と、ポリオールと、水酸基含有（メタ）アクリルモノマーと、多官能イソシアネートとを用いてなることが好ましい。 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.
　本発明においては、前記ポリオール成分が、２価のアルコールから選ばれるジオールまたは３価のアルコールから選ばれるトリオールであることが好ましい。 In the present invention, the polyol component is preferably a diol selected from divalent alcohols or a triol selected from trivalent alcohols.
　本発明においてコート層組成物は、紫外線吸収剤、ヒンダードアミン光安定剤、リン系化合物およびフェノール系酸化防止剤からなる群から選ばれる少なくとも１種類をさらに含有することが好ましい。 In the present invention, 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.
　本発明の多層シートは、基材の少なくとも一方の面にコート層を有する多層シートであって、該コート層が上記いずれかのコート層組成物を用いてなり、かつ、基材が少なくとも（メタ）アクリルウレタンポリマーまたはウレタンポリマーを含有することを特徴とする。 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.
　ここで、前記基材は、（メタ）アクリルポリマーとウレタンポリマーとを含有する複合フィルムであることができる。 Here, the base material can be a composite film containing a (meth) acrylic polymer and a urethane polymer.
　本発明において多層シートを構成する前記基材は、紫外線吸収剤、ヒンダードアミン光安定剤、リン系化合物およびフェノール系酸化防止剤からなる群から選ばれる少なくとも１種類を含有することが好ましい。 In the present invention, 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.
　本発明の粘着シートは、上記いずれか１つの多層シートの少なくとも一方の面に、粘着剤層を有することを特徴とする。 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.
　ここで、前記粘着シートは、被着体の表面を保護するための保護シートとして使用されることが好ましい。 Here, the pressure-sensitive adhesive sheet is preferably used as a protective sheet for protecting the surface of the adherend.
　本発明によれば、柔軟性に優れ、かつ、表面滑り性に優れた粘着シートを実現することができる。また、本発明によれば、コート層と基材との密着性にも優れた粘着シートを実現することができる。さらにまた、これらの粘着シートに好適な多層シート及びコート層組成物を実現することができる。 According to 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.
静摩擦係数を測定する方法を説明するための概略図である。It is the schematic for demonstrating the method to measure a static friction coefficient.
　以下、本発明について詳細に説明する。
　本発明の多層シートは、少なくともコート層と基材とを有する積層シートであり、コート層はコート層組成物を用いて形成される。 Hereinafter, the present invention will be described in detail.
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.
　本発明のコート層組成物は、少なくとも、フッ素系ポリマーと、ポリオールと、多官能イソシアネートとを用いてなる。このフッ素系ポリマーは、フルオロエチレンビニルエーテル交互共重合体であることが好ましい。但し、このフルオロエチレンビニルエーテル交互共重合体は、フルオロエチレン単位とビニルエーテル単位とが交互に並んだフルオロエチレンビニルエーテル交互共重合体であり、下記式（Ｉ）で表されるフルオロエチレンビニルエーテル交互共重合体である。 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. However, 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.
Figure JPOXMLDOC01-appb-C000003
  
 
Figure JPOXMLDOC01-appb-C000003
  
 
　上記式（Ｉ）中、Ｘはフッ素、塩素または臭素を表し、Ｒａは水素またはＣ１～Ｃ１０のアルキル基を表し、ＲｂはＣ１～Ｃ１６のアルキル基を表し、ＲｃはＣ１～Ｃ１６のアルキレン基を表し、ｍおよびｎは、それぞれ整数であり、フルオロエチレンビニルエーテル交互共重合体の重量平均分子量が１，０００～２，０００，０００となる範囲で選択される。 In the above formula (I), 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, and R c represents a C1 to C16 alkyl group. Represents an alkylene group, and 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.
　フルオロエチレンビニルエーテル交互共重合体の重量平均分子量は、１，０００～２，０００，０００、好ましくは５，０００～１，０００，０００、さらに好ましくは１０，０００～５００，０００である。本発明において、上記式（Ｉ）中のｍおよびｎは、フルオロエチレンビニルエーテル交互共重合体の重量平均分子量が１，０００～２，０００，０００となる範囲で選択される。 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. In the present invention, 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.
　フルオロエチレンビニルエーテル交互共重合体の重量平均分子量は、ＧＰＣ法により測定することができる。ＧＰＣ法の測定方法を以下に示す。すなわち、フルオロエチレンビニルエーテル交互共重合体を、ＴＨＦ溶液を用いて２．０ｇ／Ｌとなるように調整した後、１２時間静置する。その後、この溶液を０．４５μｍメンブレンフィルターでろ過し、分析装置として東ソー（株）製の「ＨＬＣ－８１２０ＧＰＣ」を用い、下記測定条件の下、ろ液についてＧＰＣ測定を行う。 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 μm 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.
測定条件：
　カラム　　　　　ＴＳＫｇｅｌ　ＧＭＨ－Ｈ（Ｓ）×２
　カラムサイズ　　７．８ｍｍＩ．Ｄ．×３００ｍｍ
　溶離液　　　　　ＴＨＦ
　流量　　　　　　０．５ｍＬ／ｍｉｎ
　検出器　　　　　ＲＩ
　カラム温度　　　４０℃
　注入量　　　　　１００μＬ Measurement condition:
Column TSKgel GMH-H (S) x 2
Column size 7.8 mmI. D. × 300mm
Eluent THF
Flow rate 0.5mL / min
Detector RI
Column temperature 40 ° C
Injection volume 100μL
　本発明のコート層組成物を構成するポリオールとしては、２価のアルコールから選ばれるジオール、または、３価のアルコールから選ばれるトリオールであることが好ましい。例えば、２価のアルコールとしては、カーボネートジオール、テトラメチレングリコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサメチレングリコール、などが挙げられ、３価のアルコールとしては、カプロラクトントリオール、グリセロール、トリメチロールプロパン、ブタントリオール、ヘキサントリオール、などが挙げられる。 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. For example, 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.
　具体的には、ポリカーボネートジオール、ポリテトラメチレンエーテルグリコール（ＰＴＭＧ）、２官能性カプロラクトンポリオール、３官能性カプロラクトンポリオール、ポリエチレングリコール、ポリプロピレングリコール、などが好ましく用いられる。 Specifically, polycarbonate diol, polytetramethylene ether glycol (PTMG), bifunctional caprolactone polyol, trifunctional caprolactone polyol, polyethylene glycol, polypropylene glycol and the like are preferably used.
　本発明のコート層組成物を構成する多官能イソシアネートとは、イソシアネート基を分子内に２個以上有するものである。本発明に用いられる多官能イソシアネートとしては、例えば、水添キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水添ジフェニルメタンジイソシアネート、エチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ノルボルネンジイソシアネート等の２官能イソシアネート、デスモジュールＮ３２００（住化バイエルウレタン（株）製）、コロネートＬ（日本ポリウレタン（株）製）、コロネートＨＬ（日本ポリウレタン（株）製）、コロネートＨＸ（日本ポリウレタン（株）製）、タケネートＤ－１４０Ｎ（三井化学ポリウレタン（株）製）、タケネートＤ－１２７（三井化学ポリウレタン（株）製）、タケネートＤ－１１０Ｎ（三井化学ポリウレタン（株）製）等の３官能イソシアネートなどが挙げられる。本発明においては、これらの多官能イソシアネートを単独で、または２種以上併用することができる。 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, 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.
　ポリオールの水酸基のモル数［ＯＨ］と、多官能イソシアネートのイソシアネート基のモル数［ＮＣＯ］との比率（［ＯＨ］／［ＮＣＯ］）は、好ましくは０．０５～０．５、さらに好ましくは０．０５～０．４、特に好ましくは０．０５～０．３である。 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.
　本発明のコート層組成物は、さらに水酸基含有（メタ）アクリルモノマーを含有することが好ましい。 The coat layer composition of the present invention preferably further contains a hydroxyl group-containing (meth) acrylic monomer.
　本発明のコート層組成物を構成する水酸基含有（メタ）アクリルモノマーとは、分子内に水酸基を１個以上有し、かつ、分子内に（メタ）アクリロイル基を１個以上有するものである。水酸基含有（メタ）アクリルモノマーとしては、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシメタクリレート、４－ヒドロキシブチルアクリレート、４－ヒドロキシブチルメタクリレート、１，４－シクロへキサンジメタノールモノアクリレート、１，４－シクロへキサンジメタノールモノメタクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、ペンタエリスリトールアクリレートなどが挙げられる。本発明においては、これらの水酸基含有（メタ）アクリルモノマーを単独で、または２種以上を併用することができる。なお、本発明においては、柔軟性の観点からは、水酸基と（メタ）アクリロイル基との間の鎖が長いものが好ましい。 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. Examples of 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. In the present invention, these hydroxyl group-containing (meth) acrylic monomers can be used alone or in combination of two or more. In the present invention, those having a long chain between the hydroxyl group and the (meth) acryloyl group are preferable from the viewpoint of flexibility.
　本発明に用いられる水酸基含有（メタ）アクリルモノマーとしては、例えば、大阪有機化学工業株式会社製の商品名「４－ＨＢＡ」（４－ヒドロキシブチルアクリレート）、商品名「Ｖ＃８０２」、商品名「Ｖ＃３００」や、株式会社ダイセル製の商品名「ＦＭ２Ｄ」、「ＦＡ２Ｄ」などを商業的に入手することができる。 Examples of the hydroxyl group-containing (meth) acrylic monomer used in the present invention 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.
　水酸基含有（メタ）アクリルモノマーの水酸基のモル数［ＯＨ］と、多官能イソシアネートのイソシアネート基のモル数［ＮＣＯ］との比率（［ＯＨ］／［ＮＣＯ］）は、好ましくは０．０５～０．５、さらに好ましくは０．０５～０．４、特に好ましくは０．０５～０．３である。 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.
　本発明のコート層組成物は、更に、触媒を含有することができる。用いられる触媒としては、例えば、ジブチル錫ジラウレート等が挙げられ、東京ファインケミカル株式会社製の商品名「ＯＬ１」を商業的に入手することができる。
　また、必要に応じて、溶媒等を使用して、例えばコート層組成物を溶媒に溶解させる等して、コート層用塗布液を形成することができる。用いられる溶媒としては、例えば、トルエン、メチルエチルケトン、ヘキサン等が挙げられる。 The coating layer composition of the present invention can further contain a catalyst. Examples of the catalyst used include dibutyltin dilaurate, and the trade name “OL1” manufactured by Tokyo Fine Chemical Co., Ltd. can be obtained commercially.
Further, if necessary, 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. Examples of the solvent used include toluene, methyl ethyl ketone, hexane and the like.
　本発明のコート層組成物は、更に、紫外線吸収剤、ヒンダードアミン光安定剤、リン系化合物、フェノール系酸化防止剤などを含有することができる。なお、ここで用いられる紫外線吸収剤、ヒンダードアミン光安定剤、リン系化合物、フェノール系酸化防止剤は、後述する基材の説明において開示するものと同様のものを使用することができる。 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. In addition, the 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.
　本発明の多層シートは、基材およびコート層を有する積層シートであり、基材の少なくとも一方の面にコート層を有する。本発明の多層シートを構成する基材は、少なくとも（メタ）アクリルウレタンポリマーまたはウレタンポリマーを含むものが好ましい。 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.
　なお、本発明において「フィルム」という場合には、シートを含み、「シート」という場合には、フィルムを含む概念とする。 In the present invention, the term “film” includes a sheet, and the term “sheet” includes a film.
　本発明において、基材に用いられるウレタンポリマーとしては、ウレタン単独重合体や共重合体が好ましく使用され、ウレタン単独重合体は、例えば、ポリオールとポリイソシアネートを反応させて得ることができる。本発明に好ましく用いられるウレタンポリマーとしては、例えばアジペート－エステル系熱可塑性ポリウレタン、ポリエーテル系熱可塑性ポリウレタン、ポリカーボネート系熱可塑性ポリウレタン、ポリカプロラクトン－エステル系熱可塑性ポリウレタン等が挙げられる。例えば、アジペート－エステル系熱可塑性ポリウレタン、ポリカプロラクトン－エステル系熱可塑性ポリウレタン等として、日本マタイ株式会社製の製品を商業的に入手することができる。 In the present invention, as the urethane polymer used for the substrate, 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. Examples of 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. For example, products manufactured by Nippon Matai Co., Ltd. can be commercially obtained as adipate-ester thermoplastic polyurethane, polycaprolactone-ester thermoplastic polyurethane, and the like.
　本発明の多層シートを構成する基材は、（メタ）アクリルウレタンポリマーを含有するものであってもよく、例えば、（メタ）アクリルポリマーとウレタンポリマーとを含有する複合フィルムであることができる。 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.
　この複合フィルム中の（メタ）アクリルポリマーとウレタンポリマーとの重量比率は、（メタ）アクリルポリマー／ウレタンポリマー＝１／９９～８０／２０の範囲内であることが好ましい。（メタ）アクリルポリマーの含有比率が１／９９未満では、前駆体混合物の粘度が高くなり、作業性が悪化する場合があり、８０／２０を超えると、フィルムとしての柔軟性や強度が得られない場合がある。 The weight ratio of (meth) acrylic polymer to urethane polymer in this composite film is preferably in the range of (meth) acrylic polymer / urethane polymer = 1/99 to 80/20. When 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. When it exceeds 80/20, flexibility and strength as a film are obtained. There may not be.
　本発明において、（メタ）アクリルポリマーは、少なくとも（メタ）アクリル酸モノマー、および、単官能（メタ）アクリルモノマーを含むアクリル成分を用いてなることが好ましく、特に、ホモポリマーのガラス転移温度（Ｔｇ）が０℃以上の単官能（メタ）アクリルモノマーを用いることが好ましい。さらに、本発明においては、（メタ）アクリルポリマーは、ホモポリマーのガラス転移温度（Ｔｇ）が０℃未満の単官能（メタ）アクリルモノマーをさらに含むアクリル成分を用いてなることが好ましい。 In the present invention, 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. ) Is preferably a monofunctional (meth) acrylic monomer having a temperature of 0 ° C. or higher. Furthermore, in this invention, it is preferable that 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.
　本発明において（メタ）アクリル酸モノマーとは、カルボキシル基を有する（メタ）アクリルモノマーであり、例えば、アクリル酸、メタクリル酸、マレイン酸、クロトン酸等が挙げられる。これらの中では特にアクリル酸が好ましい。この（メタ）アクリル酸モノマーの含有量は、後述する複合フィルム前駆体中、１重量％以上、１５重量％以下であり、２重量％以上、１０重量％以下であることが好ましい。（メタ）アクリル酸モノマーの含有量が１重量％未満では、反応に長時間を要し、フィルム化することが非常に困難であり、また、フィルムの強度が十分でない問題が生じる場合がある。（メタ）アクリル酸モノマーの含有量が１５重量％を超える場合には、フィルムの吸水率が大きくなり、耐水性に問題が生じる場合がある。本発明において（メタ）アクリル酸モノマーはウレタン成分、アクリル成分との相溶性に大きく影響するものであり、極めて重要な機能を有する必須構成要素である。 In the present invention, 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. When the content of the (meth) acrylic acid monomer exceeds 15% by weight, the water absorption rate of the film increases, which may cause a problem in water resistance. In the present invention, 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.
　本発明において（メタ）アクリルポリマー、（メタ）アクリル酸モノマーのように、「（メタ）アクリル」と表示する場合には、メタアクリル、アクリルを総称する概念とする。また、「アクリル」と表示した場合でも、一般常識上問題がなければ、メタアクリルも含む概念とする。 In the present invention, 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.
　本発明において、Ｔｇが０℃以上の単官能（メタ）アクリルモノマーとしては、例えば、アクリロイルモルホリン、イソボルニルアクリレート、ジシクロペンタニルアクリレート、ｔ－ブチルアクリレート、シクロヘキシルアクリレート、ラウリルアクリレート等が挙げられる。これらは単独で、あるいは、２種以上を併用することができる。 In the present invention, 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.
　本発明においては、Ｔｇが０℃以上の単官能（メタ）アクリルモノマーとして、アクリロイルモルホリン、イソボルニルアクリレート、および、ジシクロペンタニルアクリレートからなる群のうち少なくとも１つを用いることが好ましく、アクリロイルモルホリン及び／又はイソボルニルアクリレート、あるいは、アクリロイルモルホリン及び／又はジシクロペンタニルアクリレートを用いることが更に好ましく、特にイソボルニルアクリレートを用いることが好ましい。 In the present invention, it is preferable to use at least one of the group consisting of 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.
　Ｔｇが０℃以上の単官能（メタ）アクリルモノマーの含有量は、アクリル成分中、２０重量％以上、９９重量％以下であることが好ましく、３０重量％以上、９８重量％以下であることが更に好ましい。この単官能（メタ）アクリルモノマーの含有量が２０重量％未満では、フィルムの強度が十分でないという問題が生じることがあり、９９重量％を超えると、フィルムの剛性が高くなりすぎて脆くなる場合がある。 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.
　本発明において、Ｔｇが０℃未満の単官能（メタ）アクリルモノマーとしては、例えば、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸イソオクチル、アクリル酸イソブチル、２－メトキシエチルアクリレート、テトラヒドロフルオロフリルアクリレート、フェノキシエチルアクリレート、エトキシエチルアクリレート、３－メトキシブチルアクリレート等が挙げられる。これらは単独で、あるいは、２種以上を併用することができる。
　本発明においては、Ｔｇが０℃未満の単官能（メタ）アクリルモノマーとして、アクリル酸ｎ－ブチルを用いることが特に好ましい。 In the present invention, 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.
　Ｔｇが０℃未満の単官能（メタ）アクリルモノマーは含有されていなくても良い（含有量が０重量％）が、含有されている場合の含有量は、アクリル成分中、０重量％より多く、５０重量％以下であることが好ましく、０重量％より多く、４５重量％以下であることが更に好ましい。この単官能（メタ）アクリルモノマーの含有量が５０重量％を超える場合には、フィルムの強度が十分でない問題が生じることがある。 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.
　（メタ）アクリルモノマーは、ウレタンとの相溶性、放射線等の光硬化時の重合性や、得られる高分子量体の特性を考慮して、種類、組合せ、使用量等が適宜決定される。 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.
　本発明においては、上記（メタ）アクリルモノマーとともに、酢酸ビニル、プロピオン酸ビニル、スチレン、アクリルアミド、メタクリルアミド、マレイン酸のモノまたはジエステル、及びその誘導体、Ｎ－メチロールアクリルアミド、グリシジルアクリレート、グリシジルメタクリレート、Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルメタクリルアミド、２－ヒドロキシプロピルアクリレート、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、イミドアクリレート、Ｎ－ビニルピロリドン、オリゴエステルアクリレート、ε－カプロラクトンアクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、メトキシ化シクロドデカトリエンアクリレート、メトキシエチルアクリレート等のモノマーを共重合してもよい。なお、これら共重合されるモノマーの種類や使用量は、複合フィルムの特性等を考慮して適宜決定される。 In the present invention, together with the (meth) acrylic monomer, vinyl acetate, vinyl propionate, styrene, acrylamide, methacrylamide, mono- or diester of maleic acid, and derivatives thereof, 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, ε-caprolactone acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxylated cyclododecatriene Acrylate may be copolymerized monomer such as methoxyethyl acrylate. Note that the types and amounts of the monomers to be copolymerized are appropriately determined in consideration of the characteristics of the composite film.
　また、特性を損なわない範囲内で他の多官能モノマーを添加することもできる。多官能モノマーとしては、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート等を挙げることができ、特に好ましくは、トリメチロールプロパントリ（メタ）アクリレートである。 Also, other polyfunctional monomers can be added within a range that does not impair the characteristics. 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.
　多官能モノマーはアクリルモノマー１００重量部に対して、１重量部以上、２０重量部以下含まれることができる。多官能モノマーの含有量が１重量部以上であれば、複合フィルムの凝集力は十分であり、２０重量部以下であれば、弾性率が高くなりすぎることがなく、被着体表面の凹凸に追従することができる。 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.
　ウレタンポリマーは、ジオールとジイソシアネートとを反応させて得られる。ジオールの水酸基とイソシアネートとの反応には、一般的には触媒が用いられるが、本発明によれば、ジブチルチンジラウレート、オクトエ酸錫のような環境負荷が生じる触媒を用いなくても反応を促進させることができる。 Urethane polymer is obtained by reacting diol with diisocyanate. In general, a catalyst is used for the reaction between the hydroxyl group of the diol and the isocyanate. However, according to the present invention, the reaction is promoted without using an environmental load catalyst such as dibutyltin dilaurate or tin octoate. Can be made.
　低分子量のジオールとしては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサメチレングリコール等の２価のアルコールが挙げられる。 Examples of the low molecular weight diol include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol.
　また、高分子量のジオールとしては、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等を付加重合して得られるポリエーテルポリオール、あるいは上述の２価のアルコール、１，４－ブタンジオール、１，６－ヘキサンジオール等のアルコールとアジピン酸、アゼライン酸、セバチン酸等の２価の塩基酸との重縮合物からなるポリエステルポリオールや、アクリルポリオール、カーボネートポリオール、エポキシポリオール、カプロラクトンポリオール等が挙げられる。これらの中では、例えば、ポリオキシテトラメチレングリコール（ＰＴＭＧ）、ポリアルキレンカーボネートジオール（ＰＣＤ）等が好ましく使用される。 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.
　アクリルポリオールとしては水酸基を有するモノマーの共重合体の他、水酸基含有物と（メタ）アクリルモノマーとの共重合体等が挙げられる。エポキシポリオールとしてはアミン変性エポキシ樹脂等がある。 Examples of the acrylic polyol 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. Examples of the epoxy polyol include an amine-modified epoxy resin.
　本発明において、複合フィルムを構成するウレタンポリマーは架橋構造を含まない。ウレタンポリマーの形成に使用されるジオールは、線状（リニア）のジオールであることが好ましい。但し、ウレタンポリマーに架橋構造を形成させないという条件を満たす限りにおいて、ジオールは側鎖状のジオールまたは分岐構造を含むジオールであっても良い。すなわち、本発明の複合フィルムを構成するウレタンポリマーは架橋構造を含まないものであり、したがって、ＩＰＮ構造とは構造的に全く異なるものである。 In the present invention, 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. However, 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.
　本発明においては、上記ジオールを、アクリルモノマーへの溶解性、イソシアネートとの反応性等を考慮して、単独あるいは併用して使用することができる。強度を必要とする場合には、低分子量ジオールによるウレタンハードセグメント量を増加させると効果的である。伸びを重視する場合には、分子量の大きなジオールを単独で使用することが好ましい。また、ポリエーテルポリオールは、一般的に、安価で耐水性が良好であり、ポリエステルポリオールは、強度が高い。本発明においては、用途や目的に応じて、ポリオールの種類や量を自由に選択することができ、また、塗布する基材等の特性、イソシアネートとの反応性、アクリルとの相溶性などの観点からもポリオールの種類、分子量や使用量を適宜選択することができる。 In the present invention, the above diols can be used alone or in combination in consideration of solubility in acrylic monomers, reactivity with isocyanates, and the like. When the strength is required, it is effective to increase the amount of the urethane hard segment by the low molecular weight diol. When importance is attached to elongation, 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. In the present invention, 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.
　ジイソシアネートとしては芳香族、脂肪族、脂環族のジイソシアネート、これらのジイソシアネートの二量体、三量体等が挙げられる。芳香族、脂肪族、脂環族のジイソシアネートとしては、例えば、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、ナフチレンジイソシアネート（ＮＤＩ）、フェニレンジイソシアネート（ＰＰＤＩ）、ｍ－テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）、メチルシクロヘキサンジイソシアネート（水素化ＴＤＩ）、ジシクロヘキシルメタンジイソシアネート（水素化ＭＤＩ）、シクロヘキサンジイソシアネート（水素化ＰＰＤＩ）、ビス（イソシアナートメチル）シクロヘキサン（水素化ＸＤＩ）、ノルボルネンジイソシアネート（ＮＢＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、ブタンジイソシアネート、２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート等が挙げられる。また、これらの二量体、三量体や、ポリフェニルメタンジイソシアネートが用いられる。三量体としては、イソシアヌレート型、ビューレット型、アロファネート型等が挙げられ、適宜、使用することができる。 Examples of the diisocyanate include aromatic, aliphatic and alicyclic diisocyanates, dimers and trimers of these diisocyanates. Examples of 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.
　これらの中では、特に、メチルシクロヘキサンジイソシアネート（水素化ＴＤＩ）、ジシクロヘキシルメタンジイソシアネート（水素化ＭＤＩ）、シクロヘキサンジイソシアネート（水素化ＰＰＤＩ）、ビス（イソシアナートメチル）シクロヘキサン（水素化ＸＤＩ）、ノルボルネンジイソシアネート（ＮＢＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、ブタンジイソシアネート、２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート等の脂肪族、脂環族系のジイソシアネートが好ましく使用される。ベンゼン環を含む芳香族系のジイソシアネートを使用すると、光反応によって共役構造を有する着色物質が生成しやすいため好ましくないからであり、本発明においては、ベンゼン環を含まない、難黄変型、無黄変型の脂肪族、脂環族系のジイソシアネートが好適に使用される。 Among these, in particular, methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexane diisocyanate (hydrogenated PPDI), bis (isocyanatomethyl) cyclohexane (hydrogenated XDI), norbornene diisocyanate (NBDI). ), 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.
　これらのジイソシアネート類は単独あるいは併用で使用することができる。複合フィルムが適用される（塗布等される）支持体等の特性、アクリルモノマーへの溶解性、水酸基との反応性などの観点から、ジイソシアネートの種類、組合せ等を適宜選択すればよい。 These 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.
　本発明においては、ウレタンポリマーが、ヘキサメチレンジイソシアネート（ＨＤＩ）、水添トリレンジイソシアネート（ＨＴＤＩ）、水添４，４－ジフェニルメタンジイソシアネート（ＨＭＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、および、水添キシレンジイソシアネート（ＨＸＤＩ）からなる群から選ばれる少なくとも１種類のジイソシアネートを用いて形成されることが好ましく、水添キシレンジイソシアネートが特に好ましい。 In the present invention, 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.
　本発明において、ウレタンポリマーを形成するためのジオール成分とジイソシアネート成分の使用量は、ＮＣＯ／ＯＨ（当量比）が１．１以上、２．０以下であることが好ましく、１．１２以上、１．６０以下であることがさらに好ましく、１．１５以上、１．４０以下であることが特に好ましい。ＮＣＯ／ＯＨ（当量比）が１．１未満では、ウレタンポリマーの分子量が大きくなりすぎて、複合フィルム前駆体（シロップ溶液）の粘度が大きくなり、後続のシート化工程で作業が困難になることがある。また、ＮＣＯ／ＯＨ（当量比）が２．０を超えると、ウレタンポリマーの分子量が小さくなり、破断強度が低下しやすくなる。 In the present invention, 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. When the 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. Moreover, when NCO / OH (equivalent ratio) exceeds 2.0, the molecular weight of a urethane polymer will become small and break strength will fall easily.
　本発明においては、複合フィルムを形成するアクリル成分とウレタン成分との比率は、重量比で、アクリル成分／ウレタン成分が０．２５以上、４．００以下であり、好ましくは０．４２９以上、２．３３３以下であり、特に好ましくは０．５３８以上、１．８５７以下である。アクリル成分／ウレタン成分が０．２５未満では、シロップ溶液の粘度が大きくなり、後続のシート化工程で作業が困難になることがある。また、アクリル成分／ウレタン成分が４．００を超えると、複合フィルム中のウレタンポリマー量が２５％未満となり、引張の破断強度が低下し、実用に耐えないことがある。 In the present invention, the ratio of the acrylic component and the urethane component forming the composite film is a weight ratio, and 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. When 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. On the other hand, when 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.
　複合フィルムを構成する上記ウレタンポリマーに対し、水酸基含有アクリルモノマーを添加してもよい。水酸基含有アクリルモノマーを添加することにより、ウレタンプレポリマーの分子末端に（メタ）アクリロイル基を導入することができ、（メタ）アクリルモノマーとの共重合性が付与され、ウレタン成分とアクリル成分との相溶性が高まり、破断強度などのＳ－Ｓ特性の向上を図ることもできる。ここで使用される水酸基含有アクリルモノマーとしては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシへキシル（メタ）アクリレート等が用いられる。水酸基含有アクリルモノマーの使用量は、ウレタンポリマー１００重量部に対して、０．１～１０重量部であることが好ましく、更に好ましくは１～５重量部である。 A hydroxyl group-containing acrylic monomer may be added to the urethane polymer constituting the composite film. 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. Examples of 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.
　本発明の粘着シートの各層には、すなわち、基材、表面保護層（コート層）、粘着剤層等には、必要に応じて、通常使用される添加剤、例えば紫外線吸収剤、酸化防止剤、老化防止剤、充填剤、顔料、着色剤、難燃剤、帯電防止剤、光安定剤などを本発明の効果を阻害しない範囲内で添加することができる。これらの添加剤は、その種類に応じて通常の量で用いられる。これらの添加剤は、例えば複合フィルムを形成する場合には、ジイソシアネートとジオールとの重合反応前に、あらかじめ加えておいてもよいし、ウレタンポリマーおよびアクリルモノマーに添加してもよい。 For each layer of the pressure-sensitive adhesive sheet of the present invention, that is, for a substrate, a surface protective layer (coat layer), a pressure-sensitive adhesive layer, etc., 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.
　本発明に用いられる紫外線吸収剤（ＵＶＡ）としては、例えば、ベンゾトリアゾール系紫外線吸収剤として、２－（２－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）－２Ｈ－ベンゾトリアゾール（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　ＰＳ」）、ベンゼンプロパン酸と３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－（１，１－ジメチルエチル）－４－ヒドロキシ（Ｃ７～Ｃ９の側鎖および直鎖アルキル）とのエステル化合物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　３８４－２」）、オクチル－３－［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）フェニル］プロピオネートと２－エチルヘキシル－３－［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）フェニル］プロピオネートとの混合物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　１０９」）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　９００」）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　９２８」）、メチル－３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート／ポリエチレングリコール３００の反応生成物（例えば、チバ・ジャパン社製のＴＩＮＵＶＩＮ　１１３０」）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－クレゾール（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　Ｐ」）、２－［５－クロロ（２Ｈ）－ベンゾトリアゾール－２－イル］－４－メチル－６－（ｔｅｒｔ－ブチル）フェノール（例えば、チバ・ジャパン社製のＴＩＮＵＶＩＮ　３２６」）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノール（例えば、チバ・ジャパン社製のＴＩＮＵＶＩＮ　３２８」）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール（例えば、チバ・ジャパン社製のＴＩＮＵＶＩＮ　３２９」）、２－２’－メチレンビス［６－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール］（例えば、チバ・ジャパン社製のＴＩＮＵＶＩＮ　３６０」）、メチル－３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネートとポリエチレングリコール３００との反応生成物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　２１３」）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　５７１」）、２－［２－ヒドロキシ－３－（３，４，５，６－テトラヒドロフタルイミド－メチル）－５－メチルフェニル］ベンゾトリアゾール（例えば、住友化学社製の「Sumisorb　２５０」）、２，２’－メチレンビス［６－（ベンゾトリアゾール－２－イル）－４－ｔｅｒｔ－オクチルフェノール］（例えば、ＡＤＥＫＡ製の「ＡＤＫＳＴＡＢ　ＬＡ３１」）等が挙げられる。 Examples of the ultraviolet absorber (UVA) used in the present invention 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 (eg, “TINUVIN 384-2” manufactured by Ciba Japan), 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 Japan), 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1- Phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (eg, “TINUVIN 928” manufactured by Ciba Japan), methyl-3- (3- (2H-benzotriazole-2- Yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (eg, TINUVIN 1130 "manufactured by Ba Japan Co., Ltd.), 2- (2H-benzotriazol-2-yl) -p-cresol (for example," TINUVIN P "manufactured by Ciba Japan Co., Ltd.), 2- [5-chloro (2H ) -Benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (eg, TINUVIN 326 manufactured by Ciba Japan), 2- (2H-benzotriazol-2-yl) -4 , 6-Di-tert-pentylphenol (eg, TINUVIN 328 manufactured by Ciba Japan), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl ) Phenol (eg, TINUVIN 329 manufactured by Ciba Japan), 2-2'-methylenebis [6- (2H-benzotriazole 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (for example, TINUVIN 360 "manufactured by Ciba Japan), methyl-3- (3- (2H-benzotriazole-2) -Il) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 reaction product (eg, “TINUVIN 213” manufactured by Ciba Japan), 2- (2H-benzotriazole-2- Yl) -6-dodecyl-4-methylphenol (for example, “TINUVIN 571” manufactured by Ciba Japan), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl)- 5-methylphenyl] benzotriazole (for example, “Sumisorb 250” manufactured by Sumitomo Chemical Co., Ltd.), 2,2′-methylenebis [ - (benzotriazol-2-yl) -4-tert-octylphenol] (e.g., ADEKA made of "ADKSTAB LA31"), and the like.
　また、ヒドロキシフェニルトリアジン系紫外線吸収剤としては、例えば、２－（４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル）－５－ヒドロキシフェニルと［（Ｃ１０～Ｃ１６、主としてＣ１２～Ｃ１３のアルキルオキシ）メチル］オキシランとの反応生成物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　４００」）、２－（２，４－ジヒドロキシフェニル）－４，６－ビス－（２，４－ジメチルフェニル）－１，３，５－トリアジンと（２－エチルヘキシル）－グリシド酸エステルとの反応生成物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　４０５」）、２，４－ビス［２－ヒドロキシ－4－ブトキシフェニル］－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　４６０」）、２－(４，６－ジフェニル－１，３，５－トリアジン－２－イル)－５－[（ヘキシル）オキシ]－フェノール（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　１５７７」）、２－（２－ヒドロキシ－４－[１－オクチルオキシカルボニルエトキシ]フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジン（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　４７９」）等が挙げられる。 Examples of the hydroxyphenyl triazine-based ultraviolet absorber 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-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (for example, Ciba “TINUVIN 1577” manufactured by Japan, Inc.), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (For example, “TINUVIN 479” manufactured by Ciba Japan).
　ベンゾフェノン系紫外線吸収剤として、例えば、チバ・ジャパン社製の「ＣＨＩＭＡＳＳＯＲＢ　８１」等が挙げられる。また、ベンゾエート系紫外線吸収剤としては、例えば、２，４－ジ－tert－ブチルフェニル－３，５－ジ－tert－ブチル－４－ヒドロキシベンゾエート（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　１２０」）等が挙げられる。 Examples of the benzophenone ultraviolet absorber include “CHIMASORB 81” manufactured by Ciba Japan. Examples of the benzoate UV absorber 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.
　本発明においては、上記紫外線吸収剤を単独で、あるいは、２種類以上を併用して用いることができる。 In the present invention, the above ultraviolet absorber can be used alone or in combination of two or more.
　紫外線吸収剤の総使用量は、各層を形成するための組成物１００重量％に対して、例えば複合フィルムの場合にはフィルム前駆体１００重量％に対して、０．１重量％以上、４．０重量％以下であることが好ましく、０．５重量％以上、２．０重量％以下であることが更に好ましい。紫外線吸収剤の含有量が０．１重量％以上であれば、劣化や着色を引き起こす紫外光の吸収が十分であり、４．０重量％以下であれば、紫外線吸収剤自体による着色を引き起こすことはない。 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.
　本発明に用いられる光安定剤としては、ヒンダードアミン光安定剤（ＨＡＬＳ）であることが好ましい。本発明に用いられるヒンダードアミン光安定剤としては、例えば、コハク酸ジメチルと４－ヒドロキシ－２，２，６，６－テトラメチル－１－ピペリジンエタノールとの重合物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　６２２」）、コハク酸ジメチルと４－ヒドロキシ－２，２，６，６－テトラメチル－１－ピペリジンエタノールとの重合物とＮ，Ｎ’，Ｎ’’，Ｎ’’’－テトラキス－（４，６－ビス－（ブチル－（Ｎ－メチル－２，２，６，６－テトラメチルピペリジン－４－イル）アミノ）－トリアジン－２－イル）－４，７－ジアザデカン－１，１０－ジアミンとの１対１の反応生成物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　１１９」）、ジブチルアミン・１，３－トリアジン・Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジル－１，６－ヘキサメチレンジアミンとＮ－（２，２，６，６－テトラメチル－４－ピペリジル）ブチルアミンとの重縮合物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　２０２０」）、ポリ[{６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル}{２，２，６，６－テトラメチル－４－ピペリジル}イミノ]ヘキサメチレン{（２，６，６－テトラメチル－４－ピペリジル）イミノ}）（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　９４４」）、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケートとメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセバケートとの混合物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　７６５」）、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　７７０」）、デカン二酸ビス（２，２，６，６－テトラメチル－１－（オクチルオキシ）－４－ピペリジニル）エステル（１，１－ジメチルエチルヒドロペルオキシド）とオクタンとの反応生成物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　１２３」）、ビス(１，２，２，６，６－ペンタメチル－４－ピペ
リジル)[[３，５－ビス(１，１－ジメチルエチル)－４－ヒドロキシフェニル]メチル]ブチルマロネート（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　１４４」）、シクロヘキサンと過酸化Ｎ－ブチル－２，２，６，６－テトラメチル－４－ピペリジンアミン－２，４，６－トリクロロ－１，３，５－トリアジンとの反応生成物と２－アミノエタノールとの反応生成物（例えば、チバ・ジャパン社製の「ＴＩＮＵＶＩＮ　１５２」）、ビス(１，２，２，６，６－ペンタメチル－４－ピペリジル)セバケートとメチル－１，２，２，６，６－ペンタメチル－４－ピペリジルセバケートとの混合物（例えば、チバ・ジャパン社製「ＴＩＮＵＶＩＮ　２９２」）等が挙げられる。 The light stabilizer used in the present invention is preferably a hindered amine light stabilizer (HALS). 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- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {2,2,6,6-tetramethyl-4 -Piperidyl} imino] hexamethylene {(2,6,6-tetramethyl-4-piperidyl) imino}) (for example, “TINUVIN 944” manufactured by Ciba Japan), bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (for example, “TINUVIN 765” manufactured by Ciba Japan), (2,2,6,6-tetramethyl-4-piperidyl) sebacate (eg, “TINUVIN 770” manufactured by Ciba Japan), bis (2,2,6,6-tetramethyl-1) decanedioate Reaction product of-(octyloxy) -4-piperidinyl) ester (1,1-dimethylethyl hydroperoxide) and octane (for example, “TINUVIN 123” manufactured by Ciba Japan), bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (for example, “TINUVIN 144” manufactured by Ciba Japan) ), Cyclohexane and peroxide N-butyl-2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-tria Reaction product of 2-aminoethanol (for example, “TINUVIN 152” manufactured by Ciba Japan), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate And methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate (for example, “TINUVIN 292” manufactured by Ciba Japan).
　一般に、ウレタンポリマーでは、暗所における耐熱性や耐湿熱性が問題であり、共役構造を示す着色物質や窒素含有の着色物質が生成することが知られている。特開平９－１３０７０１６号公報および特許２６２５５０８号公報には、そのような現象を防止する目的で、フェノール系やリン系化合物、あるいは、ヒンダードアミン系光安定剤、ベンゾトリアゾール系紫外線吸収剤などが、単独、あるいは併用するなどして効果があることが知られている。 In general, it is known that 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.
　本発明に用いられるリン系化合物としては、特に限定はされないが、例えば、下記式で表される三置換ホスファイト化合物であることが望ましい。 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.
Figure JPOXMLDOC01-appb-C000004
  
 
Figure JPOXMLDOC01-appb-C000004
  
 
　上記式中、Ｒ１、Ｒ２およびＲ３は同一でも異なっていても良く、炭素原子数が１～１８の、芳香族もしくは芳香族脂肪族基、または必要に応じてエーテル基を有する直鎖もしくは分枝鎖の脂肪族基を示すか、あるいは、Ｒ１およびＲ２はリン原子および２個の酸素原子と一緒になって５員もしくは６員の複素環を形成している。ただし置換基Ｒ１、Ｒ２およびＲ３の少なくとも１つは、炭素原子数が６～１８の芳香族基または炭素原子数が９～１８の直鎖もしくは分枝鎖の脂肪族基を示す。 In the above formula, 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.
　具体的には、例えば、トリフェニルホスファイトもしくはトリス（ノニルフェニル）ホスファイトのようなアリールホスファイト；ジフェニルイソオクチルホスファイト、ジフェニルイソデシルホスファイト、ジイソデシルフェニルホスファイト、ジイソオクチルオクチルフェニルホスファイト、フェニルネオペンチルグリコールホスファイトもしくは２，４，６－トリ－ｔ－ブチルフェニル－（２－ブチル－２－エチル－１，３－プロパンジオール）ホスファイトのようなアルキル－アリールホスファイト；トリイソデシルホスファイト、トリラウリルホスファイトもしくはトリス（トリデシル）ホスファイトのようなアルキルホスファイト；ジイソデシルペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔ－ブチルフェニル）ペンタエリスリトールジホスファイトもしくはテトラフェニルジプロピレングリコールジホスファイトのような芳香族もしくは脂肪族置換のジホスファイト、などが挙げられる。 Specifically, 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 pentaerythritol diphosphite, distearyl pentaerythritol diphos Phosphite, bis (2,4-di -t- butyl-phenyl) pentaerythritol diphosphite or aromatic, such as tetraphenyl dipropylene glycol diphosphite or aliphatic substituted diphosphite, and the like.
　これらの中では、黄変の抑制効果の点で、トリイソデシルホスファイト、フェニルジイソデシルホスファイトおよびジフェニルイソデシルホスファイトが好適であり、これらの混合物を用いることが特に好適である。なお、トリイソデシルホスファイトの構造、フェニルジイソデシルホスファイトの構造、ジフェニルイソデシルホスファイトの構造、トリフェニルホスファイトの構造を下記に示す。 Among these, 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.
Figure JPOXMLDOC01-appb-C000005
  
 
Figure JPOXMLDOC01-appb-C000005
  
 
Figure JPOXMLDOC01-appb-C000006
  
 
Figure JPOXMLDOC01-appb-C000006
  
 
Figure JPOXMLDOC01-appb-C000007
  
 
Figure JPOXMLDOC01-appb-C000007
  
 
Figure JPOXMLDOC01-appb-C000008
  
 
Figure JPOXMLDOC01-appb-C000008
  
 
　本発明に用いられるフェノール系化合物としては、例えば、嵩高い置換基（例えばｔ－ブチル基、ｓｅｃ－ブチル基、ネオペンチル基など）を持つフェノール骨格を有する化合物であり、例えば下記式で表される化合物や、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、　Ｎ，Ｎ’－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオンアミド）、　ヘキサメチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、　ベンゼンプロパン酸３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシイソオクチルエステル、　ジエチル［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ホスフォネート、　２，４－ジメチル－６－（１－メチルペンタデシル）フェノール、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール（ＩＲＧＡＮＯＸ１５２０Ｌ）などを挙げることができる。 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. Compounds, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di- tert-butyl-4-hydroxyphenylpropionamide), hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], benzenepropanoic acid 3,5-bis (1,1- Dimethylethyl) -4-hydroxyisooctyl ester, diethyl [[3,5-bis (1,1-dimethylethyl -4-hydroxyphenyl] methyl] phosphonate, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, 4,6-bis (octylthiomethyl) -o-cresol (IRGANOX1520L), etc. .
Figure JPOXMLDOC01-appb-C000009
  
 
Figure JPOXMLDOC01-appb-C000009
  
 
　上記フェノール系化合物は市販品として入手可能であり、例えばIrganox1010、Irganox1010FF、Irganox1035、Irganox1035FF、Irganox1076、Irganox1076FD、Irganox1076DWJ、Irganox1098、Irganox1135、Irganox1330、Irganox1726、Irganox1425WL、Irganox1520L、Irganox245、Irganox245FF、Irganox245DWJ、Irganox259、Irganox3114、Irganox5057、Irganox565、Irganox565DD、Irganox295、Irganox1222、Irganox1141（以上、チバ・ジャパン社製）などを挙げることができる。なお、上記式で表されるフェノール系化合物は、市販品として例えば「Irganox1135」（チバ・ジャパン社製）を入手することができる。 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. In addition, the phenol type compound represented by the said formula can obtain "Irganox1135" (made by Ciba Japan) as a commercial item, for example.
　本発明においては、塗工の粘度調整のため少量の溶剤を加えてもよい。溶剤としては、通常使用される溶剤の中から適宜選択することができるが、例えば、酢酸エチル、トルエン、クロロホルム、ジメチルホルムアミド等が挙げられる。 In the present invention, 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.
　本発明において複合フィルムを形成する場合には、例えば、アクリルモノマーを希釈剤として、このアクリル系モノマー中でジオールとジイソシアネートとの反応を行ってウレタンポリマーを形成し、アクリルモノマーとウレタンポリマーとを主成分として含む混合物を支持体（必要に応じて剥離処理されている）等の上に塗布し、光重合開始剤の種類等に応じて、α線、β線、γ線、中性子線、電子線等の電離性放射線や紫外線等の放射線、可視光等を照射して硬化させ、その後、支持体等を剥離除去することにより、複合フィルムを形成することができる。あるいは、支持体等を剥離除去せずに、支持体等の上に複合フィルムが積層された形態で得ることもできる。 In the case of forming a composite film in the present invention, for example, 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. The mixture containing the components is applied onto a support (exfoliated if necessary), etc., and depending on the type of photopolymerization initiator, α rays, β rays, γ rays, neutron rays, electron beams 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 | stacked on the support body etc., without peeling and removing a support body etc.
　具体的には、ジオールをアクリルモノマーに溶解させた後、ジイソシアネート等を添加してジオールと反応させて粘度調整を行い、これを支持体等に、あるいは、必要に応じて支持体等の剥離処理面に塗工した後、低圧水銀ランプ等を用いて硬化させることにより、複合フィルムを得ることができる。この方法では、アクリルモノマーをウレタン合成中に一度に添加してもよいし、何回かに分割して添加してもよい。また、ジイソシアネートをアクリルモノマーに溶解させた後、ジオールを反応させてもよい。この方法によれば、分子量が限定されるということはなく、高分子量のポリウレタンを生成することもできるので、最終的に得られるウレタンの分子量を任意の大きさに設計することができる。 Specifically, after dissolving the diol in the acrylic monomer, diisocyanate or the like is added and reacted with the diol to adjust the viscosity, and this is applied to the support or the like, or if necessary, the release treatment of the support or the like After coating on the surface, the composite film can be obtained by curing using a low-pressure mercury lamp or the like. In this method, the acrylic monomer may be added at a time during urethane synthesis, or may be added in several divided portions. Further, after the diisocyanate is dissolved in the acrylic monomer, the diol may be reacted. According to this method, 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.
　この際、酸素による重合阻害を避けるために、基板シート等の上に塗布した混合物の上に、剥離処理したシート（セパレータ等）をのせて酸素を遮断してもよいし、不活性ガスを充填した容器内に基材を入れて、酸素濃度を下げてもよい。 At this time, in order to avoid polymerization inhibition due to oxygen, 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.
　本発明において、放射線等の種類や照射に使用されるランプの種類等は適宜選択することができ、蛍光ケミカルランプ、ブラックライト、殺菌ランプ等の低圧ランプや、メタルハライドランプ、高圧水銀ランプ等の高圧ランプ等を用いることができる。 In the present invention, 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 lamp or the like can be used.
　紫外線などの照射量は、要求されるフィルムの特性に応じて、任意に設定することができる。一般的には、紫外線の照射量は、１００～５，０００ｍＪ／ｃｍ２、好ましくは１，０００～４，０００ｍＪ／ｃｍ２、更に好ましくは２，０００～３，０００ｍＪ／ｃｍ２である。紫外線の照射量が１００ｍＪ／ｃｍ２より少ないと、十分な重合率が得られないことがあり、５，０００ｍＪ／ｃｍ２より多いと、劣化の原因となることがある。 Irradiation amounts such as ultraviolet rays can be arbitrarily set according to required film characteristics. In general, 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 . When 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.
　また、紫外線等を照射する際の温度については特に限定があるわけではなく任意に設定することができるが、温度が高すぎると重合熱による停止反応が起こり易くなり、特性低下の原因となりやすいので、通常は７０℃以下であり、好ましくは５０℃以下であり、更に好ましくは３０℃以下である。 In addition, 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.
　複合フィルムを形成する場合、ウレタンポリマーとアクリルモノマーとを主成分とする混合物には、光重合開始剤が含まれる。光重合開始剤としては、特に制限なく使用することができるが、例えば、ケタール系光重合開始剤、α－ヒドロキシケトン系光重合開始剤、α－アミノケトン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤、ベゾフェノン系光重合開始剤、チオキサントン系光重合開始剤、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤等を用いることができる。 In the case of forming a composite film, 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, α-hydroxyketone photopolymerization initiators, α-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.
　ケタール系光重合開始剤としては、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商業的に入手可能なものとしては、チバ・スペシャリティ・ケミカルズ社製の「イルガキュア６５１」等）等が挙げられる。 Examples of ketal photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, “Irgacure 651” manufactured by Ciba Specialty Chemicals, Inc. Etc.).
　α－ヒドロキシケトン系光重合開始剤としては、例えば、１－ヒドロキシシクロヘキシルフェニルケトン（商業的に入手可能なものとしては、チバ・ジャパン社製の「イルガキュア１８４」等）、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン（商業的に入手可能なものとしては、チバ・ジャパン社製の「ダロキュア１１７３」等）、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（商業的に入手可能なものとしては、チバ・ジャパン社製の「イルガキュア２９５９」等）等が挙げられる。 Examples of the α-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.
　α－アミノケトン系光重合開始剤としては、例えば、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン（商業的に入手可能なものとしては、チバ・ジャパン社製の「イルガキュア９０７」等）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（商業的に入手可能なものとしては、チバ・ジャパン社製の「イルガキュア３６９」等）等が挙げられる。 As the α-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.).
　アシルホスフィンオキサイド系光重合開始剤としては、例えば、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド（商業的に入手可能なものとしては、ＢＡＳＦ社製の「ルシリンＴＰＯ」等）等が挙げられる。 Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, “Lucirin TPO” manufactured by BASF Corporation).
　ベンゾインエーテル系光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、アニソールメチルエーテル等が挙げられる。 Examples of the benzoin ether photopolymerization initiator 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.
　アセトフェノン系光重合開始剤としては、例えば、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、４－フェノキシジクロロアセトフェノン、４－（ｔ－ブチル）ジクロロアセトフェノン等が挙げられる。 Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone.
　芳香族スルホニルクロリド系光重合開始剤としては、例えば、２－ナフタレンスルホニルクロライド等が挙げられ、光活性オキシム系光重合開始剤としては、例えば、１－フェニル－１，１－プロパンジオン－２－（ｏ－エトキシカルボニル）－オキシム等が挙げられる。 Examples of the aromatic sulfonyl chloride photopolymerization initiator 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.
　ベンゾイン系光重合開始剤としては、例えば、ベンゾイン等が挙げられ、ベンジル系光重合開始剤としては、例えば、ベンジル等が挙げられる。 Examples of the benzoin photopolymerization initiator include benzoin, and examples of the benzyl photopolymerization initiator include benzyl.
　ベンゾフェノン系光重合開始剤としては、例えば、ベンゾフェノン、ベンゾイル安息香酸、３，３’－ジメチル－４－メトキシベンゾフェノン、ポリビニルベンゾフェノン、α－ヒドロキシシクロヘキシルフェニルケトン等が挙げられる。 Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like.
　チオキサントン系光重合開始剤としては、例えば、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントン等が挙げられる。 Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
　本発明においては、塗工の粘度調整のため少量の溶剤を加えてもよい。溶剤としては、通常使用される溶剤の中から適宜選択することができるが、例えば、酢酸エチル、トルエン、クロロホルム、ジメチルホルムアミド等が挙げられる。 In the present invention, 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.
　本発明の多層シートを構成するコート層の厚みは、２～５０μｍであることが好ましく、より好ましくは５～４０μｍであり、更に好ましくは８～３０μｍである。コート層の厚みが２μｍ未満では、ピンホールなど、コート層が形成されない欠陥部位が発生しやすく、またコート層の特性が充分に発揮できない場合がある。また５０μｍを超えると、コート層の物性が多層シートの物性を低下させてしまう場合がある。 The thickness of the coating layer constituting the multilayer sheet of the present invention is preferably 2 to 50 μm, more preferably 5 to 40 μm, still more preferably 8 to 30 μm. When the thickness of the coat layer is less than 2 μm, 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. On the other hand, if it exceeds 50 μm, the physical properties of the coating layer may deteriorate the physical properties of the multilayer sheet.
　本発明の多層シートを構成する基材の厚みは、目的等に応じて、例えば被覆保護する対象物の種類や箇所等に応じて適宜選択することができ、特に限定されないが、１００μｍ以上であることが好ましく、１５０μｍ以上であることが更に好ましく、２００μｍ以上であることが特に好ましい。また、厚みの上限値は１ｍｍ程度であることが好ましい。基材を構成するフィルム等の厚みは、例えば、自動車のボディーを保護するために用いられるチッピング用途の場合には、５０～８００μｍ程度であることが好ましく、更に好ましくは１００～６００μｍ程度であることが好ましい。また、航空機用途の場合には、５０～１，０００μｍ程度、更に好ましくは２００～８００μｍ程度である。また、自動二輪用途の場合には、好ましくは５０～８００μｍ程度、更に好ましくは１００～６００μｍ程度である。 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 μm or more. It is preferably 150 μm or more, more preferably 200 μm 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 μm, and more preferably about 100 to 600 μm, 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 μm, more preferably about 200 to 800 μm. In the case of a motorcycle, it is preferably about 50 to 800 μm, more preferably about 100 to 600 μm.
　本発明においては、コート層を形成する塗布液を基材表面上に塗工した状態で熱硬化させ、皮膜形成することが好ましい。このような状態で熱硬化させることにより優れた密着性を実現することができるので、コート層は基材に対して優れた密着性を長期間保持し続けることができる。したがって、粘着シートの位置決めのためにアプリケーションシートが塗膜面上に貼付されたとしても、アプリケーションシートの剥離の際にコート層が剥がれたりすることがない。 In the present invention, 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.
　あるいは、コート層を構成する成分と基材を構成する成分とが結合して架橋点を形成することによりコート層が基材と架橋されていて架橋点を有する構造でもよい。例えば、基材がウレタン－アクリル複合フィルムである場合、コート層の形成に使用したイソシアネートに残存イソシアネート基が存在していれば、この残存イソシアネート基が、ウレタンポリマー－アクリルモノマー混合物の水酸基と反応して架橋点を形成することができる。あるいは、コート層の形成に使用されるフルオロエチレンビニルエーテル交互共重合体の水酸基が残存しているならば、複合フィルム用塗布液に存在しているイソシアネート基と反応して架橋点を形成することができる。したがって、この場合には、複合フィルム用塗布液を塗布した時に、コート層には残存イソシアネート基あるいは残存水酸基が反応しうる状態で存在していることが好ましい。また、コート層の架橋反応が完全に完了する前に複合フィルム用塗布液を塗布することが好ましい。但し、このようにしてコート層と複合フィルムとの間に架橋点を形成するためには、コート層の形成に使用されるコート層組成物は、更に水酸基含有（メタ）アクリルモノマーを含有することが必要である。 Alternatively, 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. For example, when the substrate is a urethane-acrylic composite film, if there is a residual isocyanate group in the isocyanate used to form the coat layer, this residual isocyanate group reacts with the hydroxyl group of the urethane polymer-acrylic monomer mixture. Thus, a crosslinking point can be formed. Alternatively, if 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. However, in order to form a crosslinking point between the coat layer and the composite film in this way, the coat layer composition used for forming the coat layer further contains a hydroxyl group-containing (meth) acrylic monomer. is required.
　上記したようにコート層と基材とが架橋構造を形成していれば優れた接着性を発揮することができるので、コート層は基材に対して優れた密着性を長期間保持し続けることができる。したがって、この場合でも、粘着シートの位置決めのためにアプリケーションシートが塗膜面上に貼付されたとしても、アプリケーションシートの剥離の際にコート層が剥がれたりすることがない。 As described above, if 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.
　例えば、コート層を塗布、乾燥、硬化させた後、コート層表面が半硬化状態で複合フィルム用塗布液を塗布して架橋点を形成したり、あるいは、完全に表面が硬化した状態でも残存イソシアネート基が反応しうる状態であれば、この上に複合フィルム用塗布液を塗布して架橋点を形成することができる。コート層および複合フィルムの形成に使用される成分の種類や使用量等を考慮して適宜設計されることが好ましい。例えば、残存イソシアネート基が反応しうる状態であれば、２４時間以内に複合フィルム用塗布液を塗布して光硬化反応させることにより架橋構造を形成することができる。また、残存イソシアネート基が反応しうる状態であって、５℃程度で保存されていれば、５日間以内に複合フィルム用塗布液を塗布して光硬化反応させることにより架橋構造を形成することができる。なお、イソシアネート架橋剤に、予め水酸基含有モノマーを反応させておけば、５０℃で１週間以上保存した後でも残存イソシアネート基が反応しうる状態にすることができる。 For example, after the coating layer is applied, dried and cured, 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. If the group can react, 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. In addition, if the remaining isocyanate group can react and is stored at about 5 ° C., 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.
　本発明においては、多官能イソシアネートと水酸基含有（メタ）アクリルモノマーとを反応させた反応液に、フルオロエチレンビニルエーテル交互共重合体とポリオールとを必要に応じて溶媒に溶解させて添加することによりコート層用塗布液を形成し、この溶液を用いてコート層を形成することができる。例えば、剥離処理されたポリエチレンテレフタレートフィルム上にこの溶液を塗布し、乾燥させてコート層を形成する。このコート層の上に、ウレタンポリマーおよびアクリル系モノマーを含有する混合物（複合フィルム用塗布液）を塗布し、紫外線等を照射して硬化させることにより、コート層が複合フィルムに架橋された（複合フィルムがコート層に架橋された）構造の積層体（多層シート）を得ることができる。 In the present invention, 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. For example, this solution is applied onto a polyethylene terephthalate film that has been subjected to a release treatment, and dried to form a coat layer. On this coating layer, a mixture containing a urethane polymer and an acrylic monomer (coating solution for composite film) was applied and cured by irradiating with ultraviolet rays or the like to crosslink the coating layer to the composite film (composite). A laminate (multilayer sheet) having a structure in which the film is crosslinked to the coat layer can be obtained.
　本発明において多層シートは、本発明の効果を損なわない範囲内で、基材の片面（コート層を設けない側の面）に他のフィルムを積層することができる。他のフィルムを形成する材料としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル樹脂、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂、ポリイミド（ＰＩ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニリデン樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリスチレン樹脂、アクリル樹脂、フッ素樹脂、セルロース樹脂、ポリカーボネート樹脂等のような熱可塑性樹脂のほか、熱硬化性樹脂等が挙げられる。 In the present invention, 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. Examples of other 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 In addition to 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.
　本発明の粘着シートは、基材の一方の面にコート層を有し、他方の面に粘着剤層を有する構成であることが好ましい。 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.
　この粘着剤層を形成する粘着剤は、特に限定されず、アクリル系、ゴム系、シリコン系等、一般的なものを使用することができるが、低温での接着性や高温での保持性、コスト面等を考慮するとアクリル系の粘着剤が好ましい。 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.
　アクリル系粘着剤としては、アクリル酸エステルを主体とするモノマー成分に、カルボキシル基やヒドロキシル基等の官能基を有するモノマー成分を共重合したアクリル系共重合体（２種類以上であっても良い）を含むアクリル系粘着剤を用いることができる。 As 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.
　アクリル酸エステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、ｎ－オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、２－エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ドデシル(メタ)アクリレート、トリデシル(メタ)アクリレート、テトラデシル(メタ)アクリレート、ペンタデシル(メタ)アクリレート、ヘキサデシル(メタ)アクリレート、ヘプタデシル(メタ)アクリレート、オクタデシル(メタ)アクリレート、ノナデシル(メタ)アクリレート、エイコシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、１－アダマンチル(メタ)アクリレート等が挙げられる。これらのアルキル（メタ）アクリレートは１種または２種以上を用いることができる。 Examples of 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) acrylate, isodecyl (meth) acrylate, Decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl ( And (meth) acrylate, eicosyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and the like. These alkyl (meth) acrylates can be used alone or in combination of two or more.
　上記アルキル（メタ）アクリレートに下記モノマー成分を共重合することができる。共重合可能なモノマー成分としては、例えば、（メタ）アクリル酸、イタコン酸、マレイン酸、クロトン酸、フマル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート等のカルボキシル基を含有するモノマー；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシへキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、（４－ヒドロキシメチルシクロヘキシル）－メチルアクリレート等のヒドロキシル基含有モノマー；グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート等のグリシジル基含有モノマー；アクリロニトリル、メタアクリロニトリル等のシアノアクリレート系モノマー；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、Ｎ－ビニル－２－ピペリドン、Ｎ－ビニル－３－モルホリノン、Ｎ－ビニル－２－カプロラクタム、Ｎ－ビニル－２－ピロリドン、Ｎ－ビニル－１，３－オキサジン－２－オン、Ｎ－ビニル－３，５－モルホリンジオン、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－アクリロイルピロリジン、ｔ－ブチルアミノエチル（メタ）アクリレート等の含窒素モノマー、スチレンやスチレンの誘導体、酢酸ビニル等のモノマー等が挙げられる。これらのモノマーを必要に応じて、１種又は２種以上を、（メタ）アクリル酸エステルに共重合させて使用することができる。 The following monomer components can be copolymerized with the above alkyl (meth) acrylate. Examples of 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. ; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate Hydroxyl group-containing monomers such as octyl, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) -methyl acrylate; glycidyl (meth) acrylate, methyl glycidyl (meth) Acry Glycidyl group-containing monomers such as acrylate; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl ( (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine, N-vinyl-2-piperidone, N-vinyl-3 -Morpholinone, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-cyclohexylmaleimide, N -Phenylmaleimide, N-a Leroy pyrrolidine, t- butyl aminoethyl (meth) nitrogen-containing monomers such as acrylates, styrene derivatives and styrene, monomers such as vinyl acetate and the like. One or more of these monomers can be used by copolymerizing with (meth) acrylic acid ester as required.
　本発明に用いられる粘着剤は、アクリル酸２－エチルヘキシルおよびアクリル酸イソノニルからなる群から選ばれる少なくとも１種類と、アクリル酸およびメタクリル酸からなる群から選ばれる少なくとも１種類のカルボキシル基含有モノマーとを含むことが好ましい。すなわち、本発明に用いられる粘着剤は、アクリル酸２－エチルヘキシル、アクリル酸イソノニル等を主モノマーとし、アクリル酸、メタクリル酸等のカルボキシル基含有モノマーを共重合した共重合体を使用することができる。 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. .
　粘着剤層の厚みについては、特に限定があるわけではなく任意に設定することができるが、通常は２０μｍ以上であることが好ましく、更に好ましくは３０μｍ以上、特に好ましくは４０μｍ以上である。但し、上限値は通常１００μｍ程度であることが好ましい。 The thickness of the pressure-sensitive adhesive layer is not particularly limited and can be arbitrarily set, but is usually preferably 20 μm or more, more preferably 30 μm or more, and particularly preferably 40 μm or more. However, the upper limit is usually preferably about 100 μm.
　本発明において、粘着剤層は、例えば、基材に、溶剤系、エマルジョン系の粘着剤を直接塗布し、乾燥する方法、これらの粘着剤を剥離紙に塗布し、予め粘着剤層を形成しておき、この粘着剤層を基材等に貼り合わせる方法等を適用することができる。放射線硬化型粘着剤を基材に塗布し、粘着剤層と、フィルムの両方に放射線を照射することにより、基材と粘着剤層を同時に硬化させて、形成する方法も適用することができる。 In the present invention, 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. In addition, 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.
　本発明の粘着シートは優れた表面滑り性を有する。表面滑り性は、例えば静摩擦係数の数値によって評価することができる。静摩擦係数は、ＪＩＳＫ７１２５に準じて最表面層の静摩擦係数を測定することにより求める。すなわち、所定サイズの粘着シートを標準試験板の上に固定し、粘着シートの上に滑り片を載せ、法線力（均一な圧力分布）をかけつつ滑り片を引っ張り、最大荷重を測定し、下記算出式を用いて静摩擦係数を求める。
　　　μ＝Ｆｓ／Ｆｐ
　（μ：静摩擦係数、Ｆｓ：静摩擦力（Ｎ）、Ｆｐ：法線力）
 
　本発明において、静摩擦係数は、１．５０以下であることが好ましく、１．００以下であることが更に好ましい。 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.
μ = Fs / Fp
(Μ: static friction coefficient, Fs: static friction force (N), Fp: normal force)

In the present invention, the static friction coefficient is preferably 1.50 or less, and more preferably 1.00 or less.
　本発明の粘着シートは、破断伸びが１５０％以上であり、２００％以上、１，０００％以下であることが好ましく、更に好ましくは２５０％以上、８００％以下であり、特に好ましくは３００％以上、６００％以下である。破断伸びが２００％以上であれば、貼付時に粘着シートが十分に伸びるので貼り付け作業が低下することがない。また、破断伸びが１，０００％以下であれば、貼付時に粘着シートが伸びすぎて貼り付け作業が低下することがない。 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.
　ここで破断伸びとは、粘着シート（幅１ｃｍ、長さ１３ｃｍ）を引張速度２００ｍｍ／ｍｉｎ、チャック間距離５０ｍｍ、室温（２３℃）で引張試験を行い、粘着シートが破断した時の伸びをチャック間距離（５０ｍｍ）で除した値を言う。 Here, 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).
　本発明の粘着シートは、被着体の塗装面の色等をそのまま外観に反映させるためには透明であることが要求されるが、顔料等を使用して塗装面の色と同じ色で着色したり、別の色に着色したりして、塗装代替粘着シートとして使用してもよい。 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.
　本発明の粘着シートは、粘着シートの貼り付け作業を向上させるために、例えば貼付位置決め等のために、アプリケーションシートを使用することができる。 In the pressure-sensitive adhesive sheet of the present invention, 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.
　本発明の粘着シートの製造方法について以下に述べる。例えば、基材の上にコート層用塗布液を塗布した状態で熱硬化させて多層シートを形成し、次いで、基材の面上に粘着剤層を形成して粘着シートを作成するか、あるいは、仮支持体の上に粘着剤層を形成した後、得られた多層シートの基材面上に形成した粘着剤層を重ね貼り合せて粘着シートを形成する。 The method for producing the pressure-sensitive adhesive sheet of the present invention will be described below. For example, 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.
　あるいは、基材として複合フィルムを用いる場合には、例えば、まず、剥離処理されたポリエチレンテレフタレートフィルム（仮支持体１）の剥離処理面にコート層用の塗布液を塗布してコート層を形成した後、その上に複合フィルム用の塗布液を塗布し、その上に透明のセパレータ等をのせて、その上から紫外線等を照射して基材を形成しつつ架橋点も形成し、その後、セパレータを除去する。別途、剥離処理されたポリエステルフィルム（仮支持体２）の剥離処理面に粘着剤層用の塗布液を塗布して粘着剤層を形成する。その後、この粘着剤層を、基材面上に重ねて、粘着シートを得ることができる。なお、ここでは、剥離処理されたポリエチレンテレフタレートフィルム（仮支持体１）／コート層／基材／粘着剤層／剥離処理されたポリエステルフィルム（仮支持体２）の層構成となっているが、この仮支持体１および仮支持体２や上記仮支持体は、使用時に、すなわち粘着シートが貼付適用される際に剥離除去されるものであるので、本発明の粘着シートの構成には特に含めてはいない。ただし、これらの仮支持体１、仮支持体２、仮支持体等を、必要に応じて適宜設けることは可能であるし、これらの構成は本発明の技術的範囲に属するものである。 Alternatively, when a composite film is used as the substrate, for example, 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. Thereafter, this pressure-sensitive adhesive layer can be stacked on the substrate surface to obtain a pressure-sensitive adhesive sheet. In addition, although it becomes 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.
　本発明の粘着シートは、曲面に対する柔軟性に優れているので、三次元曲面が厳しい部位に対してもきれいに貼り付けることができる。また、本発明の粘着シートは、最外表面が優れた滑り性を有しているので、貼付作業時にスキージが良好に滑り、粘着シートにシワや傷が発生することがない。また、本発明によれば、コート層が基材に強固に接着した粘着シートを実現することができ、かかる粘着シートを使用すれば、例えば貼付作業時にコート層が剥がれたりすることがない。したがって輸送機械、例えば、自動二輪、自転車、鉄道車両、船舶、スノーモービル、ゴンドラ、リフト、エスカレーター、自動車、航空機等、特に自動車、航空機、自動二輪等の塗装面を保護するための保護用の多層シート、携帯電話の導光フィルム、電極基板の封止材料、エスカレーターの手すりの装飾用フィルム、透明ガラスと組み合わせて用いる透明フィルム等の用途に好適である。
  Since 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. Therefore, 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.
　以下に実施例を用いて、本発明を詳細に説明するが、本発明はこれに限定されるものではない。なお、以下の実施例において、特にことわりがない限り、部は重量部を意味し、％は重量％を意味する。また、以下の実施例において使用された測定方法および評価方法を下記に示す。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, parts mean parts by weight and% means% by weight. The measurement methods and evaluation methods used in the following examples are shown below.
（測定方法および評価方法）
（１）柔軟性の評価
　粘着シートを、幅１０ｍｍ×長さ１６０ｍｍに切断し、引張速度２００ｍｍ／ｍｉｎ、チャック間距離１００ｍｍ、室温（２３℃）で引張試験を実施し、応力－歪み曲線を求めた。柔軟性を評価するものとして、粘着シートの５％伸張時における単位面積当たりの応力である５％モジュラスの値を求めた。 (Measurement method and evaluation method)
(1) Evaluation of flexibility The pressure-sensitive adhesive sheet is cut into a width of 10 mm and a length of 160 mm, a tensile test is performed at a tensile speed of 200 mm / min, a distance between chucks of 100 mm, and room temperature (23 ° C.) to obtain a stress-strain curve. It was. For evaluating the flexibility, a value of 5% modulus, which is a stress per unit area when the pressure-sensitive adhesive sheet is stretched 5%, was obtained.
（２）密着性の評価
　粘着シートを、３０ｍｍ×３０ｍｍのサイズに切断し、この粘着シートをステンレス板（ＳＵＳ３０４板）にハンドローラーを用いて貼り合わせた。専用治具（コーテック株式会社製、ＣＣＪ）を用いて、ＳＵＳ３０４板に達する深さの傷となるように、２ｍｍ間隔で縦横それぞれに１１本の傷をつけ、１００枡の碁盤目状を形成した。ＪＩＳ　Ｚ１５２２に準拠して、この粘着シートにセロハンテープ（２４ｍｍ幅）をハンドローラーを用いて圧着した後、貼り付けたセロハンテープ表面を指で擦って十分に圧着した。その後、高速剥離試験機（工研株式会社製）を用いて、セロハンテープ背面から３０度の角度で、７０ｍ／ｍｉｎの引張速度でセロハンテープを剥がして、コート層の剥がれ状態を評価した。すなわち、この剥離したセロハンテープの粘着面全面に小麦粉等の粉末を付着させて、粉末が一枡の面積の５０％を超える面積で付着している枡目の数を数え、下記の評価基準に従って密着性の評価を行った。
 
評価基準
３点（優）　１００枡すべてに粉末が付着している。
２点（良）　１枡以上、９９枡以下の範囲の個数で粉末が付着している。
１点（劣）　粉末の付着が認められない。
  (2) Evaluation of adhesion The pressure-sensitive adhesive sheet was cut into a size of 30 mm × 30 mm, and this pressure-sensitive adhesive sheet was bonded to a stainless steel plate (SUS304 plate) using a hand roller. Using a special jig (Cortech Co., Ltd., CCJ), 11 scratches were made in each length and width at intervals of 2 mm to form a 100 mm grid pattern so that the scratches reached the depth of the SUS304 plate. . In accordance with JIS Z1522, cellophane tape (24 mm width) was pressure-bonded to this pressure-sensitive adhesive sheet using a hand roller, and then the bonded cellophane tape surface was rubbed with a finger and sufficiently bonded. Then, using a high-speed peel tester (manufactured by Koken Co., Ltd.), 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.
（３）表面滑り性の評価
　表面滑り性の評価として静摩擦係数の値を求めた。静摩擦係数の測定方法を以下に示す。
　粘着シートを、幅８０ｍｍ×長さ１００ｍｍのサイズに切断し、この粘着シートを標準試験板（ＪＩＳＧ３１４１：日本テストパネル株式会社製）の上に貼着し、この粘着シートの上に滑り片を載せ、ＪＩＳＫ７１２５に準じて最表面層（ex. コート層）の静摩擦係数を測定した。なお、滑り片の接触面積は６３ｍｍ×６３ｍｍ、滑り片の全質量を２００ｇ（１．９６Ｎ）とし、滑り片の粘着シート表面との接触面にはスキージークロスを貼り付け、滑り速度１００ｍｍ／ｍｉｎの条件で滑り片を引っ張って測定を行った。静摩擦係数は、ＪＩＳＫ７１２５に準ずる下記算出式を用いて求めた。 (3) Evaluation of surface slipperiness The value of the static friction coefficient was calculated | required as evaluation of surface slipperiness. 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 (ex. Coat 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 | required using the following calculation formula according to JISK7125.
　　　μ＝Ｆｓ／Ｆｐ
　（μ：静摩擦係数、Ｆｓ：静摩擦力（Ｎ）、Ｆｐ：滑り片の質量によって生じる法線力（＝９．８Ｎ／ｋｇ×０．２ｋｇ）） μ = Fs / Fp
(Μ: static friction coefficient, Fs: static friction force (N), Fp: normal force generated by the mass of the sliding piece (= 9.8 N / kg × 0.2 kg))
　図１の（ａ）および（ｂ）は、静摩擦係数の測定方法を説明するための概略図である。図１の（ａ）に示すように、試料１（ex. 粘着シート）の測定面が上を向くように、試料１を相手材２に固定し、すなわち、例えば粘着シートの粘着剤層を相手材２（ex. 標準試験板）の上に貼着して固定し、試料１の測定面の上に滑り片（接触面積６３ｍｍ×６３ｍｍ）を配置し、滑り片を試験速度１００ｍｍ／ｍｉｎで引っ張る。法線力は滑り片によって生じさせるので、均一な圧力分布をかけるために、滑り片の底面を弾力性のある材料（フェルト等）で覆う。なお、試料１は直接相手材１に固定してもよいが、支持体等の補助板に取り付けて固定してもよい。また、滑り片はスプリングを介してロードセルに接続しても良い。図１の（ｂ）に示すように、力は直線的に増加して摩擦を与え、最大荷重に達する。このピークが静摩擦力（Ｆｓ）を表す。静摩擦係数は、上記算出式（μ＝Ｆｓ／Ｆｐ）から求められる。 (A) and (b) in FIG. 1 are schematic diagrams for explaining a method for measuring a static friction coefficient. As shown in FIG. 1 (a), 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. Affixed on material 2 (ex. Standard test plate) and fixed, a sliding piece (contact area 63 mm × 63 mm) is placed on the measurement surface of sample 1, and the sliding piece is pulled at a test speed of 100 mm / min. . Since the normal force is generated by the sliding piece, 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. In addition, although the 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. As shown in FIG. 1 (b), the force increases linearly to give friction and reach a maximum load. This peak represents the static friction force (Fs). The static friction coefficient is obtained from the above calculation formula (μ = Fs / Fp).
（３）総合評価
　柔軟性および滑り性の評価結果をもとにして総合評価を実施した。すなわち、コート層を設けていない、基材と粘着剤層とからなる粘着シート（比較例１、比較例３、比較例５、比較例７、比較例９、比較例１１）を基準の粘着シートとして、この基準の粘着シートの柔軟性と比較して、「モジュラス値が、基準のモジュラス値+０．３ＭＰａ以下」かつ、静摩擦係数が０．００以上、１．００以下である場合を「優」と表示し、モジュラス値が、基準の粘着シートのモジュラス値＋０．３ＭＰａより大きいが、各実施例に対応する比較例２、比較例４、比較例６、比較例８、比較例１０、比較例１２のモジュラス値よりも小さく、かつ、静摩擦係数が１．５０以下である場合を「良」と表示し、それ以外の場合を「劣」と表示した。 (3) Comprehensive evaluation Comprehensive evaluation was performed based on the evaluation results of flexibility and slipperiness. That is, a pressure-sensitive adhesive sheet based on a pressure-sensitive adhesive sheet (Comparative Example 1, Comparative Example 3, Comparative Example 5, Comparative Example 7, Comparative Example 9, Comparative Example 11), which is not provided with a coating layer and is composed of a base material and a pressure-sensitive adhesive layer. As compared with the flexibility of this standard pressure-sensitive adhesive sheet, the case where “the modulus value is the standard modulus value + 0.3 MPa or less” and the static friction coefficient is 0.00 or more and 1.00 or less is “excellent”. 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”.
（実施例１）
《コート層用塗布液の作製》
　フルオロエチレンビニルエーテルのキシレンおよびトルエンによる５０％濃度溶解液（旭硝子（株）製の「ルミフロンＬＦ６００」）を１００部と、イソシアネート系架橋剤（日本ポリウレタン（株）製の「コロネートＨＸ」）を１２．１０部と、ポリオールとして三菱化学（株）製の「ＰＴＭＧ２０００」（ポリテトラメチレングリコール、平均分子量２０００）を１０．２５部、触媒として０．３５部のジブチル錫ラウリン酸（東京ファインケミカル株式会社製の「ＯＬ１」）のキシレン希釈液（固形分濃度が０．１重量％）と、希釈溶媒として、２５．８５部のトルエン、２５．８５部のヘキサン及び５１．７０部のメチルエチルケトンを添加して、コート層用塗布液を作製した。 (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.
《多層シートの作製》
　基材として、厚さ１５０μｍのアジペート－エステル系熱可塑性ポリウレタンフィルム（日本マタイ株式会社製、硬度８５Ａ（以下、「アジペート系フィルム」と表示））を使用した。このアジペート系フィルムの上に、上記で得られたコート層用塗布液を、硬化後の厚さが１０μｍとなるように塗布し、温度１４０℃で３分間、乾燥および硬化させて、基材の一方の面にコート層を設けた多層シートを形成した。 <Production of multilayer sheet>
A 150-μm 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 μm, 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.
《粘着剤層の作製》
　モノマー成分として、２－エチルヘキシルアクリレート９０部およびアクリル酸１０部を混合した混合物に、光重合開始剤として、商品名「イルガキュア　６５１」（チバ・スペシャリティ・ケミカルズ社製）を０．０５部と、商品名「イルガキュア　１８４」（チバ・スペシャリティ・ケミカルズ社製）を０．０５部とを配合した後、粘度が約１５Ｐａ・ｓ（ＢＨ粘度計Ｎｏ．５ローター、１０ｒｐｍ、測定温度３０℃）になるまで紫外線を照射して、一部が重合したアクリル組成物（ＵＶシロップ）を作製した。 << Production of adhesive layer >>
A mixture of 90 parts of 2-ethylhexyl acrylate and 10 parts of acrylic acid as a monomer component, 0.05 parts of a trade name “Irgacure 651” (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, After blending 0.05 parts of the name “Irgacure 184” (manufactured by Ciba Specialty Chemicals), until the viscosity is about 15 Pa · s (BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30 ° C.) An acrylic composition (UV syrup) partially polymerized by irradiation with ultraviolet rays was prepared.
　得られたＵＶシロップの１００部に対して、ヘキサンジオールジアクリレートを０．０８部、ヒンダードフェノール型酸化防止剤（チバ・スペシャリティ・ケミカルズ社製の商品名「イルガノックス１０１０」）を１部添加して粘着剤組成物を作製した。 0.08 parts of hexanediol diacrylate and 1 part of hindered phenol type antioxidant (trade name “Irganox 1010” manufactured by Ciba Specialty Chemicals) are added to 100 parts of the obtained UV syrup. Thus, an adhesive composition was prepared.
　この粘着剤組成物を、仮支持体として厚さ５０μｍのポリエチレンテレフタレートフィルムの剥離処理面に、最終製品としての厚さが５０μｍになるように塗布した。 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 μm so that the final product had a thickness of 50 μm.
　この上に、セパレータとして剥離処理したＰＥＴフィルムを重ねて被覆し、次いで、ＰＥＴフィルム面にメタルハライドランプを用いて紫外線（照度２９０ｍＷ／ｃｍ２、光量４，６００ｍＪ／ｃｍ２）を照射して硬化させて、仮支持体の上に粘着剤層を形成した。その後、１４０℃で３分間乾燥させて、未反応の残存アクリル系モノマーを乾燥させ、粘着剤層を作製した。 On top of this, 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.
《粘着シートの作製》
　セパレータを除去し、得られた多層シートのコート層側の面とは反対側の面（すなわち基材面）に、粘着剤層が重なるように貼り合わせて粘着シート（コート層／アジペート系ウレタンフィルム／粘着剤層／仮支持体の層構成）を作製した。なお、表１に基材の種類と厚さ、コート層の配合量とその主剤（フルオロエチレンビニルエーテル交互共重合体）に対するモル比を示した。 <Production of adhesive sheet>
The separator is removed, and the adhesive sheet (coat layer / adipate-based urethane film) is bonded to the surface opposite to the surface on the side of the coating layer (that is, the substrate surface) of the resulting multilayer sheet so that the adhesive layer overlaps. / Adhesive layer / Temporary support layer configuration). Table 1 shows the type and thickness of the base material, the blending amount of the coat layer, and the molar ratio to the main agent (fluoroethylene vinyl ether alternating copolymer).
《測定および評価》
　得られた粘着シートについて、上記に示す評価方法に従い、柔軟性（５％モジュラス）及び表面滑り性（静摩擦係数）の評価を行い、更に、総合評価も行った。その結果を表３に示す。 <Measurement and evaluation>
About the obtained adhesive sheet, according to the evaluation method shown above, the softness | flexibility (5% modulus) and the surface slipperiness (static friction coefficient) were evaluated, and also comprehensive evaluation was also performed. The results are shown in Table 3.
（実施例２～７、比較例１～２）
　コート層用塗布液の作製において、表１に示す配合のコート層組成物を用いて作製した以外は実施例１と同様にして、コート層、多層シートおよび粘着シートを作製した。なお、比較例１はコート層が設けられていないものであり、粘着シートは基材および粘着剤層からなる。この粘着シートは、評価の際には基準の粘着シートとした。得られた粘着シートについて、実施例１と同様の測定および評価を行った。その結果を表３に示す。 (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. In addition, 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.
（実施例８、比較例３，４）
　基材として、厚さ２９０μｍのアジペート系フィルム（日本マタイ株式会社製、硬度８７Ａ（以下、「アジペート系フィルム」と表示））を使用し、コート層用塗布液として表２に示す配合のものを使用した以外は実施例１と同様にして、コート層、多層シートおよび粘着シートを作製した。なお、比較例３はコート層が設けられていないものであり、粘着シートは基材および粘着剤層からなる。この粘着シートは、評価の際には基準の粘着シートとした。得られた粘着シートについて、実施例１と同様の測定および評価を行った。その結果を表４に示す。 (Example 8, Comparative Examples 3 and 4)
As the base material, an adipate film having a thickness of 290 μm (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. In addition, 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.
（実施例９、比較例５，６）
　基材として、厚さ１５０μｍのカプロラクトン系フィルム（日本マタイ株式会社製、硬度８７Ａ（以下、「カプロラクトン系フィルム」と表示））を使用し、コート層用塗布液として表２に示す配合のものを使用した以外は実施例１と同様にして、コート層、多層シートおよび粘着シートを作製した。なお、比較例５はコート層が設けられていないものであり、粘着シートは基材および粘着剤層からなる。この粘着シートは、評価の際には基準の粘着シートとした。得られた粘着シートについて、実施例１と同様の測定および評価を行った。その結果を表４に示す。 (Example 9, Comparative Examples 5 and 6)
As a substrate, a caprolactone film having a thickness of 150 μm (manufactured by Nippon Matai Co., Ltd., hardness 87A (hereinafter referred to as “caprolactone 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. In addition, 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.
（実施例１０、比較例７，８）
　基材として、厚さ２９０μｍのカプロラクトン系フィルム（日本マタイ株式会社製、硬度８７Ａ（以下、「カプロラクトン系フィルム」と表示））を使用し、コート層用塗布液として表２に示す配合のものを使用した以外は実施例１と同様にして、コート層、多層シートおよび粘着シートを作製した。なお、比較例３はコート層が設けられていないものであり、粘着シートは基材および粘着剤層からなる。この粘着シートは、評価の際には基準の粘着シートとした。得られた粘着シートについて、実施例１と同様の測定および評価を行った。その結果を表４に示す。 (Example 10, Comparative Examples 7 and 8)
As a base material, a caprolactone film having a thickness of 290 μm (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. In addition, 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.
Figure JPOXMLDOC01-appb-T000010
  
Figure JPOXMLDOC01-appb-T000010
  
Figure JPOXMLDOC01-appb-T000011
  
Figure JPOXMLDOC01-appb-T000011
  
Figure JPOXMLDOC01-appb-T000012
  
Figure JPOXMLDOC01-appb-T000012
  
Figure JPOXMLDOC01-appb-T000013
  
Figure JPOXMLDOC01-appb-T000013
  
（実施例１１、比較例９および１０）
《複合フィルム用塗布液の作製》
　冷却管、温度計、および攪拌装置を備えた反応容器に、アクリル系モノマーとして、アクリル酸（ＡＡ）を５部、イソボルニルアクリレート（ＩＢＸＡ）を３５部、アクリル酸ｎ－ブチル（ＢＡ）を１０部と、ポリオールとして、ポリオキシテトラメチレングリコール（ＰＴＭＧ）（数平均分子量６５０、三菱化学（株）製）を３６．４部とを投入し、攪拌しながら、水添キシリレンジイソシアネート（ＨＸＤＩ）の１３．６部を滴下し、６５℃で１０時間反応させて、ウレタンポリマー－アクリル系モノマー混合物（複合フィルム前駆体）を得た。 (Example 11, Comparative Examples 9 and 10)
<< Preparation of coating solution for composite film >>
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 5 parts of acrylic acid (AA), 35 parts of isobornyl acrylate (IBXA), and n-butyl acrylate (BA) are used as acrylic monomers. 10 parts and 36.4 parts of polyoxytetramethylene glycol (PTMG) (number average molecular weight 650, manufactured by Mitsubishi Chemical Corporation) as a polyol were added and stirred with hydrogenated xylylene diisocyanate (HXDI). 13.6 parts of was added dropwise and reacted at 65 ° C. for 10 hours to obtain a urethane polymer-acrylic monomer mixture (composite film precursor).
　その後、得られたウレタンポリマー－アクリル系モノマー混合物の１００部に対して、光重合開始剤として、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（チバ・スペシャリティ・ケミカルズ（株）製の「ＩＲＧＡＣＵＲＥ８１９」）を０．１５９部、トリメチロールプロパントリアクリレート（ＴＭＰＴＡ）を３．０部、ヒドロキシフェニルトリアジン系紫外線吸収剤として、チバ・スペシャリティ・ケミカルズ（株）製の「ＴＩＮＵＶＩＮ　４００」を１．２５部と、ヒンダードアミン系光安定剤として、チバ・スペシャリティ・ケミカルズ（株）製の「ＴＩＮＵＶＩＮ　１２３」を１．２５部添加し、充分に攪拌して添加剤等を完全に溶解させ、ウレタンポリマーとアクリル系モノマーの混合物（複合フィルム用塗布液）を得た。但し、ポリイソシアネート成分およびポリオール成分の使用量は、ＮＣＯ／ＯＨ（当量比）＝１．２５であった。 Thereafter, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for 100 parts of the obtained urethane polymer-acrylic monomer mixture. “IRGACURE819” manufactured by Ciba Specialty Chemicals Co., Ltd. as 0.159 parts, 3.0 parts of trimethylolpropane triacrylate (TMPTA), and a hydroxyphenyltriazine-based UV absorber. 1.25 parts and 1.25 parts of “TINUVIN 123” manufactured by Ciba Specialty Chemicals Co., Ltd. as a hindered amine-based light stabilizer are added and thoroughly stirred to dissolve the additives and the like. A mixture of polymer and acrylic monomer ( To obtain a slip film coating solution). However, the usage-amount of the polyisocyanate component and the polyol component was NCO / OH (equivalent ratio) = 1.25.
《ウレタン-アクリル複合フィルムの作製》
　仮支持体として剥離処理したポリエチレンテレフタレートフィルム（厚さ７５μｍ）上に、得られた複合フィルム用塗布液を、硬化後の厚さが１４０μｍとなるように塗布し、この上にセパレータとして剥離処理したポリエチレンテレフタレートフィルムを重ねた。このＰＥＴフィルム面に、メタルハライドランプを用いて紫外線（照度２１０ｍＷ／ｃｍ２、光量４，０００ｍＪ／ｃｍ２）を照射して硬化させて、アクリルポリマーとウレタンポリマーを有する複合フィルム（以下、「ＵＡ－Ａ基材」と表示）を作製した。 <Production of urethane-acrylic composite film>
On the polyethylene terephthalate film (thickness 75 μm) subjected to release treatment as a temporary support, the obtained coating solution for composite film was applied so that the thickness after curing was 140 μm, and release treatment was performed thereon as a separator. A polyethylene terephthalate film was stacked. This PET film surface is cured by irradiating with ultraviolet rays (illuminance: 210 mW / cm 2 , light amount: 4,000 mJ / cm 2 ) using a metal halide lamp, and a composite film having an acrylic polymer and a urethane polymer (hereinafter referred to as “UA-”). A base material ") was prepared.
　コート層用塗布液の種類および配合量を表５に示すものに変更し、ＵＡ－Ａ基材の上に該コート層用塗布液を塗布した以外は実施例１と同様にして、多層シートおよび粘着シートを作製した。得られた粘着シートについて、実施例１と同様の測定および評価を行った。その結果を表６に示す。 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.
（実施例１２、比較例１１および１２）
《複合フィルム用塗布液の作製》
　冷却管、温度計、および攪拌装置を備えた反応容器に、アクリル系モノマーとして、アクリル酸（ＡＡ）を４．５部、イソボルニルアクリレート（ＩＢＸＡ）を２７部、アクリル酸ｎ－ブチル（ＢＡ）を１３．５部と、ポリオールとして、ポリオキシテトラメチレングリコール（ＰＴＭＧ）（数平均分子量６５０、三菱化学（株）製）を３８．５部とを投入し、攪拌しながら、イソホロンジイソシアネート（ＩＰＤＩ）の１６．５部を滴下し、６５℃で５時間反応させた。その後、４－ヒドロキシブチルアクリレートを４．３５部滴下した後、６５℃で１時間反応させ、ウレタンポリマー－アクリル系モノマー混合物（複合フィルム前駆体）を得た。 (Example 12, Comparative Examples 11 and 12)
<< Preparation of coating solution for composite film >>
In a reaction vessel equipped with a condenser, a thermometer and a stirrer, 4.5 parts of acrylic acid (AA), 27 parts of isobornyl acrylate (IBXA), n-butyl acrylate (BA) as acrylic monomers ) And 18.5 parts of polyoxytetramethylene glycol (PTMG) (number average molecular weight 650, manufactured by Mitsubishi Chemical Corporation) as a polyol and 38.5 parts as a polyol, while stirring, isophorone diisocyanate (IPDI) 16.5 parts) was added dropwise and reacted at 65 ° C. for 5 hours. Thereafter, 4.35 parts of 4-hydroxybutyl acrylate was added dropwise and reacted at 65 ° C. for 1 hour to obtain a urethane polymer-acrylic monomer mixture (composite film precursor).
　その後、得られたウレタンポリマー－アクリル系モノマー混合物の１００部に対して、光重合開始剤として、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（チバ・スペシャリティ・ケミカルズ（株）製の「ＩＲＧＡＣＵＲＥ８１９」）を０．１５９部、トリメチロールプロパントリアクリレート（ＴＭＰＴＡ）を８．１部添加し、充分に攪拌して添加剤等を完全に溶解させ、ウレタンポリマーとアクリル系モノマーの混合物（複合フィルム用塗布液）を得た。但し、ポリイソシアネート成分およびポリオール成分の使用量は、ＮＣＯ／ＯＨ（当量比）＝１．２５であった。 Thereafter, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for 100 parts of the obtained urethane polymer-acrylic monomer mixture. 0.159 parts of “IRGACURE819” and 8.1 parts of trimethylolpropane triacrylate (TMPTA) were added, and the mixture was thoroughly stirred to completely dissolve the additives, and the mixture of urethane polymer and acrylic monomer. (Coating liquid for composite film) was obtained. However, the usage-amount of the polyisocyanate component and the polyol component was NCO / OH (equivalent ratio) = 1.25.
《ウレタン－アクリル複合フィルムの作製》
　仮支持体として剥離処理したポリエチレンテレフタレートフィルム（厚さ７５μｍ）上に、得られた複合フィルム用塗布液を、硬化後の厚さが２４０μｍとなるように塗布し、この上にセパレータとして剥離処理したポリエチレンテレフタレートフィルムを重ねた。このＰＥＴフィルム面に、メタルハライドランプを用いて紫外線（照度２１０ｍＷ／ｃｍ２、光量４，０００ｍＪ／ｃｍ２）を照射して硬化させて、アクリルポリマーとウレタンポリマーを有する複合フィルム（以下、「ＵＡ‐Ｂ基材」と表示）を作製した。 << Preparation of urethane-acrylic composite film >>
On the polyethylene terephthalate film (thickness 75 μm) subjected to release treatment as a temporary support, the obtained coating solution for composite film was applied so that the thickness after curing was 240 μm, and release treatment was performed thereon as a separator. A polyethylene terephthalate film was stacked. This PET film surface is cured by irradiating with ultraviolet rays (illuminance: 210 mW / cm 2 , light amount: 4,000 mJ / cm 2 ) using a metal halide lamp, and a composite film (hereinafter referred to as “UA-”) having an acrylic polymer and a urethane polymer. B base material ") was prepared.
　コート層用塗布液の種類および配合量を表５に示すものに変更し、ＵＡ－Ｂ基材の上に該コート層用塗布液を塗布した以外は実施例１と同様にして、多層シートおよび粘着シートを作製した。得られた粘着シートについて、実施例１と同様の測定および評価を行った。その結果を表６に示す。 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.
Figure JPOXMLDOC01-appb-T000014
  
Figure JPOXMLDOC01-appb-T000014
  
Figure JPOXMLDOC01-appb-T000015
  
Figure JPOXMLDOC01-appb-T000015
  
（表１～６中の注記）
　Ａ：　フルオロエチレンビニルエーテル交互共重合体　「ＬＦ６００」（旭硝子（株）製）　
　Ｂ－１：　イソシアネート系架橋剤　「コロネートＨＸ」（日本ポリウレタン工業（株）製）　“Ｃ／ＨＸ”と表示
　Ｂ－２：　イソシアネート系架橋剤　「コロネートＨＬ」（日本ポリウレタン工業（株）製）　“Ｃ／ＨＬ”と表示
　ポリオール：
　・「ＰＴＭＧ２０００」（ポリテトラメチレングリコール（平均分子量２０００）、三菱化学（株）製）
　・「ＰＴＭＧ１０００」（ポリテトラメチレングリコール（平均分子量１０００）、三菱化学（株）製）
　・「Ｔ５６５０Ｅ」（ポリカーボネートジオール（平均分子量５００）、旭化成ケミカルズ（株）製）
　・「ＰＬＡＣＣＥＬ　３０５」（３官能カプロラクトンポリオール（平均分子量５５０）、ダイセル化学工業（株）製）　“３０５”と表示
　触媒：　ジブチル錫ジラウレート（ＤＢＴＤＬ）（「ＯＬ１」、東京ファインケミカル（株）製）、但し、キシレン希釈液（ラウリン酸ジブチル錫の濃度０．０１重量％）を使用 (Notes in Tables 1 to 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 caprolactone polyol (average molecular weight 550), manufactured by Daicel Chemical Industries, Ltd.) Displayed as "305" Catalyst: Dibutyltin dilaurate (DBTDL) ("OL1", manufactured by Tokyo Fine Chemical Co., Ltd.), However, use xylene diluted solution (concentration 0.01% by weight of dibutyltin laurate)
　表３から明らかなように、本発明の粘着シートである実施例１～７は、比較例１の粘着シート（基準）と同等の５％モジュラスの値を示し、比較例２の５％モジュラスの値よりも小さいことが分かった。これは、ポリオールを含有するコート層組成物を用いてコート層を形成した粘着シートは、基材自体が有する優れた柔軟性を維持していることを示すものである。ポリオールの添加により、コート層中の架橋点間分子量が増加したためと考えられる。 As is apparent from Table 3, 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.
　本発明の効果を得るためには、ポリオールの分子量は３００以上であることが好ましく、さらに好ましくは５００以上であり、特に好ましくは１，０００以上であることも分かった。ただし、外観の白濁性の観点から、ポリオールの分子量は１０，０００以下であることが好ましく、さらに好ましくは８，０００以下であり、特に好ましくは５，０００以下である。また、柔軟性の効果を得るためには、主剤に対するポリオールのモル比が０．２以上であることが好ましく、更に好ましくは０．２５以上であり、特に好ましくは０．５以上であることも分かった。ただし、外観の白濁性の観点から、ポリオールのモル比は、０．７以下であることが好ましい。 In order to obtain the effect of the present invention, it was also found that the molecular weight of the polyol is preferably 300 or more, more preferably 500 or more, and particularly preferably 1,000 or more. However, 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. In order to obtain the effect of flexibility, 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.
　実施例２および実施例５より、硬化剤の種類としてイソシアヌレート環を有するＣ／ＨＸよりもトリメチロールプロパンのアダクトタイプであるＣ／ＨＬを配合したコート層組成物を用いて粘着シートを作製した方が、より柔軟性に優れていることが分かった。 From Example 2 and Example 5, the adhesive sheet was produced using the coating layer composition which mix | blended C / HL which is an adduct type of trimethylolpropane rather than C / HX which has an isocyanurate ring as a kind of hardening | curing agent. It turned out that it is more flexible.
　また、表３から明らかなように、本発明の実施例１～７の粘着シートは、比較例２に比べて、表面滑り性に優れており、特に実施例１～４および実施例６の粘着シートが極めて優れた滑り性を示すことが分かった。 As is clear from Table 3, 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.
　また、表４から明らかなように、本発明の粘着シートである実施例８は、比較例３の粘着シート（基準）と同等の５％モジュラスの値を示し、比較例４の５％モジュラスの値よりも小さいことが分かったし、また、本発明の粘着シートである実施例９は、比較例５の粘着シート（基準）と同等の５％モジュラスの値を示し、比較例６の５％モジュラスの値よりも小さいことが分かったし、また、本発明の粘着シートである実施例１０は、比較例７の粘着シート（基準）と同等の５％モジュラスの値を示し、比較例８の５％モジュラスの値よりも小さいことが分かった。これは、ポリオールを含有するコート層組成物を用いてコート層を形成した粘着シートは、基材自体が有する優れた柔軟性を維持していることを示すものであり、また、実施例８～１０は表面滑り性についても優れていることが分かった。すなわち、ここでも、上記表３と同様の効果が認められたのである。 Further, as apparent from Table 4, 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). It was found to be less than the value of 5% modulus. 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. 10 was also found to be excellent in terms of surface slipperiness. That is, the same effect as in Table 3 was also observed here.
　また、表６から明らかなように、本発明の粘着シートである実施例１１は、比較例９の粘着シート（基準）と同等の５％モジュラスの値を示し、比較例１０の５％モジュラスの値よりも小さいことが分かったし、また、本発明の粘着シートである実施例１２は、比較例１１の粘着シート（基準）と同等の５％モジュラスの値を示し、比較例１２の５％モジュラスの値よりも小さいことが分かった。これは、ポリオールを含有するコート層組成物を用いてコート層を形成した粘着シートは、基材自体が有する優れた柔軟性を維持していることを示すものであり、また、実施例１１～１２は表面滑り性についても優れていることが分かった。すなわち、ここでも、上記表３と同様の効果が認められたのである。 Further, as is apparent from Table 6, 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.
　すなわち、本発明の粘着シートは、複合フィルムを用いて、少なくとも、フッ素系ポリマー、ポリオール、及び、多官能イソシアネートを用いてなるコート層を有し、優れた柔軟性と優れた滑り性とを同時に達成できるものであることが分かった。 That is, 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.
（実施例１３）
《コート層用塗布液の作製》
　水酸基含有（メタ）アクリルモノマーとして４－ヒドロキシブチルアクリレート（大阪有機化学工業（株）製、「４－ＨＢＡ」）を１．４７部と、イソシアネート系架橋剤（日本ポリウレタン（株）製の「コロネートＨＸ」）を２２．１９部とを混合し、室温（２３℃）で４日間放置して反応させ反応液を得た。次いで、この反応液に、フルオロエチレンビニルエーテルのキシレンおよびトルエンによる５０％濃度溶解液（旭硝子（株）製の「ルミフロンＬＦ６００」）を１００部と、ポリオールとして旭化成ケミカルズ（株）製の「Ｔ５６５２」（ポリカーボネートジオール、平均分子量２０００）を５１．２５部と、触媒として０．３５部のジブチル錫ラウリン酸（東京ファインケミカル株式会社製の「ＯＬ１」）のキシレン希釈液（固形分濃度が０．１重量％）と、希釈溶媒として、５３．７７部のトルエン、１０７．５５部のヘキサン及び５３．７７部のメチルエチルケトンとを添加して、コート層用塗布液を作製した。 (Example 13)
<< Preparation of coating layer coating liquid >>
1.47 parts of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., “4-HBA”) as a hydroxyl group-containing (meth) acrylic monomer and an isocyanate-based crosslinking agent (“Coronate” manufactured by Nippon Polyurethane Co., Ltd.) HX ") was mixed with 22.19 parts and allowed to react at room temperature (23 ° C) for 4 days to obtain a reaction solution. Next, 100 parts of a 50% concentration solution of fluoroethylene vinyl ether in xylene and toluene (“Lumiflon LF600” manufactured by Asahi Glass Co., Ltd.) and “T5652” manufactured by Asahi Kasei Chemicals Co., Ltd. as a polyol were added to this reaction solution. Polycarbonate diol having an average molecular weight of 2000) of 51.25 parts and 0.35 parts of dibutyltin lauric acid (“OL1” manufactured by Tokyo Fine Chemical Co., Ltd.) as a catalyst in a xylene dilution (solids concentration 0.1% by weight) ) And 53.77 parts of toluene, 107.55 parts of hexane and 53.77 parts of methyl ethyl ketone as diluent solvents were added to prepare a coating layer coating solution.
《複合フィルム用塗布液の作製》
　冷却管、温度計、および攪拌装置を備えた反応容器に、アクリル系モノマーとして、アクリル酸（ＡＡ）を５部、イソボルニルアクリレーと（ＩＢＸＡ）を３５部、アクリル酸ｎ－ブチル（ＢＡ）を１０部と、ポリオールとして、ポリオキシテトラメチレングリコール（ＰＴＭＧ）（数平均分子量６５０、三菱化学（株）製）を３６．４部とを投入し、攪拌しながら、水添キシリレンジイソシアネート（ＨＸＤＩ）の１３．６部を滴下し、６５℃で１０時間反応させて、ウレタンポリマー－アクリル系モノマー混合物（複合フィルム前駆体）を得た。 << Preparation of coating solution for composite film >>
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 5 parts of acrylic acid (AA), 35 parts of isobornyl acrylate and (IBXA) as acrylic monomers, n-butyl acrylate (BA ) And 10 parts of polyoxytetramethylene glycol (PTMG) (number average molecular weight 650, manufactured by Mitsubishi Chemical Corporation) as a polyol, and 36.4 parts of hydrogenated xylylene diisocyanate (with stirring) 13.6 parts of (HXDI) was added dropwise and reacted at 65 ° C. for 10 hours to obtain a urethane polymer-acrylic monomer mixture (composite film precursor).
　その後、得られたウレタンポリマー－アクリル系モノマー混合物の１００部に対して、光重合開始剤として、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（チバ・スペシャリティ・ケミカルズ（株）製の「ＩＲＧＡＣＵＲＥ８１９」）を０．１５９部、トリメチロールプロパントリアクリレート（ＴＭＰＴＡ）を３．０部、ヒドロキシフェニルトリアジン系紫外線吸収剤として、チバ・スペシャリティ・ケミカルズ（株）製の「ＴＩＮＵＶＩＮ　４００」を１．２５部と、ヒンダードアミン系光安定剤として、チバ・スペシャリティ・ケミカルズ（株）製の「ＴＩＮＵＶＩＮ　１２３」を１．２５部添加し、充分に攪拌して添加剤等を完全に溶解させ、ウレタンポリマーとアクリル系モノマーの混合物（複合フィルム用塗布液）を得た。但し、ポリイソシアネート成分およびポリオール成分の使用量は、ＮＣＯ／ＯＨ（当量比）＝１．２５であった。 Thereafter, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals Co., Ltd.) was used as a photopolymerization initiator for 100 parts of the obtained urethane polymer-acrylic monomer mixture. “IRGACURE819” manufactured by Ciba Specialty Chemicals Co., Ltd. as 0.159 parts, 3.0 parts of trimethylolpropane triacrylate (TMPTA), and a hydroxyphenyltriazine-based UV absorber. 1.25 parts and 1.25 parts of “TINUVIN 123” manufactured by Ciba Specialty Chemicals Co., Ltd. as a hindered amine-based light stabilizer are added and thoroughly stirred to dissolve the additives and the like. A mixture of polymer and acrylic monomer ( To obtain a slip film coating solution). However, the usage-amount of the polyisocyanate component and the polyol component was NCO / OH (equivalent ratio) = 1.25.
《コート層の作製》
　得られたコート層用塗布液を、仮支持体１として剥離処理したポリエチレンテレフタレートフィルム（厚さ７５μｍ）の上に硬化後の厚みが１０μｍとなるように塗布し、温度１４０℃で３分間乾燥および硬化させてコート層を形成した。 << Preparation of coat layer >>
The resulting coating layer coating solution was applied on a polyethylene terephthalate film (thickness 75 μm) peel-treated as temporary support 1 so that the thickness after curing was 10 μm, dried at 140 ° C. for 3 minutes, and Cured to form a coat layer.
《多層シートの作成》
　形成したコート層の上に、作製した複合フィルム用塗布液を、硬化後の厚みが２９０μｍ（コート層の厚みも含めると３００μｍ）となるように塗布し、この上にセパレータとして剥離処理したポリエチレンテレフタレート（ＰＥＴ）フィルムを重ねた。このＰＥＴフィルム面に、メタルハライドランプを用いて紫外線（照度２１０ｍＷ／ｃｍ２、光量４，０００ｍＪ／ｃｍ２）を照射して硬化させて、仮支持体１の上にコート層および複合フィルムを有する多層シート（セパレータを備えている）形成した。 <Creation of multilayer sheet>
On the formed coating layer, the prepared coating solution for composite film was applied so that the thickness after curing was 290 μm (300 μm 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.
《粘着剤層の作製》
　モノマー成分として、２－エチルヘキシルアクリレート９０部およびアクリル酸１０部を混合した混合物に、光重合開始剤として、商品名「イルガキュア　６５１」（チバ・スペシャリティ・ケミカルズ社製）を０．０５部と、商品名「イルガキュア　１８４」（チバ・スペシャリティ・ケミカルズ社製）を０．０５部とを配合した後、粘度が約１５Ｐａ・ｓ（ＢＨ粘度計Ｎｏ．５ローター、１０ｒｐｍ、測定温度３０℃）になるまで紫外線を照射して、一部が重合したアクリル組成物（ＵＶシロップ）を作製した。 << Production of adhesive layer >>
A mixture of 90 parts of 2-ethylhexyl acrylate and 10 parts of acrylic acid as a monomer component, 0.05 parts of a trade name “Irgacure 651” (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, After blending 0.05 parts of the name “Irgacure 184” (manufactured by Ciba Specialty Chemicals), until the viscosity is about 15 Pa · s (BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30 ° C.) An acrylic composition (UV syrup) partially polymerized by irradiation with ultraviolet rays was prepared.
　得られたＵＶシロップの１００部に対して、ヘキサンジオールジアクリレートを０．０８部、ヒンダードフェノール型酸化防止剤（チバ・スペシャリティ・ケミカルズ社製の商品名「イルガノックス１０１０」）を１部添加して粘着剤組成物を作製した。 0.08 parts of hexanediol diacrylate and 1 part of hindered phenol type antioxidant (trade name “Irganox 1010” manufactured by Ciba Specialty Chemicals) are added to 100 parts of the obtained UV syrup. Thus, an adhesive composition was prepared.
　この粘着剤組成物を、仮支持体２として厚み５０μｍのポリエチレンテレフタレートフィルムの剥離処理面に、最終製品としての厚みが５０μｍになるように塗布した。 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 μm so that the final product had a thickness of 50 μm.
　この上に、セパレータとして剥離処理したＰＥＴフィルムを重ねて被覆し、次いで、ＰＥＴフィルム面にメタルハライドランプを用いて紫外線（照度２９０ｍＷ／ｃｍ２、光量４，６００ｍＪ／ｃｍ２）を照射して硬化させて、仮支持体２の上に粘着剤層を形成した。その後、１４０℃で３分間乾燥させて、未反応の残存アクリル系モノマーを乾燥させ、粘着剤層を作製した。 On top of this, 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. Thus, 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.
《粘着シートの作製》
　セパレータを除去し、得られた多層シートのコート層側の面とは反対側の面（すなわち基材面）に、粘着剤層が重なるように貼り合わせて粘着シート（仮支持体１／コート層／複合フィルム／粘着剤層／仮支持体２の層構成）を作製した。 <Production of adhesive sheet>
The separator is removed, and the resulting multilayer sheet is bonded to the surface opposite to the surface on the coat layer side (that is, the base material surface) so that the pressure-sensitive adhesive layer overlaps with the pressure-sensitive adhesive sheet (temporary support 1 / coat layer) / Composite film / adhesive layer / layer structure of temporary support 2).
《測定および評価》
　得られた粘着シートについて、上記に示す評価方法に従い、柔軟性（５％モジュラス）及び密着性（碁盤目試験）の評価を行った。その結果を表９に示す。
なお、表９には、ポリオールの種類とその分子量、主剤（フルオロエチレンビニルエーテル交互共重合体）に対するポリオールのモル比、および、主剤（フルオロエチレンビニルエーテル交互共重合体）に対する水酸基含有（メタ）アクリル系モノマーのモル比も併せて記載した。 <Measurement and evaluation>
About the obtained adhesive sheet, according to the evaluation method shown above, the softness | flexibility (5% modulus) and adhesiveness (cross-cut test) were evaluated. The results are shown in Table 9.
Table 9 shows the types and molecular weights of polyols, the molar ratio of polyol to the main agent (fluoroethylene vinyl ether alternating copolymer), and the hydroxyl group-containing (meth) acrylic type relative to the main agent (fluoroethylene vinyl ether alternating copolymer). The molar ratio of monomers is also shown.
（実施例１４～２３、比較例１３～１４）
　コート層用塗布液の種類および配合量を表７に示すものに変更した以外は実施例１３と同様にして、コート層、多層シートおよび粘着シートを作製した。得られた粘着シートについて、実施例１３と同様にして、上記に示す評価方法に従い、柔軟性（５％モジュラス）及び密着性（碁盤目試験）の評価を行った。その結果を表９に示す。 (Examples 14 to 23, Comparative Examples 13 to 14)
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. About the obtained adhesive sheet, it carried out similarly to Example 13, and evaluated the softness | flexibility (5% modulus) and adhesiveness (cross-cut test) according to the evaluation method shown above. The results are shown in Table 9.
（実施例２４～２９）
　コート層用塗布液の種類および配合量を表８に示すものに変更した以外は実施例１３と同様にして、コート層、多層シートおよび粘着シートを作製した。得られた粘着シートについて、実施例１３と同様にして、上記に示す評価方法に従い、柔軟性（５％モジュラス）及び密着性（碁盤目試験）の評価を行った。その結果を表９に示す。 (Examples 24 to 29)
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 | flexibility (5% modulus) and adhesiveness (cross-cut test) according to the evaluation method shown above. The results are shown in Table 9.
Figure JPOXMLDOC01-appb-T000016
  
Figure JPOXMLDOC01-appb-T000016
  
Figure JPOXMLDOC01-appb-T000017
  
Figure JPOXMLDOC01-appb-T000017
  
Figure JPOXMLDOC01-appb-T000018
  
Figure JPOXMLDOC01-appb-T000018
  
表７～９中の注記）
　Ａ：　フルオロエチレンビニルエーテル交互共重合体　「ＬＦ６００」（旭硝子（株）製）　
　Ｂ：　イソシアネート系架橋剤　「コロネートＨＸ」（日本ポリウレタン工業（株）製）　“Ｃ／ＨＸ”と表示
　Ｃ：　水酸基含有（メタ）アクリルモノマー　「４－ＨＢＡ」（４－ヒドロキシブチルアクリレート、大阪有機化学工業（株）製）
　ポリオール：
　・「Ｔ５６５２」（ポリカーボネートジオール（平均分子量２０００）、旭化成ケミカルズ（株）製）
　・「Ｔ５６５０Ｅ」（ポリカーボネートジオール（平均分子量５００）、旭化成ケミカルズ（株）製）
　・「ＰＴＭＧ２０００」（ポリテトラメチレングリコール（平均分子量２０００）、三菱化学（株）製）
　・「ＰＬＡＣＣＥＬ２２０ＥＢ」（２官能カプロラクトンポリオール（平均分子量２０００）、ダイセル化学工業（株）製）　“２２０ＥＢ”と表示
　・「ＰＬＡＣＣＥＬ　３０５」（３官能カプロラクトンポリオール（平均分子量５５０）、ダイセル化学工業（株）製）　“３０５”と表示
　・「ＰＴＭＧ１０００」（ポリテトラメチレングリコール（平均分子量１０００）、三菱化学（株）製）
　触媒：　ジブチル錫ジラウレート（ＤＢＴＤＬ）（「ＯＬ１」、東京ファインケミカル（株）製）、但し、キシレン希釈液（ラウリン酸ジブチル錫の濃度０．０１重量％）を使用 Notes in Tables 7-9)
A: Fluoroethylene vinyl ether alternating copolymer “LF600” (Asahi Glass Co., Ltd.)
B: Isocyanate-based crosslinking agent “Coronate HX” (manufactured by Nippon Polyurethane Industry Co., Ltd.) Indicated as “C / HX” C: Hydroxyl group-containing (meth) acrylic monomer “4-HBA” (4-hydroxybutyl acrylate, Osaka Organic Chemistry) (Manufactured by Kogyo Co., Ltd.)
Polyol:
"T5652" (polycarbonate diol (average molecular weight 2000), manufactured by Asahi Kasei Chemicals Corporation)
・ "T5650E" (polycarbonate diol (average molecular weight 500), manufactured by Asahi Kasei Chemicals Corporation)
・ "PTMG2000" (polytetramethylene glycol (average molecular weight 2000), manufactured by Mitsubishi Chemical Corporation)
・ "PLACCEL220EB" (bifunctional caprolactone polyol (average molecular weight 2000), manufactured by Daicel Chemical Industries, Ltd.) "220EB" is displayed. "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)
表８中の注記）
　水酸基含有（メタ）アクリル系モノマー：　
　・Ｃ－２　「Ｖ＃８０２」（水酸基含有多官能アクリルモノマー、大阪有機化学工業（株）製） Notes in Table 8)
Hydroxyl group-containing (meth) acrylic monomer:
・ C-2 “V # 802” (hydroxyl group-containing polyfunctional acrylic monomer, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Figure JPOXMLDOC01-appb-C000019
  
 
Figure JPOXMLDOC01-appb-C000019
  
 
　・Ｃ－３　「Ｖ＃３００」（水酸基含有三官能アクリルモノマー、大阪有機化学工業（株）製） ・ C-3 "V # 300" (Hydroxyl-containing trifunctional acrylic monomer, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Figure JPOXMLDOC01-appb-C000020
  
 
Figure JPOXMLDOC01-appb-C000020
  
 
　・Ｃ－４　「ＦＭ２Ｄ」（水酸基含有メタクリルモノマー、（株）ダイセル製）
　・Ｃ－５　「ＦＡ２Ｄ」）水酸基含有アクリルモノマー、（株）ダイセル製） C-4 “FM2D” (hydroxyl group-containing methacrylic monomer, manufactured by Daicel Corporation)
C-5 “FA2D”) Hydroxyl group-containing acrylic monomer (manufactured by Daicel Corporation)
Figure JPOXMLDOC01-appb-C000021
  
 
Figure JPOXMLDOC01-appb-C000021
  
 
　表９から明らかなように、本発明の粘着シートである実施例１３～２９は、比較例１３および比較例１４の粘着シートと比べて、５％モジュラスの値が小さく、柔軟性に優れていることが分かった。また、本発明の効果を得るためには、ポリオールの分子量は３００以上であることが好ましく、さらに好ましくは５００以上であり、特に好ましくは１，０００以上であることも分かった。ただし、外観の白濁性の観点から、ポリオールの分子量は１０，０００以下であることが好ましく、さらに好ましくは８，０００以下であり、特に好ましくは５，０００以下である。また、柔軟性の効果を得るためには、主剤に対するポリオールのモル比が０．２以上であることが好ましく、更に好ましくは０．２５以上であり、特に好ましくは０．５以上であることも分かった。ただし、外観の白濁性の観点から、ポリオールのモル比は、０．７以下であることが好ましい。 As is apparent from Table 9, Examples 13 to 29, which are the pressure-sensitive adhesive sheets of the present invention, have a smaller value of 5% modulus and excellent flexibility than the pressure-sensitive adhesive sheets of Comparative Examples 13 and 14. I understood that. Moreover, in order to acquire the effect of this invention, it became clear that 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. However, 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. In order to obtain the effect of flexibility, 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.
　また、表９から、本発明の実施例１３～２２，２４～２８の粘着シートは、比較例１３に比べて、コート層と基材との密着性に優れており、特に実施例１３～１５、２６～２８の粘着シートが極めて優れた密着性を示すことが分かった。この理由は、特定配合のコート層用塗布液の作製において、イソシアネート系架橋剤に予め水酸基含有（メタ）アクリルモノマーを反応させてなるコート層用塗布液を用いて成るコート層の上に、複合フィルム用塗布液を塗布して、このコート層と複合フィルム層とを架橋させているからである。また、密着性を発揮するための水酸基含有（メタ）アクリルモノマーのモル比は、主剤に対して、好ましくは０．１以上であり、更に好ましくは０．２以上であり、特に好ましくは０．３以上である。ただし、（メタ）アクリルモノマーのモル比は、伸び特性（破断伸度）の観点から０．５以下であることが好ましい。 Also, from Table 9, 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. In addition, 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. However, the molar ratio of the (meth) acrylic monomer is preferably 0.5 or less from the viewpoint of elongation characteristics (breaking elongation).
　多官能モノマーであるＶ＃８０２の構造は、骨格の剛直性が高いこと、および、アクリロイル基同士の距離が近いため、反応点は増加せず、密着性向上には至らなかった、と考えられる。むしろ、４ＨＢＡに比べＶ＃８０２では、立体障害により反応性が劣ることが推測される。密着性を向上させるためには、アクリル基同士および水酸基との距離がある程度（程度は不明）離れており、骨格が長鎖で柔軟性を持つ方がより好ましいと考えられる。 It is considered that the structure of 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.
　すなわち、本発明によれば、少なくとも、フッ素系ポリマー、ポリオール、水酸基含有（メタ）アクリル系モノマーおよび多官能イソシアネートを用いてなるコート層を有する粘着シートを実現することができ、かかる粘着シートは、優れた柔軟性と優れた密着性とを同時に達成できることが分かった。 That is, according to the present invention, it is possible to realize 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.
　なお、実施例１３～２２，２４～２８および比較例１３～１４についても、柔軟性および密着性の評価結果を基にして総合評価を実施した。すなわち、比較例１３の柔軟性の値を基準値とし、柔軟性がこの基準値（２．０２ＭＰａ）より小さく、かつ、密着性の評価点が２である場合を「良」、柔軟性が基準値より小さく、かつ、密着性の評価点が３である場合を「優」、それ以外の場合を「不可」と表示したところ、実施例１３～１５，２６～２８が「優」、実施例１６～２２，２４～２５，２９が「良」、比較例１４が「不可」であった。なお、実施例２３の粘着シートは密着性において劣ったものであるが、コート層用塗布液を用いて成るコート層の上に、複合フィルム用塗布液を塗布して架橋点を形成するためには、水酸基含有（メタ）アクリルモノマーをコート層用塗布液に配合することが必要である。特定配合のコート層用塗布液の作製において、イソシアネート系架橋剤に予め水酸基含有（メタ）アクリルモノマーを反応させてなるコート層用塗布液を用いて成るコート層の上に、複合フィルム用塗布液を塗布して、このコート層と複合フィルム層とを架橋させているからである。また、密着性を発揮するための水酸基含有（メタ）アクリルモノマーのモル比は、主剤に対して、好ましくは０．１以上であり、更に好ましくは０．２以上であり、特に好ましくは０．３以上である。ただし、（メタ）アクリルモノマーのモル比は、伸び特性（破断伸度）の観点から０．５以下であることがこのましい。 In addition, 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”. In addition, although 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. In the preparation of a coating solution for a coating layer having a specific composition, 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. In addition, 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. However, the molar ratio of the (meth) acrylic monomer is preferably 0.5 or less from the viewpoint of elongation characteristics (breaking elongation).
　多官能モノマーであるＶ＃８０２の構造は、骨格の剛直性が高いこと、および、アクリロイル基同士の距離が近いため、反応点は増加せず、密着性向上には至らなかった、と考えられる。むしろ、４ＨＢＡに比べＶ＃８０２では、立体障害により反応性が劣ることが推測される。密着性を向上させるためには、アクリル基同士および水酸基との距離がある程度（程度は不明）離れており、骨格が長鎖で柔軟性を持つ方がより好ましいと考えられる。 It is considered that the structure of 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.
　すなわち、少なくとも、フッ素系ポリマー、ポリオール、水酸基含有（メタ）アクリル系モノマーおよび多官能イソシアネートを用いてなるコート層を有する粘着シートは、優れた柔軟性と優れた密着性とを同時に達成できるものであることが分かった。 That is, 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.
　本発明の粘着シートは、複雑な部位や曲面等への柔軟性が要求される粘着シートとして好適に使用することができる。また、本発明の粘着シートは、フッ素樹脂によるコート層組成物を用いてなるコート層を有するため、滑り性に優れており、貼付時の作業性が良好である。更に、本発明によれば、コート層と基材との密着性に優れた粘着シートを実現することができる。また、本発明におけるコート層組成物は防汚性にも優れており、例えば、屋外の天候、溶剤、ほこり、油脂および海洋環境などを含む有害環境にさらされる塗膜表面を保護するための粘着シートあるいは装飾用の粘着シートや多層シートとして使用することができる。また、自動車のボディー等の塗膜を保護するためのチッピングテープ、ボディープロテクションフィルム用の粘着シートや多層シートとしても好適である。 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.

Claims (10)

  1. 　　少なくとも、フッ素系ポリマーと、ポリオールと、多官能イソシアネートとを用いてなることを特徴とするコート層組成物。 A coating layer composition comprising at least a fluorine-based polymer, a polyol, and a polyfunctional isocyanate.
  2. 　前記フッ素系ポリマーが、下記式（Ｉ）で表されるフルオロエチレンビニルエーテル交互共重合体であることを特徴とする請求項１に記載のコート層組成物。
    Figure JPOXMLDOC01-appb-C000001
      
     
    （式中、Ｘはフッ素、塩素または臭素を表し、Ｒａは水素またはＣ１～Ｃ１０のアルキル基を表し、ＲｂはＣ１～Ｃ１６のアルキル基を表し、ＲｃはＣ１～Ｃ１６のアルキレン基を表し、ｍおよびｎは、それぞれ整数であり、フルオロエチレンビニルエーテル交互共重合体の重量平均分子量が１，０００～２，０００，０００となる範囲で選択される。）
          The coat layer composition according to claim 1, wherein the fluoropolymer is a fluoroethylene vinyl ether alternating copolymer represented by the following formula (I).
    Figure JPOXMLDOC01-appb-C000001

    (In the formula, X represents fluorine, chlorine or bromine, R a represents hydrogen or a C1-C10 alkyl group, R b represents a C1-C16 alkyl group, and 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.)
  3. 　前記コート層組成物が、さらに水酸基含有（メタ）アクリルモノマーを含有することを特徴とする請求項１または２に記載のコート層組成物。 The coating layer composition according to claim 1 or 2, wherein the coating layer composition further contains a hydroxyl group-containing (meth) acrylic monomer.
  4. 　前記ポリオール成分が、２価のアルコールから選ばれるジオールまたは３価のアルコールから選ばれるトリオールであることを特徴とする請求項１から３のいずれか１項に記載のコート層組成物。 The coating layer composition according to any one of claims 1 to 3, wherein the polyol component is a diol selected from divalent alcohols or a triol selected from trivalent alcohols.
  5. 　更に、紫外線吸収剤、ヒンダードアミン光安定剤、リン系化合物およびフェノール系酸化防止剤からなる群から選ばれる少なくとも１種類を含有する請求項１から４のいずれか１項に記載のコート層組成物。 Furthermore, the coating layer composition of any one of Claim 1 to 4 containing at least 1 sort (s) chosen from the group which consists of a ultraviolet absorber, a hindered amine light stabilizer, a phosphorus compound, and a phenolic antioxidant.
  6. 　基材の少なくとも一方の面にコート層を有する多層シートであって、該コート層が請求項１から５のいずれか１項に記載のコート層組成物を用いてなり、かつ、基材が少なくとも（メタ）アクリルウレタンポリマーまたはウレタンポリマーを含有することを特徴とする多層シート。 A multilayer sheet having a coating layer on at least one surface of a substrate, wherein the coating layer is formed using the coating layer composition according to any one of claims 1 to 5, and the substrate is at least A multilayer sheet comprising (meth) acrylic urethane polymer or urethane polymer.
  7. 　前記基材が、（メタ）アクリルポリマーとウレタンポリマーとを含有する複合フィルムであることを特徴とする請求項６に記載の多層シート。 The multilayer sheet according to claim 6, wherein the base material is a composite film containing a (meth) acrylic polymer and a urethane polymer.
  8. 　前記基材が、紫外線吸収剤、ヒンダードアミン光安定剤、リン系化合物およびフェノール系酸化防止剤からなる群から選ばれる少なくとも１種類を含有することを特徴とする請求項６または７に記載の多層シート。 The multilayer sheet according to claim 6 or 7, wherein the substrate 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. .
  9. 　請求項６から８のいずれか１項に記載の多層シートの少なくとも一方の面に、粘着剤層を有することを特徴とする粘着シート。 A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer on at least one surface of the multilayer sheet according to any one of claims 6 to 8.
  10. 　前記粘着シートが被着体の表面を保護するための保護シートとして使用されることを特徴とする請求項９に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 9, wherein the pressure-sensitive adhesive sheet is used as a protective sheet for protecting the surface of the adherend.
PCT/JP2013/076367 2012-10-01 2013-09-27 Coating layer composition WO2014054542A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012219059 2012-10-01
JP2012-219059 2012-10-01
JP2013092715 2013-04-25
JP2013-092715 2013-04-25

Publications (1)

Publication Number Publication Date
WO2014054542A1 true WO2014054542A1 (en) 2014-04-10

Family

ID=50434870

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/076367 WO2014054542A1 (en) 2012-10-01 2013-09-27 Coating layer composition

Country Status (2)

Country Link
JP (1) JP2014224220A (en)
WO (1) WO2014054542A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135394A1 (en) * 2017-01-19 2018-07-26 パナソニックＩｐマネジメント株式会社 Coating composition, optical member, and illuminator

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6718226B2 (en) * 2015-12-11 2020-07-08 旭化成株式会社 Fluorine coating composition
WO2018150502A1 (en) 2017-02-15 2018-08-23 リンテック株式会社 Roll
WO2018216113A1 (en) * 2017-05-23 2018-11-29 リンテック株式会社 Roll and method for manufacturing roll
JP7259855B2 (en) * 2018-06-13 2023-04-18 Ａｇｃ株式会社 Decorative film, composition, method for producing decorative film, method for producing three-dimensional molded article with decorative film
JP7365777B2 (en) * 2019-03-20 2023-10-20 リンテック株式会社 How to make adhesive film

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6135243A (en) * 1984-07-27 1986-02-19 大成化工株式会社 Plastic article coated with paint containing polymer including fluorine and manufacture thereof
JPS61157384A (en) * 1984-12-28 1986-07-17 Dainippon Toryo Co Ltd Method for painting automobile body
JPS62212471A (en) * 1986-03-13 1987-09-18 Dainippon Ink & Chem Inc Paint resin composition
JPH04106117A (en) * 1990-08-28 1992-04-08 Dainippon Ink & Chem Inc Fluorinated vinyl polymer composition
JPH04292677A (en) * 1991-03-22 1992-10-16 Tonen Corp Coating composition
JPH08295840A (en) * 1995-04-27 1996-11-12 Asahi Glass Co Ltd Resin composition for coating material
JPH08319455A (en) * 1995-05-26 1996-12-03 Asahi Glass Co Ltd Coating composition
JPH10147746A (en) * 1996-11-20 1998-06-02 Daikin Ind Ltd Stain-resistant-film-forming composition and article coated therewith
JPH10211681A (en) * 1997-01-30 1998-08-11 Bridgestone Corp Member for oa equipment
JP2002317142A (en) * 2001-04-23 2002-10-31 Daido Toryo Kk Low polluting coating material and method for forming low polluting coating film
WO2007063698A1 (en) * 2005-11-30 2007-06-07 Daikin Industries, Ltd. Coating composition for solar cell protective covers
JP2008144178A (en) * 2007-12-28 2008-06-26 Kaneka Corp Curable resin composition for top coating and coated article coated with the same
JP2009155487A (en) * 2007-12-27 2009-07-16 Creative Products Tashiro:Kk Fluorine-containing coating agent, coating object, and manufacturing method of coating object
JP2009155500A (en) * 2007-12-27 2009-07-16 Sakai Silk Screen:Kk Antifouling paint composition and antiadhesive body
JP2010260937A (en) * 2009-05-01 2010-11-18 Tohpe Corp Clear-coating composition and coated article comprising the same

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6135243A (en) * 1984-07-27 1986-02-19 大成化工株式会社 Plastic article coated with paint containing polymer including fluorine and manufacture thereof
JPS61157384A (en) * 1984-12-28 1986-07-17 Dainippon Toryo Co Ltd Method for painting automobile body
JPS62212471A (en) * 1986-03-13 1987-09-18 Dainippon Ink & Chem Inc Paint resin composition
JPH04106117A (en) * 1990-08-28 1992-04-08 Dainippon Ink & Chem Inc Fluorinated vinyl polymer composition
JPH04292677A (en) * 1991-03-22 1992-10-16 Tonen Corp Coating composition
JPH08295840A (en) * 1995-04-27 1996-11-12 Asahi Glass Co Ltd Resin composition for coating material
JPH08319455A (en) * 1995-05-26 1996-12-03 Asahi Glass Co Ltd Coating composition
JPH10147746A (en) * 1996-11-20 1998-06-02 Daikin Ind Ltd Stain-resistant-film-forming composition and article coated therewith
JPH10211681A (en) * 1997-01-30 1998-08-11 Bridgestone Corp Member for oa equipment
JP2002317142A (en) * 2001-04-23 2002-10-31 Daido Toryo Kk Low polluting coating material and method for forming low polluting coating film
WO2007063698A1 (en) * 2005-11-30 2007-06-07 Daikin Industries, Ltd. Coating composition for solar cell protective covers
JP2009155487A (en) * 2007-12-27 2009-07-16 Creative Products Tashiro:Kk Fluorine-containing coating agent, coating object, and manufacturing method of coating object
JP2009155500A (en) * 2007-12-27 2009-07-16 Sakai Silk Screen:Kk Antifouling paint composition and antiadhesive body
JP2008144178A (en) * 2007-12-28 2008-06-26 Kaneka Corp Curable resin composition for top coating and coated article coated with the same
JP2010260937A (en) * 2009-05-01 2010-11-18 Tohpe Corp Clear-coating composition and coated article comprising the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135394A1 (en) * 2017-01-19 2018-07-26 パナソニックＩｐマネジメント株式会社 Coating composition, optical member, and illuminator
JPWO2018135394A1 (en) * 2017-01-19 2019-12-19 パナソニックＩｐマネジメント株式会社 Paint composition, optical member and lighting device
JP7241298B2 (en) 2017-01-19 2023-03-17 パナソニックＩｐマネジメント株式会社 Coating composition, optical member and lighting device

Also Published As

Publication number Publication date
JP2014224220A (en) 2014-12-04

Similar Documents

Publication Publication Date Title
JP6340257B2 (en) Adhesive sheet
JP5374227B2 (en) Adhesive sheet for coating film protection
JP5297876B2 (en) Composite film
JP6340258B2 (en) Adhesive sheet
JP2014145034A (en) Multilayer adhesive sheet
JP7055227B2 (en) Multi-layer adhesive sheet
WO2014054542A1 (en) Coating layer composition
WO2011062187A1 (en) Laminate film
JP2011121359A (en) Multilayered sheet
JP6302676B2 (en) Multilayer adhesive sheet
JP5302616B2 (en) Protective adhesive sheet
JP5193816B2 (en) Composite film and method for producing the composite film
JP2015007192A (en) Coat layer composition
JP2006142667A (en) Polyolefinic laminated film and pressure-sensitive adhesive film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13843601

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13843601

Country of ref document: EP

Kind code of ref document: A1