WO2018181453A1 - Film stratifié adhésif et structure - Google Patents

Film stratifié adhésif et structure Download PDF

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Publication number
WO2018181453A1
WO2018181453A1 PCT/JP2018/012701 JP2018012701W WO2018181453A1 WO 2018181453 A1 WO2018181453 A1 WO 2018181453A1 JP 2018012701 W JP2018012701 W JP 2018012701W WO 2018181453 A1 WO2018181453 A1 WO 2018181453A1
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WIPO (PCT)
Prior art keywords
film
adhesive
adhesive resin
meth
ito
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PCT/JP2018/012701
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English (en)
Japanese (ja)
Inventor
広樹 池沼
恭三 栗田
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三井化学東セロ株式会社
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Application filed by 三井化学東セロ株式会社 filed Critical 三井化学東セロ株式会社
Priority to JP2019509960A priority Critical patent/JP6715390B2/ja
Priority to CN201880019582.4A priority patent/CN110431205B/zh
Publication of WO2018181453A1 publication Critical patent/WO2018181453A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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

Definitions

  • the present invention relates to an adhesive laminated film and a structure.
  • a transparent conductive film on which an indium tin oxide (ITO) film is formed is used for touch panels and electronic paper.
  • a surface protective film may be bonded to the transparent conductive film in order to prevent the surface from being soiled or damaged.
  • Patent Document 1 Japanese Patent Laid-Open No. 2015-202681.
  • Patent Document 1 is a surface protective film for protecting the surface opposite to the surface on which the transparent conductive film of the transparent conductive film is formed, and has a coating layer on at least one surface of the laminated polyester film, There is described a surface protective film for a conductive film, characterized in that the ester cyclic trimer precipitation amount on the surface of the coating layer is 1.2 mg / m 2 or less when heated at 150 ° C. for 90 minutes.
  • the heat treatment may be performed in a state where the surface protective film is attached to the ITO film side of the transparent conductive film.
  • the present inventors have a paste residue phenomenon that a part of the adhesive resin layer remains on the ITO film after the heat treatment. It was found that there is a case.
  • the present invention has been made in view of the above circumstances, and provides an adhesive laminated film capable of suppressing adhesive residue on the ITO film when heat-treated while being attached to the ITO film. It is.
  • the inventors of the present invention have made extensive studies in order to achieve the above problems.
  • the scale of the peel strength ratio before and after the heat treatment between the ITO film and the adhesive resin layer suppresses adhesive residue on the ITO film when the heat treatment is performed in a state of being attached to the ITO film.
  • the present invention has been completed by obtaining the knowledge that it is effective as a design guideline for an adhesive film.
  • the following adhesive laminated film and structure are provided.
  • An adhesive laminated film for protecting the surface of an indium tin oxide (ITO) film, A base material layer, and an adhesive resin layer provided on one surface of the base material layer The peel strength between the ITO film deposited on the base film and the adhesive resin layer, measured by the following method, is P 0 [N / 25 mm], and the adhesive resin layer is applied to the base film.
  • the above-mentioned ITO film and the above-mentioned adhesive resin layer after pasting the above-mentioned adhesive laminated film on the above-mentioned ITO film so as to be in contact with the deposited ITO film, and then heat-treating the obtained structure at 150 ° C.
  • Adhesive laminated film P 1 / P 0 is 1.0 to 25. (Measurement method of peeling strength P 0)
  • the adhesive laminate film is attached to the ITO film so that the adhesive resin layer is in contact with the ITO film deposited on the base film.
  • the adhesive laminated film was peeled from the ITO film in the direction of 180 degrees under the conditions of 23 ° C. and a tensile speed of 300 mm / min, and the strength (N / 25 mm) at that time was peel strength. and P 0.
  • the peel strength (P 0) is adhesive laminated film is not more than 0.01 N / 25 mm or more 1.0 N / 25 mm.
  • Adhesive laminated film above peel strength (P 1) is less than 0.1 N / 25 mm or more 1.0 N / 25 mm.
  • the adhesive resin layer is an adhesive laminated film containing a (meth) acrylic adhesive resin.
  • the adhesive laminated film whose thickness of the said adhesive resin layer is 1 micrometer or more and 50 micrometers or less.
  • the resin constituting the base layer is polyolefin, polyester, polyamide, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyetherimide, ethylene / vinyl acetate copolymer, polyacrylonitrile, polycarbonate, polystyrene.
  • An adhesive laminate film comprising one or more selected from ionomer, polysulfone, polyethersulfone and polyphenylene ether.
  • ITO indium tin oxide
  • an adhesive laminated film capable of suppressing the adhesive residue on the ITO film when the heat treatment is performed in a state of being attached to the ITO film.
  • FIG. 1 is a cross-sectional view schematically showing an example of the structure of an adhesive laminated film 50 according to an embodiment of the present invention.
  • an adhesive laminated film 50 is an adhesive laminated film for protecting the surface of an indium tin oxide (ITO) film, and includes a base material layer 10 and a base material layer. 10, and an adhesive resin layer 20 provided on one surface. Then, the adhesive laminated film 50 according to this embodiment is measured by the following method, the peel strength P 0 between the ITO film deposited on the substrate film and the adhesive resin layer 20 [N / 25 mm The adhesive laminate film 50 was attached to the ITO film so that the adhesive resin layer 20 was in contact with the ITO film deposited on the base film, and then the resulting structure was heat-treated at 150 ° C. for 60 minutes.
  • ITO indium tin oxide
  • P 1 / P 0 is 1.0 or more and 25 or less.
  • the adhesive laminate film 50 is attached to the ITO film so that the adhesive resin layer 20 is in contact with the ITO film deposited on the base film.
  • the adhesive laminate film 50 is peeled from the ITO film in the direction of 180 degrees under the conditions of 23 ° C. and a pulling speed of 300 mm / min.
  • the strength (N / 25 mm) at that time is peel strength P 0 .
  • the scale of the peel strength ratio before and after the heat treatment between the ITO film and the adhesive resin layer suppresses adhesive residue on the ITO film when the heat treatment is performed in a state of being attached to the ITO film. It was found for the first time that it was effective as a design guideline for adhesive films.
  • the adhesive laminated film 50 according to the present embodiment has the above-mentioned P 1 / P 0 within the above range, whereby the adhesive on the ITO film when the heat treatment is performed in a state of being attached to the ITO film. The rest can be suppressed.
  • the upper limit value of P 1 / P 0 is 25 or less, but the adhesive residue on the ITO film when the heat treatment is performed in a state of being attached to the ITO film is more From the viewpoint of further suppression, it is preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less.
  • the peel strength (P 0 ) is set to be 0.1 from the viewpoint of further improving the initial adhesive force and suppressing the pressure-sensitive adhesive laminated film 50 from floating from the ITO film. It is preferably 01 N / 25 mm or more, more preferably 0.02 N / 25 mm or more, and further preferably 0.03 N / 25 mm or more.
  • the adhesive laminate film 50 is preferably 1.0 N / 25 mm or less, more preferably 0.5 N / 25 mm or less, and still more preferably 0.2 N / 25 mm or less.
  • the peel strength (P 1 ) is preferably from 0.1 N / 25 mm to 1.0 N / 25 mm.
  • the P 1 / P 0 in the range as described above constitutes for example, the types and proportions of the components constituting the adhesive resin layer 20, an adhesive resin layer 20 adhesive It is necessary to highly control the type and content ratio of each monomer in the conductive resin.
  • the glass transition temperature of the adhesive resin constituting the adhesive resin layer 20, the type and content ratio of each monomer in the adhesive resin constituting the adhesive resin layer 20 are the above P 1 / It cited as a factor for controlling the P 0.
  • the total thickness of the pressure-sensitive adhesive laminated film 50 according to this embodiment is preferably 2 ⁇ m or more and 550 ⁇ m or less, more preferably 6 ⁇ m or more and 330 ⁇ m or less, and further preferably 12 ⁇ m or more and 165 ⁇ m, from the viewpoint of the balance between mechanical properties and handleability. It is as follows.
  • the base material layer 10 is a layer provided for the purpose of improving the handling properties, mechanical properties, heat resistance, and other properties of the adhesive laminated film 50.
  • the base material layer 10 is not specifically limited, For example, a resin film is mentioned.
  • Examples of the resin constituting the substrate layer 10 include polyolefins such as polyethylene, polypropylene, poly (4-methyl-1-pentene), and poly (1-butene); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like.
  • Polyester such as nylon-6, nylon-66, polymetaxylene adipamide; polyacrylate; polymethacrylate; polyvinyl chloride; polyvinylidene chloride; polyimide; polyetherimide; ethylene-vinyl acetate copolymer;
  • One or more selected from acrylonitrile, polycarbonate, polystyrene, ionomer, polysulfone, polyethersulfone, polyphenylene ether, and the like can be given.
  • one or two or more selected from polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyimide are preferable from the viewpoint of excellent balance of heat resistance, transparency, mechanical strength, price, and the like.
  • Polypropylene, polyethylene At least one selected from terephthalate and polyethylene naphthalate is more preferable.
  • the base material layer 10 may be a single layer or two or more layers.
  • the form of the resin film used to form the base material layer 10 may be a stretched film or a film stretched in a uniaxial direction or a biaxial direction. From the viewpoint of improving the heat resistance and mechanical strength of the film, a film stretched in a uniaxial direction or a biaxial direction is preferable.
  • the thickness of the base material layer 10 is preferably 1 ⁇ m or more and 500 ⁇ m or less, more preferably 5 ⁇ m or more and 300 ⁇ m or less, and further preferably 10 ⁇ m or more and 150 ⁇ m or less from the viewpoint of obtaining good film properties.
  • the base material layer 10 may be subjected to a surface treatment in order to improve adhesion with other layers. Specifically, corona treatment, plasma treatment, undercoat treatment, primer coat treatment, or the like may be performed.
  • the adhesive resin layer 20 is a layer that is provided on one surface side of the base material layer 10 and adheres to the surface of the ITO film, and is a layer for attaching the adhesive laminated film 50 to the ITO film. is there.
  • the adhesive resin layer 20 contains an adhesive resin (P).
  • the adhesive resin (P) include (meth) acrylic adhesive resins, silicone adhesive resins, urethane adhesive resins, olefin adhesive resins, and styrene adhesive resins. Among these, a (meth) acrylic adhesive resin is preferable from the viewpoint of facilitating adjustment of adhesive strength.
  • (meth) acrylic-type adhesive resin used for the adhesive resin layer 20 the copolymer containing the structural unit (A) derived from the (meth) acrylic-acid alkylester is mentioned, for example.
  • (meth) acrylic acid alkyl ester means acrylic acid alkyl ester, methacrylic acid alkyl ester, or a mixture thereof.
  • the (meth) acrylic pressure-sensitive adhesive resin according to this embodiment includes, for example, a mixture containing a (meth) acrylic acid alkyl ester monomer and another monomer copolymerizable with the (meth) acrylic acid alkyl ester monomer. It can be obtained by polymerization.
  • Examples of the (meth) acrylic acid alkyl ester monomer that forms the structural unit (A) derived from the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
  • (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferable, and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is more preferable.
  • Specific examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. These may be used alone or in combination of two or more.
  • the content of the structural unit (A) derived from the (meth) acrylic acid alkyl ester is the sum of all the structural units in the (meth) acrylic adhesive resin.
  • it is 100 mass%, it is preferable that it is 50 to 95 mass%, and it is more preferable that it is 55 to 92 mass%.
  • the (meth) acrylic adhesive resin according to this embodiment is derived from other monomers copolymerizable with the (meth) acrylic acid alkyl ester monomer from the viewpoint of improving cohesion, heat resistance, crosslinkability, and the like.
  • a structural unit (B) is further included.
  • the monomer that forms the structural unit (B) include cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.
  • Carboxyl group-containing monomers maleic anhydride, itaconic anhydride and other acid anhydride group-containing monomers; hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic Hydroxybutyl, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclo Hydroxyl group-containing monomers such as (xyl) methyl methacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth ) A sulfonic acid
  • cyanoacrylate monomers carboxyl group-containing monomers, hydroxyl group-containing monomers, (N-substituted) amide monomers, epoxy group-containing acrylic monomers, and polyfunctional monomers are preferable, and acrylonitrile , Methacrylonitrile, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate More preferably, one or more selected from (meth) acrylamide, N-methylol (meth) acrylamide, glycidyl (meth) acrylate and divinylbenzene.
  • the content of the structural unit (B) is 5 masses when the total of all structural units in the (meth) acrylic adhesive resin is 100 mass%. % To 50% by mass, more preferably 8% to 45% by mass, and still more preferably 10% to 40% by mass.
  • the adhesive resin (P) is preferably used in combination of two or more resins having different glass transition temperatures. More specifically, an adhesive resin (P1) having a glass transition temperature of preferably 5 ° C. or higher and 50 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and further preferably 15 ° C. or higher and 30 ° C. or lower; It is used in combination with an adhesive resin (P2) having a temperature of preferably ⁇ 50 ° C.
  • the adhesive resin (P1) it is possible to further suppress the adhesive residue on the ITO film when the heat treatment is performed in a state of being attached to the ITO film. Further, by including the adhesive resin (P2), the initial adhesive force can be further improved.
  • the content of the adhesive resin (P1) included in the adhesive resin layer 20 is When the total content of the adhesive resin (P1) and the adhesive resin (P2) is 100% by mass, the adhesive residue on the ITO film when the heat treatment is performed in a state of being attached to the ITO film is further suppressed. From the viewpoint, it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 65% by mass or more, still more preferably 70% by mass or more, and 75% by mass. The above is particularly preferable. Also, increasing the content of the adhesive resin (P1), or to reduce the value of P 1, or can reduce the value of P 1 / P 0.
  • the content of the adhesive resin (P1) contained in the resin layer 20 is preferably 80% by mass or more, and more preferably 85% by mass or more.
  • the content of the adhesive resin (P1) included in the adhesive resin layer 20 is When the total content of the adhesive resin (P1) and the adhesive resin (P2) is 100% by mass, it is preferably 97% by mass or less, and 95% by mass from the viewpoint of obtaining even better initial adhesive strength. More preferably, it is more preferably 93% by mass or less. Further, decreasing the content of the adhesive resin (P1), or increasing the value of P 1, or can increase the value of P 1 / P 0.
  • the production of the (meth) acrylic adhesive resin according to this embodiment can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations.
  • solution polymerization in radical polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
  • the polymerization initiator is not particularly limited.
  • Azo initiators such as 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057); sodium persulfate, Persulfates such as potassium persulfate and ammonium persulfate; di
  • the said polymerization initiator may be used independently, and may mix and use 2 or more types.
  • the amount of the polymerization initiator used is preferably 0.005 to 1 part by mass and more preferably 0.02 to 0.6 part by mass with respect to 100 parts by mass of the monomer.
  • a chain transfer agent may be used in the polymerization.
  • a chain transfer agent By using a chain transfer agent, the molecular weight of the (meth) acrylic adhesive resin can be appropriately adjusted.
  • the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. These chain transfer agents may be used alone or in combination of two or more.
  • the amount of the chain transfer agent used is, for example, 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the monomer.
  • Examples of the emulsifier used for emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate, polyoxyethylene alkyl ether ammonium sulfate, and polyoxyethylene alkylphenyl ether sodium sulfate.
  • the content of the adhesive resin (P) in the adhesive resin layer 20 according to this embodiment is 100% by mass of the entire adhesive resin layer 20 from the viewpoint of the balance between the initial adhesive force and the suppression of adhesive residue. Is preferably 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 99% by mass or less, further preferably 80% by mass or more and 98% by mass or less, and 85% by mass. % To 97% by mass is particularly preferable.
  • the adhesive resin layer 20 has a crosslinkable functional group in one molecule in addition to the adhesive resin (P). It is preferable to further include a crosslinking agent having two or more.
  • cross-linking agents include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, resorcin diglycidyl ether, etc.
  • Epoxy compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane, toluene diisocyanate triadduct, polyisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate; trimethylolpropane-tri- ⁇ -aziridinylpropio , Tetramethylolmethane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide), N, N′-toluene-2 , 4-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ - (2-methylaziridine) propionate, and the like; N, N, N ′, N′-tetraglycidyl
  • the content of the crosslinking agent in the adhesive resin layer 20 according to the present embodiment is based on 100 parts by mass of the adhesive resin (P) from the viewpoint of improving the balance between the initial adhesive force and the suppression of adhesive residue. It is preferable that it is 0.1 mass part or more and 10 mass parts or less, 0.5 mass part or more and 8 mass parts or less are more preferable, and 1 mass part or more and 6 mass parts or less are more preferable.
  • the adhesive resin layer 20 preferably further includes a surfactant in addition to the adhesive resin (P) from the viewpoint of adjusting the adhesive force and cohesive force of the adhesive resin (P).
  • a surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
  • Examples of the cationic surfactant include dodecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, didodecyldimethylammonium chloride, ditetradecyldimethylammonium.
  • Chloride dihexadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, dodecylbenzyldimethylammonium chloride, hexadecylbenzyldimethylammonium chloride, octadecylbenzyldimethylammonium chloride, palmityltrimethylammonium chloride, oleyltrimethyl Nmo chloride, di Val Michiru benzyl ammonium chloride, dioleyl benzyl ammonium chloride, and the like.
  • anionic surfactant examples include alkyl diphenyl ether disulfonates such as diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, sodium alkyl diphenyl ether disulfonate; sodium dodecylbenzene sulfonate, dodecylbenzene Alkyl benzene sulfonates such as ammonium sulfonate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; aliphatic carboxylates such as fatty acid sodium and potassium oleate; sulfate salts containing polyoxyalkylene units (eg, polyoxy Sodium ethylene alkyl ether sulfate, polyoxyethylene alkyl ether Polyoxyethylene alkyl ether sulf
  • nonionic surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, A polyoxyalkylene unit-containing ether compound such as a polyoxyalkylene alkyl phenyl ether compound such as polyoxyethylene nonylphenyl ether, a polyoxyalkylene polycyclic phenyl ether compound such as polyoxyethylene polycyclic phenyl ether; a polyoxyethylene monolaurate; Polyoxyalkylene alkyl ester compounds such as polyoxyethylene monostearate and polyoxyethylene monooleate; Polyoxyalkylene alkylamine compounds such as shea polyoxyethylene alkyl amine; sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate
  • amphoteric surfactants examples include lauryl betaine and lauryl dimethylamine oxide.
  • surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
  • nonionic surfactants are preferable, and polyoxyalkylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, and polyoxyethylene oleyl ether are more preferable, and polyoxyethylene More preferred are alkyl ether compounds.
  • the content of the surfactant in the adhesive resin layer 20 according to this embodiment is based on 100 parts by mass of the adhesive resin (P) from the viewpoint of improving the balance between the initial adhesive force and the suppression of adhesive residue. 0.1 parts by mass or more and 15 parts by mass or less is preferable, 0.5 parts by mass or more and 10 parts by mass or less are more preferable, and 1 part by mass or more and 8 parts by mass or less are more preferable.
  • the content of the surfactant in the adhesive resin layer 20 according to the present embodiment is such that the paste on the ITO film when stored or transported under heat treatment or high temperature and high humidity while being attached to the ITO film.
  • the mass of adhesive resin layer 20 is the mass of adhesive resin and surfactant, Further, when an additive such as a plasticizer is included, the mass is also a total value.
  • the mass of the surfactant and the mass of the adhesive resin layer 20 are masses of solids from which the solvent and moisture are removed.
  • the adhesive resin layer 20 is made of a tackifier, a plasticizer, an anti-aging agent, an antioxidant, a colorant (pigment, dye, etc.), a softener, a light stabilizer, an ultraviolet absorber, and a polymerization inhibitor as necessary.
  • other components such as inorganic or organic fillers, metal powders, particulates, and foils may be further blended.
  • the thickness of the adhesive resin layer 20 is not particularly limited, but is preferably 1 ⁇ m or more and 50 ⁇ m or less, and more preferably 1 ⁇ m or more and 30 ⁇ m or less from the viewpoint of the balance between the initial adhesive strength and the suppression of adhesive residue. It is preferably 2 ⁇ m or more and 15 ⁇ m or less, more preferably 3 ⁇ m or more and 12 ⁇ m or less.
  • a release film may be further laminated on the pressure-sensitive adhesive resin layer 20.
  • the release film include a polyester film subjected to a release treatment.
  • the adhesive laminated film 50 according to the present embodiment can be obtained, for example, by forming the adhesive resin layer 20 on one surface of the base material layer 10.
  • the adhesive resin layer 20 is formed, for example, by applying an adhesive containing an adhesive resin (P) and, if necessary, a crosslinking agent, a surfactant, and other components on the base material layer 10. Can do.
  • the adhesive may be used as a coating solution by dissolving the adhesive resin (P), if necessary, a crosslinking agent, a surfactant, and other components in an organic solvent, or an aqueous emulsion by emulsifying in water. May be used as Further, when the pressure-sensitive adhesive is liquid, it may be used as it is.
  • a conventionally known application method such as a roll coater method, a reverse roll coater method, a gravure roll method, a bar coat method, a comma coater method, a die coater method or the like is adopted. it can.
  • the drying conditions of the applied pressure-sensitive adhesive are not particularly limited, but in general, drying is preferably performed for 10 seconds to 10 minutes in a temperature range of 80 to 200 ° C. More preferably, it is dried at 80 to 170 ° C. for 15 seconds to 5 minutes.
  • the pressure-sensitive adhesive after the pressure-sensitive adhesive has been dried, it may be heated at 40 to 80 ° C. for about 5 to 300 hours.
  • the base material layer 10 and the adhesive resin layer 20 may be formed by coextrusion molding, or formed by laminating (laminating) the film-like base material layer 10 and the film-like adhesive resin layer 20. May be.
  • the pressure-sensitive adhesive used to form the pressure-sensitive resin layer 20 is a water-based emulsion
  • the organic solvent include lower aliphatic alcohols such as methanol, ethanol, isopropanol (IPA), n-butanol, and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether; Examples include diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and hydrophilic organic solvents such as diacetone alcohol.
  • diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether are preferable.
  • These organic solvents may be used alone or in combination of two or more.
  • one or more of toluene, xylene, hexane, heptane ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be used.
  • the amount of the organic solvent used is 0.1 to 15 parts by mass with respect to 100 parts by mass of the adhesive resin (P) from the viewpoint of improving the balance between the initial adhesive strength and the suppression of adhesive residue. Is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass.
  • FIG. 2 is a cross-sectional view schematically showing an example of the structure of the structure 100 according to the embodiment of the present invention.
  • the structure 100 according to the present embodiment includes an indium tin oxide (ITO) film 70 and a surface protective film attached to the ITO film 70, and the surface protective film is the present embodiment. It is the adhesive laminated film 50 which concerns on this.
  • the ITO film 70 is formed on the base material layer 90, for example. Since the structure 100 according to the present embodiment includes the adhesive laminated film 50 as a surface protective film, the adhesive resin layer is not formed on the ITO film even when heat treatment at a high temperature such as crystallization treatment of the ITO film is performed. The adhesive residue phenomenon that a part remains is hard to occur. Therefore, it is possible to perform a heat treatment such as a crystallization treatment of the ITO film while suppressing contamination of the ITO film.
  • the base material layer 90 is preferably a soft material that is colorless and transparent in the visible light region and can form an ITO film.
  • polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); cycloolefin resins; polycarbonate resins; polyimide resins; cellulose resins.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • cycloolefin resins polycarbonate resins
  • polyimide resins polyimide resins
  • cellulose resins a soft material that is colorless and transparent in the visible light region and can form an ITO film.
  • polyethylene terephthalate PET
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • cycloolefin resins polycarbonate resins
  • polyimide resins polyimide resins
  • the method for forming the ITO film on the base material layer 90 is not particularly limited as long as it is a method capable of forming a uniform thin film.
  • sputtering, vapor deposition, various CVD, spin coat method, roll coat method, spray coating, dipping coating and the like can be mentioned.
  • Base material layer 1 Polypropylene (PP) film (manufactured by Toray Film Processing Co., Ltd., product name: 3701J, thickness: 40 ⁇ m)
  • Crosslinking agent 1 Sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Corporation, product name: Denacol EX-614)
  • Surfactant 1 Polyoxyethylene alkyl ether (manufactured by Kao Corporation, product name: Emulgen 705)
  • Organic solvent 1 Diethylene glycol monobutyl ether
  • Adhesive resin 1 In a polymerization reactor equipped with a reflux condenser, 51.69 parts by mass of deionized water, 0.23 parts by mass of potassium persulfate as a polymerization initiator, 19.30 parts by mass of 2-ethylhexyl acrylate, 19.30 parts of butyl acrylate. Parts by weight, 3.68 parts by weight of acrylonitrile, 2.30 parts by weight of methacrylic acid, 2.76 parts by weight of acrylamide, 0.23 parts by weight of divinylbenzene, 0.51 parts by weight of sodium alkyldiphenyl ether disulfonate as a surfactant Then, emulsion polymerization was carried out at 70 ° C. for 8 hours with stirring under a nitrogen atmosphere, and the obtained emulsion was neutralized with 25% aqueous ammonia. By the above procedure, an adhesive resin solution containing 44.5% by mass of adhesive resin 1 was obtained.
  • Adhesive resin 2 In a polymerization reactor equipped with a reflux condenser, 54.81 parts by mass of deionized water, 0.22 parts by mass of potassium persulfate as a polymerization initiator, 25.40 parts by mass of butyl acrylate, 12.41 parts by mass of methyl methacrylate, Methacrylic acid-2-hydroxyethyl 4.00 parts by weight, methacrylic acid 0.89 parts by weight, acrylamide 0.45 parts by weight, glycidyl methacrylate 1.33 parts by weight, surfactant sodium alkyldiphenyl ether disulfonate 0.49 parts
  • Emulsion polymerization was carried out at 70 ° C. for 8 hours with stirring under a nitrogen atmosphere, and the resulting emulsion was neutralized with 25% aqueous ammonia. By the above procedure, an adhesive resin solution containing 45.0% by mass of adhesive resin 2 was obtained.
  • Adhesive resin 3 In a polymerization reactor equipped with a reflux condenser, 54.78 parts by mass of deionized water, 0.22 parts by mass of potassium persulfate as a polymerization initiator, 29.39 parts by mass of butyl acrylate, 10.23 parts by mass of acrylonitrile, methacrylic acid -1.77 parts by mass of hydroxyethyl, 1.78 parts by mass of acrylic acid, 1.34 parts by mass of acrylamide, and 0.49 parts by mass of sodium alkyldiphenyl ether disulfonate as a surfactant are added and stirred under a nitrogen atmosphere. Then, emulsion polymerization was carried out at 70 ° C. for 8 hours, and the obtained emulsion was neutralized with 25% aqueous ammonia. By the above procedure, an adhesive resin solution containing 44.5% by mass of adhesive resin 3 was obtained.
  • Example 1 Each component was mixed in the ratio shown in Table 1 to obtain an adhesive 1.
  • the pH was adjusted to 7 using ammonia water, and the viscosity of the pressure-sensitive adhesive was adjusted to 100 mPa ⁇ s using pure water.
  • Examples 2 to 10 and Comparative Example 1 A pressure-sensitive adhesive laminated film was obtained in the same manner as in Example 1 except that each of the pressure-sensitive adhesives prepared in the ratio shown in Table 1 was used instead of the pressure-sensitive adhesive 1.
  • the pH was adjusted to a range of 6.5 to 8.5 using ammonia water, and the viscosity of each adhesive was adjusted to 100 to 200 mPa ⁇ s using pure water.
  • the following evaluation was performed about the obtained adhesive laminated film. The obtained results are shown in Table 1.
  • peel strength P 0 between the measurement ITO film and the adhesive resin layer of the peel strength P 0 conforms to JIS Z0237 was measured by the following method.
  • Adhesive laminate film is applied to ITO film under pressure of 2kg / cm and application speed of 2m / min so that adhesive resin layer is in contact with ITO film deposited on polyester film (P02) It was.
  • a tensile tester ORIENTEC Co., RTA-1210A
  • the adhesive laminated film was peeled from the ITO film in the direction of 180 ° at 23 ° C. and a tensile speed of 300 mm / min, and the strength ( N / 25 mm) was defined as the peel strength (P 0 ).
  • the adhesive laminated film was affixed to the ITO film so that the adhesive resin layer was in contact with the ITO film deposited on the polyester film (P02, manufactured by Takumi Photoelectric Co., Ltd.).
  • the obtained structure was heat-treated at 150 ° C. for 60 minutes.
  • a tensile tester ORIENTEC Co., RTA-1210A
  • the adhesive laminated film was peeled from the ITO film in the direction of 180 ° at 23 ° C. and a tensile speed of 300 mm / min, and the strength ( N / 25 mm) was defined as the peel strength (P 1 ).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un film stratifié adhésif (50) protégeant la surface d'un oxyde d'étain et d'indium (ITO), le film stratifié adhésif (50) étant pourvu d'une couche de matériau de base (10) et d'une couche de résine adhésive (20) disposée sur une surface de la couche de matériau de base (10). En outre, dans ce film stratifié adhésif (50), le rapport P1/P0 est de 1,0 à 25, où P0 [N/25 mm] est la résistance au pelage entre un film ITO déposé en phase vapeur sur un film de matériau de base et la couche de résine adhésive (20), et P1 [N/25 mm] est la résistance au pelage entre le film ITO et la couche de résine adhésive (20) après que le film stratifié adhésif (50) soit fixé au film ITO, qui a été déposé en phase vapeur sur le film de matériau de base, de telle sorte que la couche de résine adhésive (20) soit en contact avec le film ITO, puis la structure résultante est traitée thermiquement pendant 60 minutes à 150 °C.
PCT/JP2018/012701 2017-03-29 2018-03-28 Film stratifié adhésif et structure WO2018181453A1 (fr)

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CN110431205B (zh) 2021-11-30
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CN110431205A (zh) 2019-11-08
TW201839080A (zh) 2018-11-01
JPWO2018181453A1 (ja) 2019-11-07

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