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WO2014119357A1 - Feuille adhésive multicouche - Google Patents

Feuille adhésive multicouche Download PDF

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Publication number
WO2014119357A1
WO2014119357A1 PCT/JP2014/050351 JP2014050351W WO2014119357A1 WO 2014119357 A1 WO2014119357 A1 WO 2014119357A1 JP 2014050351 W JP2014050351 W JP 2014050351W WO 2014119357 A1 WO2014119357 A1 WO 2014119357A1
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WO
WIPO (PCT)
Prior art keywords
adhesive sheet
meth
sensitive adhesive
acrylate
multilayer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2014/050351
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English (en)
Japanese (ja)
Inventor
康徳 山本
中川　善夫
栄一 井本
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Nitto Denko Corp
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Nitto Denko Corp
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Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of WO2014119357A1 publication Critical patent/WO2014119357A1/fr
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C09J133/00—Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
    • 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
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane in the substrate

Definitions

  • the present invention relates to a multilayer pressure-sensitive adhesive sheet, and particularly to a protective multilayer pressure-sensitive adhesive sheet excellent in sticking workability.
  • a transparent adhesive sheet may be affixed to prevent damage to the painted surface of bodies such as automobiles.
  • 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-mentioned problems, and an object of the present invention is to provide a multilayer pressure-sensitive adhesive sheet that has surface slipperiness and curved surface followability and is excellent in pasting workability. .
  • the multilayer pressure-sensitive adhesive sheet of the present invention is a multilayer pressure-sensitive adhesive sheet having at least a surface protective layer, a base material layer, and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is provided on one surface of the base material layer,
  • the surface protective layer is provided on the other surface of the base material layer, the static friction coefficient of the surface protective layer is 0.05 or more and 1.50 or less, and exceeds 0% of the multilayer adhesive sheet.
  • the maximum stress value in a 10% stretched state is in the range of 0.5 MPa or more and 4.0 MPa or less.
  • the surface protective layer preferably contains a urethane polymer as a main component.
  • the urethane polymer is preferably a water-based urethane polymer or a solvent-based urethane polymer.
  • the maximum stress value in the state of exceeding 0% and reaching 100% of the surface protective layer is in the range of 5.0 MPa or more and 24.0 MPa or less.
  • the maximum stress value in a stretched state exceeding 0% and 10% of the base material layer is in a range of 0.5 MPa or more and less than 3.5 MPa.
  • the base material layer preferably contains at least a urethane-based polymer.
  • the base material layer is preferably a urethane polymer, or a composite film containing a (meth) acrylic polymer and a urethane polymer.
  • the multilayer adhesive sheet is preferably used as a protective sheet for protecting the surface of the adherend.
  • the multilayer pressure-sensitive adhesive sheet has a curved surface followability and can be adhered neatly even in a portion where the three-dimensional curved surface is severe, and also has a good surface slipperiness, and has excellent pasting workability. Can be realized.
  • the multilayer pressure-sensitive adhesive sheet of the present invention is a laminated sheet having at least a pressure-sensitive adhesive layer, a base material layer, and a surface protective layer.
  • the surface protective layer is disposed on the outermost surface of the multilayer pressure-sensitive adhesive sheet, and the static friction coefficient of the surface protective layer needs to be 0.05 to 1.50, preferably 0.05 to 1.00. It is particularly preferably 0.05 to 0.5. If the static friction coefficient of the surface protective layer is less than 0.05 or greater than 1.50, good surface slipperiness cannot be realized.
  • This surface protective layer preferably contains a urethane-based polymer as a main component.
  • the urethane polymer is preferably a water-based urethane polymer or a solvent-based urethane polymer.
  • the urethane polymer needs to be liquefied for processing or the like, but the urethane liquefied using an organic solvent such as toluene is called a solvent-based urethane polymer, and many of the urethane polymers are organic solvent-based.
  • water-based urethane polymers are urethanes liquefied using water instead of organic solvents, and water-based urethane polymers are environmentally friendly materials because they can be liquefied without using organic solvents. It can be said.
  • water-based urethane polymer examples include a carbonate-based polymer, a polycarbonate-based polymer, an ester-based polymer, an ether-based polymer, and an ester / acrylic polymer.
  • ester-based water-based urethane polymer products made by ADEKA Co., Ltd. "HUX 232" (100% modulus 25N / mm 2), the trade name of "HUX-380" (100 modulus 8.4N / mm 2), the trade name of "HUX-210" (100% modulus 2.1N / mm 2) are commercially available.
  • polycarbonate-based water-based urethane polymers include ADEKA Corporation's trade name “HUX-561” (100% modulus 5 N / mm 2 ) and trade name “HUX-564”.
  • ether-based water-based urethane polymers include ADEKA Corporation's trade name “HUX-350” (100% modulus 25 N / mm 2 ) and trade name “HUX-”. as 550 "(100% modulus 27N / mm 2 (10%) ) and those commercially available Gerare, the aqueous urethane polymer of an ester / acrylic, K.K. ADEKA "HUX 401" (100% modulus 19N / mm 2), and the like as those commercially available.
  • those having a static friction coefficient of the surface protective layer within the scope of the present invention can be appropriately selected and used.
  • the surface protective layer constituting the multilayer pressure-sensitive adhesive sheet of the present invention preferably satisfies a specific physical property value, for example, the maximum stress value in a stretched state exceeding 0% to 100% exceeds 5.0 MPa,
  • the pressure is preferably 24.0 MPa or less, more preferably 10.0 MPa or more and 20.0 MPa or less, and particularly preferably 12.5 MPa or more and 17.5 MPa or less.
  • the maximum stress value of the surface protective layer is 5.0 to 24.0 MPa, it is easy to realize both the flexibility and the surface slip properties in a balanced manner.
  • the maximum stress value means that the surface protective layer is subjected to a tensile test at a tensile speed of 200 mm / min, a distance between chucks of 30 mm, a room temperature of 20 ° C., and a thickness of 500 ⁇ m, and a stress-strain curve is obtained.
  • the base material layer constituting the multilayer pressure-sensitive adhesive sheet of the present invention is particularly limited as long as the maximum stress value in the stretched state exceeding 0% and up to 10% of the multilayer pressure-sensitive adhesive sheet satisfies 0.5 to 4.0 MPa.
  • a urethane polymer is included, and a film made of a urethane polymer or a composite film including a (meth) acrylic polymer and a urethane polymer is preferable.
  • the urethane polymer includes a homopolymer of urethane, a copolymer of urethane and another polymer other than urethane, and the like.
  • the base material layer preferably has a maximum stress value of more than 0.5 MPa and less than 3.5 MPa, more preferably 1.0 MPa or more, exceeding 0% of the base material layer and up to 10%. 3.0 MPa or less, particularly preferably 1.5 MPa or more and 2.0 MPa or less. If the maximum stress value in the stretched state exceeding 0% and 10% of the base material layer is 0.5 to 3.5 MPa, good curved surface followability can be achieved. Moreover, when this maximum stress value is too low (for example, less than 0.5 MPa), the handling property (ease of handling of the tape) when affixing to a large-area adherend is lowered.
  • the maximum stress value means that a base material layer (width 10 mm, length 160 mm) is subjected to a tensile test at a tensile speed of 200 mm / min, a distance between chucks of 100 mm, and 23 ° C. to obtain a stress-strain curve.
  • the maximum value (maximum stress value) of the stress per unit area from 0% to 10% of the stretched state.
  • the urethane polymer used for the base material layer a urethane homopolymer or copolymer satisfying the stress value is preferably used.
  • the urethane homopolymer is obtained by reacting a polyol and a polyisocyanate.
  • the urethane-based polymer preferably used in the present invention include adipate / ester-based thermoplastic polyurethane, polyether-based thermoplastic polyurethane, polycarbonate-based thermoplastic polyurethane, and polycaprolactone-based thermoplastic polyurethane.
  • a product made by Nippon Matai Co., Ltd. can be commercially obtained as an adipate ester-based thermoplastic polyurethane.
  • the base material layer constituting the multilayer pressure-sensitive adhesive sheet of the present invention is preferably 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. It may not be possible.
  • 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 of a homopolymer. It is preferable to use a monofunctional (meth) acrylic monomer having a temperature (Tg) of 0 ° C. or higher. Furthermore, in this invention, it is preferable that a (meth) acrylic-type polymer uses the acrylic component which further contains the monofunctional (meth) acrylic-type 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-based 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. If the content of the (meth) acrylic acid monomer is less than 1% by weight, it takes a long time 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 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.
  • 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.
  • the term “film” includes a sheet
  • the term “sheet” includes a film.
  • (meth) acryl” is displayed as in the case of a (meth) acrylic polymer and a (meth) acrylic acid monomer
  • the term “methacrylic” and “acrylic” are collectively used. 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, and lauryl acrylate. It is done. These may be used alone or in combination of two or more.
  • acryloylmorpholine isobornyl acrylate, and dicyclopentanyl acrylate as a monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher. It is more preferable to use acryloyl 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 higher is preferably 20 wt% or more and 99 wt% or less in the acrylic component, and is 30 wt% or more and 98 wt% or less. Is more preferable. If the content of the monofunctional (meth) acrylic monomer is less than 20% by weight, there may be a problem that the strength of the film is not sufficient, and if it exceeds 99% by weight, the rigidity of the film becomes too high and becomes brittle. There is a case.
  • 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, tetrahydro Examples include fluorofuryl 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 a 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 if contained, the content is from 0% by weight in the acrylic component.
  • the amount is preferably 50% by weight or less, more preferably more than 0% by weight and 45% by weight or less.
  • 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 cyclododecatrie 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 monomer having a hydroxyl group, a copolymer of a hydroxyl group-containing substance and an acrylic monomer, and the like.
  • epoxy polyol examples include an amine-modified epoxy resin.
  • the urethane polymer does not contain 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 includes 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 preferable.
  • HDI hexamethylene diisocyanate
  • HMDI hydrogenated 4,4-diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • HXDI isophorone diisocyanate
  • 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 of acrylic component / urethane component of 0.25 or more and 4.00 or less, preferably 0.4 or more, 2 .4 or less, particularly preferably 0.5 or more and 1.9 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.
  • a (meth) acryloyl group can be introduced at the molecular end of the urethane prepolymer, and a copolymerizability with a (meth) acrylic monomer is imparted. It is also possible to improve the SS characteristics such as the breaking strength.
  • 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.
  • 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 composite film includes, for example, an acrylic monomer as a diluent, a reaction between diol and diisocyanate in the acrylic monomer to form a urethane polymer, and the acrylic monomer and the urethane polymer as main components.
  • a composite film can be formed by irradiating and curing radiation such as actinic radiation and 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 all at once during the 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 mainly composed of urethane polymer and acrylic monomer 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.
  • additives that are usually used as necessary, for example, ultraviolet absorbers, antioxidants, anti-aging 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.
  • the ultraviolet absorber When adding an ultraviolet absorber, the ultraviolet absorber is preferably added to the substrate layer or the surface protective layer.
  • the ultraviolet absorber examples include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (for example, “TINUVIN PS manufactured by Ciba Japan Co., Ltd.) as a benzotriazole-based ultraviolet absorber.
  • 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 is preferably 0.1% by weight or more and 4.0% by weight or less with respect to 100% by weight of the base material layer. More preferably, the content is 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 A polycondensate of 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine (for example, manufactured by Ciba Japan Co., Ltd.) “TINUVIN 2020”), poly [ ⁇ 6- (1,
  • the thickness of the surface protective layer constituting the multilayer pressure-sensitive adhesive sheet of the present invention is preferably 2 to 50 ⁇ m, more preferably 5 to 40 ⁇ m, still more preferably 8 to 30 ⁇ m. If the thickness of the surface protective layer is less than 2 ⁇ m, a defect site where the surface protective layer is not formed, such as pinholes, is likely to occur, and the characteristics of the surface protective layer may not be fully exhibited. Moreover, when it exceeds 50 micrometers, the physical property of a surface protective layer may reduce the physical property of a base material layer.
  • the thickness of the base material layer constituting the multilayer pressure-sensitive adhesive 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 preferable that it is 150 micrometers or more, and it is especially preferable that it is 200 micrometers or more. Moreover, it is preferable that the upper limit of thickness is about 1 mm.
  • the thickness of the base material layer 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 an automobile body. 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.
  • the surface protective layer can be formed using, for example, a surface protective layer coating solution made of a water-based urethane polymer or a solvent-based urethane polymer.
  • a laminate multilayer sheet
  • a surface protective layer coating solution made of a water-based urethane polymer or a solvent-based urethane polymer.
  • a laminate multilayer sheet
  • a surface protective layer coating solution can be obtained by applying a surface protective layer coating solution on a base material layer, drying and curing to form a surface protective layer.
  • a surface protective layer coating solution is applied onto the peeled PET film and dried to form a surface protective layer.
  • a laminate multi-layer sheet
  • the multilayer sheet can be laminated with another film on the base material layer as long as the effects of the present invention are not impaired.
  • materials for forming other films include polyester resins such as polyethylene terephthalate (PET), polyolefin resins such as polyethylene (PE) and polypropylene (PP), polyimide (PI), and polyetheretherketone (PEEK).
  • thermoplastic resins such as polyvinyl chloride (PVC), polyvinylidene chloride resins, polyamide resins, polyurethane resins, polystyrene resins, acrylic resins, fluorine resins, cellulose resins, polycarbonate resins, etc.
  • thermosetting resins thermosetting resins.
  • the multilayer pressure-sensitive adhesive sheet of the present invention preferably has a structure having a surface protective layer as an outermost surface layer on one surface of the base material layer and a pressure-sensitive adhesive layer on the other surface.
  • 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 the base material layer and drying, or applying these pressure-sensitive adhesives to release paper to form a pressure-sensitive adhesive layer in advance.
  • a method of bonding the pressure-sensitive adhesive layer to the base material layer 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 layer, and both the pressure-sensitive adhesive layer and the film are irradiated with radiation to simultaneously cure and form the base material layer and the pressure-sensitive adhesive layer. it can.
  • the static friction coefficient of a multilayer adhesive sheet is calculated
  • ⁇ Fs / Fp ( ⁇ : static friction coefficient, Fs: static friction force (N), Fp: normal force)
  • the maximum stress value in the stretched state exceeding 0% to 10% of the multilayer pressure-sensitive adhesive sheet needs to be 0.5 to 4.0 MPa, preferably 1.0 MPa or more, 3 0.0 MPa or less, particularly preferably 1.5 MPa or more and 2.0 MPa or less.
  • the maximum stress value in the 10% stretched state exceeding 0% of the multilayer pressure-sensitive adhesive sheet is 0.5 to 4.0 MPa, good curved surface followability can be achieved.
  • this maximum stress value is too low (for example, less than 0.5 MPa), the handling property (ease of handling of the tape) when affixing to a large-area adherend is lowered.
  • the maximum stress value means that a multilayer pressure-sensitive adhesive sheet (width 10 mm, length 160 mm) is subjected to a tensile test at a tensile speed of 200 mm / min, a distance between chucks of 100 mm, and 23 ° C. to obtain a stress-strain curve.
  • the maximum value of stress per unit area from 1% to 10% elongation.
  • the multilayer pressure-sensitive adhesive sheet of the present invention is required to be transparent in order to reflect the color and the like of the coated surface of the adherend in the appearance as it is, but with the same color as the color of the painted surface using a pigment or the like. It may be colored or colored in another color and used as a paint substitute adhesive sheet.
  • an application sheet can be used for, for example, sticking positioning and the like in order to improve the work of attaching the pressure-sensitive adhesive sheet.
  • the multilayer pressure-sensitive adhesive sheet of the present invention has excellent followability to a curved surface, and exhibits excellent pasting workability even on an adherend having a severe three-dimensional curved surface. Therefore, it is suitable as a pressure-sensitive adhesive sheet for protecting an adherend having a large area (attachment) and an adherend having a severe three-dimensional curved surface.
  • a pressure-sensitive adhesive sheet for protecting an adherend having a large area (attachment) and an adherend having a severe three-dimensional curved surface.
  • for protection to protect painted surfaces of transport machines for example, motorcycles, bicycles, rail cars, ships, snowmobiles, gondola, lifts, escalators, automobiles, airplanes, etc., especially automobiles, airplanes, motorcycles, etc.
  • Suitable for applications such as multilayer adhesive 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.
  • Measurement method and evaluation method (1) Measurement of maximum stress value A multilayer pressure-sensitive adhesive sheet was cut into a width of 10 mm and a length of 160 mm, a tensile test was performed at a tensile speed of 200 mm / min, a distance between chucks of 100 mm, and 23 ° C. to obtain a stress-strain curve. . The maximum value (maximum stress value) of the stress per unit area when the multilayer adhesive sheet was stretched by 0% to 10% was determined.
  • 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. Multilayer adhesive sheet) faces upward, that is, for example, the adhesive layer of the multilayer adhesive sheet.
  • a sliding piece contact area 63 mm ⁇ 63 mm
  • the sliding piece is tested at a test speed of 100 mm / min. Pull on.
  • the sample 1 may be directly fixed to the counterpart material 2, but 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 standard for scoring “surface slipperiness” and “curved surface followability” is 4 points for a very good level, 3 points for a problem-free level, 2 points for a level that needs a little improvement, and a level that requires improvement. Is one point, and is shown as an average value of three workers.
  • the pasting workability was evaluated based on the following evaluation criteria.
  • the total score of the pasting workability means the score of curved surface followability + the score of surface slipperiness. Evaluation criteria: “Excellent” The total score for pasting workability is 5 points or more “Good” The total score for pasting workability is greater than 4.5 points and less than 5 points “Inferior” The total score for pasting workability is 4.5 points or less
  • Example 1 Preparation of coating solution for surface protective layer >> A water-based urethane polymer (trade name “F-8082D” manufactured by Daiichi Kogyo Co., Ltd.) was prepared as a coating solution for the surface protective layer.
  • the maximum stress value (100% stress value) in the stretched state of the surface protective layer using this coating solution from 0% to 100% is 24 MPa (catalog value) and is shown in Table 1.
  • a 140- ⁇ m thick adipate-ester thermoplastic polyurethane film (manufactured by Nippon Matai Co., Ltd., hardness 86A) was used.
  • adipate-based thermoplastic polyurethane film (adipate-based TPU film)
  • the prepared coating solution for the surface protective layer is applied so that the thickness after curing is 10 ⁇ m, and dried and cured at a temperature of 80 ° C. for 3 minutes. Then, a surface protective layer was formed on one surface of the base material layer.
  • a pressure-sensitive adhesive composition was prepared by adding 0.3 part of hexanediol diacrylate to 100 parts of the obtained UV syrup.
  • the pressure-sensitive adhesive composition was applied as a release liner to a release-treated surface of a 50 ⁇ m-thick polyethylene terephthalate film (PET film) so that the final product had a thickness of 50 ⁇ m.
  • PET film polyethylene terephthalate film
  • 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
  • a metal halide lamp irradiating with ultraviolet rays (illuminance 290 mW / cm 2 , light amount 4,600 mJ / cm 2 ) using a metal halide lamp.
  • the separator was removed, and the resulting multilayer sheet was bonded to the surface opposite to the surface protective layer side surface (that is, the base material layer surface) using a hand roller so that the adhesive layer overlapped, and the thickness was 200 ⁇ m.
  • a multilayer pressure-sensitive adhesive sheet (surface protective layer / base material layer / pressure-sensitive adhesive layer) was produced. In this multilayer adhesive sheet, a release liner is provided on the adhesive layer.
  • Example 2 As shown in Table 1, the coating solution for the surface protective layer was changed to a water-based urethane polymer (trade name “HUX-401” manufactured by ADEKA Co., Ltd.). A multilayer pressure-sensitive adhesive sheet having a surface protective layer on one side and a pressure-sensitive adhesive layer on the other side was prepared. About the obtained multilayer adhesive sheet and the surface protective layer, the static friction coefficient, the maximum stress value, and the sticking workability were evaluated in the same manner as in Example 1 according to the evaluation method described above. The results are shown in Tables 1 and 2.
  • Example 3 As shown in Table 1, the surface protective layer coating liquid was changed to a water-based urethane polymer (trade name “HUX-564” manufactured by ADEKA Corporation) as shown in Table 1.
  • a multilayer pressure-sensitive adhesive sheet having a surface protective layer on one side and a pressure-sensitive adhesive layer on the other side was prepared.
  • the static friction coefficient, the maximum stress value, and the sticking workability were evaluated in the same manner as in Example 1 according to the evaluation method described above. The results are shown in Tables 1 and 2.
  • Example 4 As shown in Table 1, the type of coating solution for the surface protective layer was changed to an aqueous urethane polymer (trade name “HUX-232” manufactured by ADEKA Co., Ltd.). A multilayer pressure-sensitive adhesive sheet having a surface protective layer on the surface and a pressure-sensitive adhesive layer on the other surface was produced. About the obtained multilayer adhesive sheet and the surface protective layer, the static friction coefficient, the maximum stress value, and the sticking workability were evaluated in the same manner as in Example 1 according to the evaluation method described above. The results are shown in Tables 1 and 2.
  • Example 1 In the same manner as in Example 1, except that the type of coating solution for the surface protective layer was changed to a water-based urethane polymer (trade name “F-2968D” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as shown in Table 1.
  • a multilayer pressure-sensitive adhesive sheet having a surface protective layer on one side of the layer and a pressure-sensitive adhesive layer on the other side was prepared.
  • the static friction coefficient, the maximum stress value, and the sticking workability were evaluated in the same manner as in Example 1 according to the evaluation method described above. The results are shown in Tables 1 and 2.
  • Example 2 A multilayer pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the type of the surface protective layer coating liquid was changed to a fluorine-based coating liquid as shown in Table 1. That is, a 50% solution of fluoroethylene vinyl ether in xylene and toluene (trade name “Lumiflon LF600” manufactured by Asahi Glass Co., Ltd.) and an isocyanate cross-linking agent (trade name “Coronate HX” manufactured by Nippon Polyurethane Industry Co., Ltd.) ), 9.49 parts of dibutyltin lauric acid (trade name “OL1” manufactured by Tokyo Fine Chemical Co., Ltd.) as a catalyst, 0.35 part of a xylene diluted solution (solids concentration 0.1%), and a diluent solvent
  • a fluorine-based coating solution was prepared by mixing at a ratio of 76.41 parts of toluene as the fluorine-based surface protective layer on one surface of the base material
  • Example 3 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one surface of the base material layer was produced in the same manner as in Example 1 except that the surface protective layer was not provided. About the obtained adhesive sheet, it carried out similarly to Example 1, and evaluated the static friction coefficient of the base material layer, the maximum stress value, and the sticking workability
  • F-8082D Water-based urethane polymer (Daiichi Kogyo Seiyaku Co., Ltd.)
  • HUX-401 Water-based urethane polymer (manufactured by ADEKA Corporation)
  • HUX-564 Water-based urethane polymer (manufactured by ADEKA Corporation)
  • HUX-232 Water-based urethane polymer (manufactured by ADEKA Corporation)
  • F-2968D Water-based urethane polymer (Daiichi Kogyo Seiyaku Co., Ltd.)
  • LF600 Fluoroethylene vinyl ether alternating copolymer (Asahi Glass Co., Ltd.)
  • Coreonate HX Isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • the multilayer adhesive sheets of Examples 1 to 4 of the present invention have a smaller maximum stress value in the stretched state of 0% to 10% than the adhesive sheet of Comparative Example 2. , Found to be excellent in flexibility.
  • the maximum stress value in the stretched state of the surface protective layer from 0% to 100% is preferably 24 MPa or less, more preferably 19 MPa or less, particularly Preferably it is 5 MPa or less.
  • the multilayer adhesive sheets of Examples 1 to 4 of the present invention were superior in the slipperiness (static friction coefficient) of the surface protective layer as compared with Comparative Examples 1 and 3.
  • the maximum stress value in the stretched state of the surface protective layer from 0% to 100% is preferably 5 MPa or more, more preferably 19 MPa or more, and particularly preferably 24 MPa or more.
  • the maximum stress value in the stretched state of the surface protective layer from 0% to 100% is within a range of 5 MPa or more and 24 MPa or less. It is necessary to adjust in consideration of the balance between flexibility and surface slipperiness.
  • the multilayer pressure-sensitive adhesive sheet of the present invention can be suitably used as a multilayer pressure-sensitive adhesive sheet that requires flexibility to a curved surface or the like, and is particularly suitable for an adherend (adherent) having a severe three-dimensional curved surface. It can be used for the application and has excellent workability. For example, it can be used as a pressure-sensitive adhesive sheet or a decorative pressure-sensitive adhesive sheet for protecting a coating film surface exposed to harmful environments including outdoor weather, solvents, dust, fats and oils, and marine environments. Further, it is also suitable as a chipping tape for protecting a coating film of an automobile body or the like, an adhesive sheet for a body protection film, or a multilayer sheet.

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Abstract

[Problème] Produire une feuille adhésive multicouche pouvant s'adapter facilement à des surfaces incurvées et présentant une excellente aptitude à la pose. [Solution] Feuille adhésive multicouche comprenant au moins une couche de protection superficielle, une couche de substrat et une couche adhésive. La couche adhésive est disposée sur une face de la couche de substrat et la couche de protection superficielle est disposée sur l'autre face de la couche de substrat. Le coefficient de frottement statique de la couche de protection superficielle est de 0,05 à 1,50, et la valeur de contrainte maximale de la feuille adhésive multicouche, lorsqu'elle est étirée de plus de 0 % à 10 %, est dans une plage de 0,5 MPa à 4,0 MPa.
PCT/JP2014/050351 2013-01-29 2014-01-10 Feuille adhésive multicouche Ceased WO2014119357A1 (fr)

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JP6856475B2 (ja) * 2017-08-24 2021-04-07 リンテック株式会社 粘着フィルムおよびその製造方法
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