WO2014119426A1 - Feuille adhésive multicouche - Google Patents

Feuille adhésive multicouche Download PDF

Info

Publication number
WO2014119426A1
WO2014119426A1 PCT/JP2014/051113 JP2014051113W WO2014119426A1 WO 2014119426 A1 WO2014119426 A1 WO 2014119426A1 JP 2014051113 W JP2014051113 W JP 2014051113W WO 2014119426 A1 WO2014119426 A1 WO 2014119426A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive sheet
meth
sensitive adhesive
multilayer
acrylate
Prior art date
Application number
PCT/JP2014/051113
Other languages
English (en)
Japanese (ja)
Inventor
康徳 山本
中川　善夫
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=51262141&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014119426(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2014119426A1 publication Critical patent/WO2014119426A1/fr

Links

Images

Classifications

    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/006—Presence of (meth)acrylic 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
    • 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 more particularly to a multilayer pressure-sensitive adhesive sheet excellent in solvent resistance, surface slipperiness and curved surface followability.
  • a transparent adhesive sheet may be affixed to prevent damage to the painted surface of bodies such as automobiles.
  • This pressure-sensitive adhesive sheet requires solvent resistance for use outdoors, and this pressure-sensitive adhesive sheet is directly affixed to the painted surface manually using a squeegee or the like.
  • problems such as dirt on the hands, or inability to apply cleanliness particularly in areas where the three-dimensional curved surface is severe.
  • 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.
  • an adhesive sheet in which a fluorine coating layer is provided on a substrate made of IPN is known (see, for example, JP-T-2001-520127).
  • a pressure-sensitive adhesive sheet for protecting a coating film for example, see JP-A-2009-299053
  • the flexibility was insufficient, and it was 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 multilayer pressure-sensitive adhesive sheet excellent in solvent resistance, surface slipperiness and curved surface followability.
  • 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 surface protective layer contains N, N-dimethylformamide (DMF) insoluble matter, 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 50% by weight or more of N, N-dimethylformamide (DMF) insoluble matter.
  • DMF N, N-dimethylformamide
  • 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 surface protective layer preferably contains 5 to 12 parts by weight of a crosslinking agent with respect to 100 parts by weight of the urethane polymer.
  • 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.
  • a multilayer pressure-sensitive adhesive sheet that has excellent solvent resistance, has curved surface followability, can be neatly adhered even at a severe three-dimensional curved surface, and has good surface slipperiness. 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 contains N, N-dimethylformamide (DMF) insoluble matter.
  • the surface protective layer is arrange
  • This surface protective layer is preferably composed mainly of a urethane-based polymer.
  • the base resin of the surface protective layer is preferably a urethane-based polymer.
  • 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.
  • ether-based water-based urethane polymer examples include a product name“ HUX-350 ”(100% modulus 25 N / mm 2 ) manufactured by ADEKA Corporation, and a product name“ HUX-550 "(100% modulus 27N / mm 2 (10%) ) such as those commercially available Mentioned and, as the water-based 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.
  • Two or more water-based polyurethanes may be used in combination.
  • the surface protective layer constituting the multilayer pressure-sensitive adhesive sheet of the present invention preferably contains a crosslinking agent.
  • the content of the crosslinking agent is preferably 5 parts by weight or more and 12 parts by weight or less, more preferably 5 parts by weight or more and 11 parts by weight or less, with respect to 100 parts by weight of the base resin constituting the surface protective layer. Particularly preferably, it is 5 parts by weight or more and 9 parts by weight or less.
  • the crosslinking agent is contained in an amount of 5 parts by weight or more and 12 parts by weight or less, an appropriate gel fraction can be easily realized.
  • crosslinking agent preferably used for the surface protective layer examples include an oxazoline crosslinking agent, a carbodiimide crosslinking agent, and an epoxy crosslinking agent.
  • an oxazoline crosslinking agent the trade name “(registered trademark) Epocross WS-700” (oxazoline group-containing water-soluble polymer, manufactured by Nippon Shokubai Co., Ltd.), the trade name “(registered trademark) Epocross WS-500” (oxazoline) Group-containing water-soluble polymer (manufactured by Nippon Shokubai Co., Ltd.), and the like.
  • carbodiimide-based crosslinking agents examples include the trade name “(registered trademark) Carbodilite E-02” (carbodiimide group-containing water-soluble). Polymer, manufactured by Nisshinbo Co., Ltd.), trade name “(registered trademark) Carbodilite E-01” (carbodiimide group-containing water-soluble polymer, manufactured by Nisshinbo Co., Ltd.), and the like.
  • epoxy-based crosslinking agent the trade name “(registered trademark) GL-PEP” (epoxy group-containing water-soluble polymer, Made day-shi synthesis Co., Ltd.), trade name “(registered trademark) Denacol EX-313” (epoxy group-containing water-soluble polymer, manufactured by Nagase Chemtex Co., Ltd.) and the like as those commercially available.
  • the surface protective layer can further contain additives such as a repellent, a thickener, a light stabilizer, and an ultraviolet absorber.
  • a repellent leveling agent
  • examples of the repellent (leveling agent) include polyether-based modified siloxane, sodium perfluoroalkenyloxybenzene sulfonate, polyester-based modified siloxane, and aralkyl-modified siloxane.
  • examples of the light stabilizer include, for example, water dispersion Type hindered amine light stabilizers and the like
  • examples of the ultraviolet absorber include water-dispersed benzotriazole-based ultraviolet absorbers.
  • the surface protective layer preferably has a static friction coefficient of 0.05 to 1.50, more preferably 0.05 to 1.00, and particularly preferably 0.05 to 0.5.
  • the static friction coefficient of the surface protective layer is 0.05 or more and 1.50 or less, good surface slipperiness can be realized.
  • the maximum stress value in the stretched state exceeding 0% to 100% of the surface protective layer is 5.0 MPa or more and 24.0 MPa or less, and more preferably. Is 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 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, 20 ° C. and a thickness of 500 ⁇ m to obtain a stress-strain curve, and 0% to 100% of the surface protective layer 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.
  • 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.
  • 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.
  • “including as a main component” means containing 50% by weight or more, preferably containing 90% by weight or more, and also containing 100%.
  • 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.
  • the composite film contains commonly used additives such as UV absorbers, antioxidants, anti-aging agents, fillers, pigments, colorants, flame retardants, antistatic agents, light stabilizers, etc. It can add within the range which does not inhibit the effect of this invention. These additives are used in normal amounts depending on the type. These additives may be added in advance before the polymerization reaction between the diisocyanate and the diol, or may be added before the urethane polymer and the acrylic monomer are polymerized.
  • additives such as UV absorbers, antioxidants, anti-aging agents, fillers, pigments, colorants, flame retardants, antistatic agents, light stabilizers, etc. It can add within the range which does not inhibit the effect of this invention. These additives are used in normal amounts depending on the type. These additives may be added in advance before the polymerization reaction between the diisocyanate and the diol, or may be added before the urethane polymer and the acrylic monomer are polymerized.
  • 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 Reactive organisms 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 preferably 0.1% by weight or more and 4.0% by weight or less, based on 100% by weight of the film precursor, and is 0.5% by weight or more and 2.0% by weight More preferably, it is as follows. 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,
  • 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.
  • 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 140 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 stretched state exceeding 0% and up to 10% of the multilayer pressure-sensitive adhesive sheet is from 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 (easy 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 is excellent in followability to a curved surface and can be suitably used for an adherend having a severe three-dimensional curved surface. Moreover, the multilayer pressure-sensitive adhesive sheet of the present invention is excellent in solvent resistance, for example, as a film for surface protection and decoration of adherends exposed to harmful environments such as outdoor weather, solvents, dust, fats and oils and marine environments. Can be used. Also, for protection to protect the body painted surface of transport machinery, for example, motorcycles, bicycles, railway vehicles, ships, snowmobiles, gondola, lifts, escalators, automobiles, aircrafts, etc., especially automobiles, aircrafts, motorcycles, etc. It is also suitable as a multilayer adhesive sheet, body protection film, and the like.
  • 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 obtained multilayer pressure-sensitive adhesive sheet (width 30 mm, length 50 mm) was attached to a black panel (KINO-1210TW: manufactured by Kansai Paint Co., Ltd.) and multilayer adhesive with a cloth impregnated with ethanol. The surface of the sheet was rubbed 20 times, and then the multilayer adhesive sheet was evaluated in two stages. The evaluation was performed based on the following evaluation criteria. (Evaluation criteria) ⁇ The cloudiness (dissolution) of the multilayer adhesive sheet is not confirmed. X The cloudiness (dissolution) of the multilayer pressure-sensitive adhesive sheet is confirmed.
  • 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.
  • a coating solution for the surface protective layer 55.88 parts of an aqueous urethane polymer (a carbonate polyurethane emulsion (main agent), trade name “F-2954D-5” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), an aqueous urethane polymer (first 44.12 parts of carbonate-based polyurethane emulsion (main agent) manufactured by Kogyo Kagaku Co., Ltd., trade name “Superflex 460”), and 5 “Epocross WS-700” (produced by Nippon Shokubai Co., Ltd.) as the oxazoline-based cross-linking agent .81 parts, as a leveling agent, 0.1 part of a polyether-based modified siloxane (trade name “BYK-349”, manufactured by Big Chemie Japan Co., Ltd.) and sodium perfluoroalkenyloxybenzenesul
  • a polyether-based modified siloxane trade name “BYK
  • the foam was removed using a defoaming device (2000 rpm, 10 min) to prepare a coating solution for a surface protective layer.
  • the maximum stress value of the surface protective layer using this coating solution in the 0% to 100% stretched state was 6.45 MPa (calculated 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 140 ° 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 amount of coating solution for the surface protective layer is 45.78 parts for the trade name “F-2954D-5”, 54.22 parts for the trade name “Superflex 460”, and the trade name “Epocross WS”. -700 "is 5.81 parts, the trade name" BKY-349 "is 0.1 part, the trade name” Futgent 100 (1% diluted solvent) "is 1.00 parts, and the trade name” Leoleate 216 "is 1. 00 parts, the product name “UC-606” was changed to 0.80 parts, and the product name “UC-3140” was changed to 0.20 parts. 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.
  • Example 3 A multilayer pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the type of the coating solution for the surface protective layer was changed to a fluorine-based coating solution as shown in Table 2. That is, a 50% concentration solution of fluoroethylene vinyl ether in xylene and toluene (trade name “Lumiflon LF600” manufactured by Asahi Glass Co., Ltd.) and an isocyanate crosslinking agent (trade name “Coronate manufactured by Nippon Polyurethane Industry Co., Ltd.”) 9.49 parts of HX "), 0.35 parts of xylene diluted solution (solid content concentration 0.1%) of dibutyltin lauric acid (trade name” OL1 "manufactured by Tokyo Fine Chemical Co., Ltd.) as a catalyst, A fluorine-based coating solution was prepared by mixing in a proportion of 76.41 parts of toluene as a diluting solvent.
  • a protective layer was formed, and an adhesive layer was formed on the other surface to produce a multilayer adhesive sheet.About the obtained multilayer adhesive sheet and surface protective layer The static friction coefficient, the maximum stress value, the gel fraction, the solvent resistance, and the pasting workability were evaluated in accordance with the evaluation method described above in the same manner as in Example 1. It shows in Table 2.
  • Example 4 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 multilayer adhesive sheet, it carried out similarly to Example 1, and performed the measurement of the static friction coefficient, the measurement of the maximum stress value, the evaluation of solvent resistance, and the evaluation of sticking workability according to the evaluation method shown above. The results are shown in Table 2.
  • Example 5 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the base material layer was changed to caprolactone-based polyurethane (manufactured by Nippon Matai Co., Ltd.) and no surface protective layer was provided, and the same measurement as in Example 1 was performed. And evaluated. The results are shown in Table 2.
  • F-2954D-5 Carbonate polyurethane emulsion (main agent) (Daiichi Kogyo Seiyaku Co., Ltd.) Superflex 460: Carbonate polyurethane emulsion (main agent) (Daiichi Kogyo Seiyaku Co., Ltd.)
  • Epocross WS-700 Oxazoline-based crosslinking agent (manufactured by Nippon Shokubai Co., Ltd.)
  • BYK-349 Leveling agent, polyether-based modified siloxane (manufactured by Big Chemie-Japan Co., Ltd.) Footage 100: Leveling agent, sodium perfluoroalkenyloxybenzenesulfonate (manufactured by Neos)
  • Rheorate 216 Thickener (made by Elementis Japan)
  • UC-606 Water dispersion type light stabilizer (manufactured by ADEKA Corporation)
  • UC-3140 Water-dispersed light
  • the multilayer pressure-sensitive adhesive sheets of Examples 1 and 2 of the present invention have higher solvent resistance than the pressure-sensitive adhesive sheets of Comparative Examples 1 and 2 to which no crosslinking agent is added. I found it excellent. This is considered to be due to the improvement of the solvent resistance by the addition of the crosslinking agent.
  • the surface protective layer needs to contain a crosslinking agent.
  • the crosslinking agent is 5 parts by weight or more with respect to 100 parts by weight of the base resin of the surface protective layer, The content is preferably 12 parts by weight or less, more preferably 5 parts by weight or more and 11 parts by weight or less, and particularly preferably 5 parts by weight or more and 9 parts by weight or less.
  • the multilayer adhesive sheets of Examples 1 and 2 have a lower maximum stress value in a stretched state of 0% to 10% than the multilayer adhesive sheet of Comparative Example 3 having a fluorine-based surface protective layer, and are flexible. It was found to be excellent.
  • the multilayer pressure-sensitive adhesive sheets of Examples 1 and 2 retain the same flexibility as that of Comparative Example 4 of the pressure-sensitive adhesive sheet consisting of only the base material layer and the pressure-sensitive adhesive layer without providing the surface protective layer, and have solvent resistance. It was also found to be excellent in slipperiness. Therefore, according to the present invention, a multilayer adhesive sheet excellent in all of flexibility, slipperiness and solvent resistance could be realized.
  • 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 particularly suitable for an adherend having a severe three-dimensional curved surface. Can do.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

[Problème] Produire une feuille adhésive multicouche ayant une bonne résistance aux solvants, une surface glissant et pouvant s'adapter à des surfaces incurvées. [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. La couche de protection superficielle contient un N, N-diméthylformamide (DMF), qui est insoluble, 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/JP2014/051113 2013-01-29 2014-01-21 Feuille adhésive multicouche WO2014119426A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-014525 2013-01-29
JP2013014525 2013-01-29

Publications (1)

Publication Number Publication Date
WO2014119426A1 true WO2014119426A1 (fr) 2014-08-07

Family

ID=51262141

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/051113 WO2014119426A1 (fr) 2013-01-29 2014-01-21 Feuille adhésive multicouche

Country Status (2)

Country Link
JP (3) JP6681654B2 (fr)
WO (1) WO2014119426A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015019726A1 (fr) * 2013-08-05 2015-02-12 日東電工株式会社 Feuille adhésive
WO2019030914A1 (fr) * 2017-08-10 2019-02-14 株式会社寺岡製作所 Feuille adhésive

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6513371B2 (ja) * 2014-11-06 2019-05-15 日東電工株式会社 表面保護シート
MX2017012451A (es) * 2015-03-31 2018-02-15 Jnc Corp Agente de recubrimiento, película de recubrimiento, articulo de laminado y superficie protegida.
JP6810528B2 (ja) * 2016-03-29 2021-01-06 スリーエム イノベイティブ プロパティズ カンパニー ライセンスプレート用グラフィックフィルム及びライセンスプレート、並びにそれらの製造方法
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

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000191993A (ja) * 1998-12-25 2000-07-11 Minnesota Mining & Mfg Co <3M> 接着シ―ト、接着シ―ト用保護フィルム、床面保護構造体、および接着シ―トの製造方法
JP2003027016A (ja) * 2001-06-26 2003-01-29 Three M Innovative Properties Co 接着シート、及びマーキングフィルム
JP2003062948A (ja) * 2001-08-10 2003-03-05 Three M Innovative Properties Co 防汚染性保護フィルム及び接着シート
WO2004065510A1 (fr) * 2003-01-22 2004-08-05 Lintec Corporation Feuille d'adhesif autocollant, procede de protection de surface de plaquette a semiconducteur et procede de traitement
JP2005511356A (ja) * 2001-12-07 2005-04-28 スリーエム イノベイティブ プロパティズ カンパニー 保護ポリウレタン層を含む多層シート
JP2007522957A (ja) * 2003-10-28 2007-08-16 スリーエム イノベイティブ プロパティズ カンパニー 装飾性保護フィルム
WO2009051059A1 (fr) * 2007-10-19 2009-04-23 Sekisui Chemical Co., Ltd. Bande adhésive pour la protection d'un photomasque
JP2011012127A (ja) * 2009-06-30 2011-01-20 Three M Innovative Properties Co マーキングフィルム
JP2011103449A (ja) * 2009-10-15 2011-05-26 Achilles Corp 半導体製造工程用テープの基材フィルム
JP2012224683A (ja) * 2011-04-15 2012-11-15 Nitto Denko Corp 粘着シート

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4831742B1 (fr) * 1968-03-01 1973-10-01
DE69827142T2 (de) * 1998-11-11 2006-03-09 Minnesota Mining And Manufacturing Co., St. Paul Mehrschichtige Folie enthaltend eine Polyurethanschutzschicht
BRPI0610999A2 (pt) * 2005-04-29 2010-08-10 3M Innovative Properties Co pelìcula protetora em múltiplas camadas, e, método para fabricar uma pelìcula protetora em múltiplas camadas
JP5426387B2 (ja) * 2006-10-04 2014-02-26 スリーエム イノベイティブ プロパティズ カンパニー 多層ポリウレタン保護フィルムの製造方法
JP5399625B2 (ja) * 2007-11-13 2014-01-29 日東電工株式会社 複合フィルム
EP2287264A4 (fr) * 2008-05-14 2013-09-04 Nitto Denko Corp Feuille adhésive pour la protection d un film de revêtement
JP5441376B2 (ja) * 2008-08-01 2014-03-12 日産自動車株式会社 皮革用防汚塗料組成物、並びに、塗装物品およびその製造方法
JP5302616B2 (ja) * 2008-10-14 2013-10-02 日東電工株式会社 保護用粘着シート

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000191993A (ja) * 1998-12-25 2000-07-11 Minnesota Mining & Mfg Co <3M> 接着シ―ト、接着シ―ト用保護フィルム、床面保護構造体、および接着シ―トの製造方法
JP2003027016A (ja) * 2001-06-26 2003-01-29 Three M Innovative Properties Co 接着シート、及びマーキングフィルム
JP2003062948A (ja) * 2001-08-10 2003-03-05 Three M Innovative Properties Co 防汚染性保護フィルム及び接着シート
JP2005511356A (ja) * 2001-12-07 2005-04-28 スリーエム イノベイティブ プロパティズ カンパニー 保護ポリウレタン層を含む多層シート
WO2004065510A1 (fr) * 2003-01-22 2004-08-05 Lintec Corporation Feuille d'adhesif autocollant, procede de protection de surface de plaquette a semiconducteur et procede de traitement
JP2007522957A (ja) * 2003-10-28 2007-08-16 スリーエム イノベイティブ プロパティズ カンパニー 装飾性保護フィルム
WO2009051059A1 (fr) * 2007-10-19 2009-04-23 Sekisui Chemical Co., Ltd. Bande adhésive pour la protection d'un photomasque
JP2011012127A (ja) * 2009-06-30 2011-01-20 Three M Innovative Properties Co マーキングフィルム
JP2011103449A (ja) * 2009-10-15 2011-05-26 Achilles Corp 半導体製造工程用テープの基材フィルム
JP2012224683A (ja) * 2011-04-15 2012-11-15 Nitto Denko Corp 粘着シート

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015019726A1 (fr) * 2013-08-05 2015-02-12 日東電工株式会社 Feuille adhésive
US10392533B2 (en) 2013-08-05 2019-08-27 Nitto Denko Corporation Adhesive sheet
WO2019030914A1 (fr) * 2017-08-10 2019-02-14 株式会社寺岡製作所 Feuille adhésive
JPWO2019030914A1 (ja) * 2017-08-10 2020-09-03 株式会社寺岡製作所 接着シート
US11781042B2 (en) 2017-08-10 2023-10-10 Teraoka Seisakusho Co., Ltd. Adhesive sheet

Also Published As

Publication number Publication date
JP2014167099A (ja) 2014-09-11
JP2021073114A (ja) 2021-05-13
JP2020050880A (ja) 2020-04-02
JP7055227B2 (ja) 2022-04-15
JP6681654B2 (ja) 2020-04-15

Similar Documents

Publication Publication Date Title
JP6340257B2 (ja) 粘着シート
JP5374227B2 (ja) 塗膜保護用粘着シート
JP7055227B2 (ja) 多層粘着シート
JP2014145034A (ja) 多層粘着シート
JP6340258B2 (ja) 粘着シート
US20110058950A1 (en) Protecting film for blade of wind power generator
JP2012046723A (ja) アプリケーションテープ
WO2010026980A1 (fr) Film composite
JP6302676B2 (ja) 多層粘着シート
WO2014054542A1 (fr) Composition de couche de revêtement
JP2011121359A (ja) 多層シート
JP5302616B2 (ja) 保護用粘着シート
JP5193816B2 (ja) 複合フィルム及び該複合フィルムの製造方法
JP2015007192A (ja) コート層組成物

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: 14746281

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: 14746281

Country of ref document: EP

Kind code of ref document: A1