WO2018181452A1 - Film stratifié adhésif et structure associée - Google Patents

Film stratifié adhésif et structure associée Download PDF

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Publication number
WO2018181452A1
WO2018181452A1 PCT/JP2018/012700 JP2018012700W WO2018181452A1 WO 2018181452 A1 WO2018181452 A1 WO 2018181452A1 JP 2018012700 W JP2018012700 W JP 2018012700W WO 2018181452 A1 WO2018181452 A1 WO 2018181452A1
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Prior art keywords
film
adhesive
meth
adhesive resin
mass
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PCT/JP2018/012700
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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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Publication of WO2018181452A1 publication Critical patent/WO2018181452A1/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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

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. As a result, by using an adhesive resin layer containing a structural unit derived from (meth) acrylonitrile as the adhesive resin layer constituting the adhesive laminated film, the heat treatment was performed in a state of being attached to the ITO film. The present invention has been completed by finding that it is possible to suppress adhesive residue on the ITO film.
  • the following adhesive laminated film and structure are provided.
  • the pressure-sensitive adhesive resin layer includes a (meth) acrylic pressure-sensitive adhesive resin, and the (meth) acrylic pressure-sensitive adhesive resin includes a structural unit derived from the (meth) acrylonitrile.
  • Adhesiveness with a peel strength (P 0 ) between the ITO film deposited on the base film and the adhesive resin layer measured by the following method of 0.01 N / 25 mm or more and 1.0 N / 25 mm or less Laminated film.
  • 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.
  • [5] In the adhesive laminated film according to any one of the above [1] to [4], When 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, and then the resulting structure is heated at 150 ° C.
  • the peel strength (P 1 ) between the ITO film deposited on the base film and the adhesive resin layer, measured by the following method, is 0.1 N / 25 mm or more and 1.0 N / 25 mm or less.
  • 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.
  • An indium tin oxide (ITO) film A surface protective film affixed to the ITO film, A structure in which the surface protective film is the adhesive laminated film according to any one of [1] to [7].
  • 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. And in the adhesive laminated film 50 which concerns on this embodiment, the adhesive resin layer 20 contains the structural unit derived from (meth) acrylonitrile.
  • ITO indium tin oxide
  • the adhesive laminated film 50 includes the adhesive resin layer 20 including a structural unit derived from (meth) acrylonitrile, so that the ITO film is subjected to heat treatment in a state of being attached to the ITO film. It is possible to suppress the adhesive residue on the top.
  • the content of the structural unit derived from (meth) acrylonitrile in the pressure-sensitive adhesive resin layer 20 is on the ITO film when the heat treatment is performed in a state of being attached to the ITO film.
  • the total amount of the adhesive resin layer 20 is preferably 10% by mass or more, more preferably 12% by mass or more, and more preferably 15% by mass, based on 100% by mass. The above is particularly preferable.
  • content of the structural unit derived from the (meth) acrylonitrile in the adhesive resin layer 20 is the adhesive force to the ITO film
  • the entire adhesive resin layer 20 is 100% by mass, it is preferably 30% by mass or less, more preferably 28% by mass or less, and 25% by mass or less. More preferably, it is particularly preferably 23% by mass or less.
  • the content ratio of the structural unit derived from (meth) acrylonitrile in the adhesive resin (P) constituting the adhesive resin layer 20 and the content ratio of the adhesive resin (P) in the adhesive resin layer 20 is controlled.
  • the initial adhesive force is further improved, and from the viewpoint of suppressing the pressure-sensitive adhesive laminated film 50 from being lifted from the ITO film, the base is measured by the following method.
  • the peel strength (P 0 ) between the ITO film deposited on the material film and the adhesive resin layer 20 is preferably 0.01 N / 25 mm or more, more preferably 0.02 N / 25 mm or more, More preferably, it is 0.03 N / 25 mm or more.
  • the peel strength (P 0 ) between the ITO film deposited on the base film and the adhesive resin layer 20 is preferably 1.0 N / 25 mm or less, and more preferably 0.5 N / 25 mm or less. Preferably, it is 0.2 N / 25 mm 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. Next, using a tensile tester, the adhesive laminate film 50 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 determined as the peel strength. To do.
  • the adhesive laminated 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, and then the obtained structure is obtained.
  • the peel strength (P 1 ) between the ITO film deposited on the base film and the adhesive resin layer 20 measured by the following method is 0.1 N / 25 mm or more. It is preferable that it is 1.0 N / 25 mm or less.
  • the adhesive laminated film 50 is 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 is defined as the peel strength.
  • 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 includes a structural unit derived from (meth) acrylonitrile, and includes, for example, an adhesive resin (P) including a structural unit derived from (meth) acrylonitrile.
  • an adhesive resin (P) including a structural unit derived from (meth) acrylonitrile examples include (meth) acrylic adhesive resin, silicone adhesive resin, urethane adhesive resin, olefin adhesive resin, and styrene resin. Adhesive resin etc. are mentioned. Among these, (meth) acrylic adhesive resins are preferred from the viewpoint of facilitating adjustment of the content of structural units derived from (meth) acrylonitrile.
  • Examples of the (meth) acrylic adhesive resin used for the adhesive resin layer 20 include a structural unit (A) derived from (meth) acrylic acid alkyl ester and a structural unit (B) derived from (meth) acrylonitrile.
  • a copolymer is mentioned.
  • (meth) acrylic acid alkyl ester means acrylic acid alkyl ester, methacrylic acid alkyl ester, or a mixture thereof.
  • the (meth) acrylic adhesive resin according to the present embodiment includes, for example, a (meth) acrylic acid alkyl ester monomer, a (meth) acrylonitrile monomer, and a (meth) acrylic acid alkyl ester monomer and (meth) as necessary. It can be obtained by copolymerizing a mixture containing an acrylonitrile monomer and another monomer copolymerizable.
  • 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%.
  • Examples of the (meth) acrylonitrile monomer that forms the structural unit (B) derived from (meth) acrylonitrile include acrylonitrile, methacrylonitrile, and mixtures thereof.
  • the content of the structural unit (B) derived from (meth) acrylonitrile is 100% by mass of the total of all structural units in the (meth) acrylic adhesive resin. Is preferably 10% by mass to 30% by mass, more preferably 12% by mass to 28% by mass, further preferably 15% by mass to 25% by mass, and more preferably 15% by mass. % Or more and 23% by mass or less is particularly preferable.
  • the (meth) acrylic adhesive resin according to this embodiment can be copolymerized with a (meth) acrylic acid alkyl ester monomer and a (meth) acrylonitrile monomer from the viewpoint of improving cohesion, heat resistance, crosslinkability, and the like.
  • the structural unit (C) derived from other monomers may further be included.
  • Examples of the monomer that forms the structural unit (C) include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride, Acid anhydride group-containing monomers such as itaconic anhydride; hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy (meth) acrylate Hydroxyl group-containing monomers such as hexyl, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate; styrene Contains sulfonic acid groups such as
  • Monomers hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl Recall di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinyl
  • polyfunctional monomers such as benzene, butyl di (meth) acrylate, and hexyl di (meth) acrylate
  • olefin monomers such as isoprene, butadiene, and isobutylene
  • vinyl ether monomers such as methyl vinyl ether and ethyl
  • carboxyl group-containing monomers hydroxyl group-containing monomers, (N-substituted) amide monomers, epoxy group-containing acrylic monomers and polyfunctional monomers are preferred, and acrylic acid, methacrylic acid , Itaconic acid, maleic acid, fumaric acid, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylamide, N-methylol
  • One or more selected from (meth) acrylamide, glycidyl (meth) acrylate and divinylbenzene are more preferred.
  • the content of the structural unit (C) is 0 mass when the total of all the structural units in the (meth) acrylic adhesive resin is 100% by mass. % To 40% by mass, more preferably 0.5% to 30% by mass, and still more preferably 1% to 20% 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 while having a better initial adhesive force.
  • the adhesive resin (P) containing a structural unit derived from (meth) acrylonitrile is used in combination of two or more resins having different contents of the structural unit derived from (meth) acrylonitrile. More specifically, the structural unit derived from (meth) acrylonitrile is preferably 15% by mass or more and 30% by mass or less, more preferably 17% by mass with respect to a total of 100% by mass of all the structural units in the adhesive resin (P).
  • the structural unit derived from (meth) acrylonitrile is preferably 3% by mass or more and 15% by mass with respect to 100% by mass of the total of the structural units in the adhesive resin (P1) containing 28% by mass or more and 28% by mass or less. It is more preferable to use in combination with an adhesive resin (P2) containing less than 5% by mass, more preferably 5% by mass to 13% by mass.
  • 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 adhesive resin layer 20 contains the adhesive resin (P1) and adhesive resin (P2) from which the content of the structural unit derived from (meth) acrylonitrile differs
  • the adhesive resin contained in the adhesive resin layer 20 ( The content of P1) is on the ITO film when the heat treatment is performed in a state of being attached to the ITO film when the total content of the adhesive resin (P1) and the adhesive resin (P2) is 100% by mass.
  • it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 65% by mass or more, and 70% by mass or more. Is even more preferable, with 75% by mass or more being particularly preferable.
  • 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 adhesive resin layer 20 contains the adhesive resin (P1) and adhesive resin (P2) from which the content of the structural unit derived from (meth) acrylonitrile differs
  • the adhesive resin contained in the adhesive resin layer 20 ( The content of P1) is 97% by mass or less from the viewpoint of obtaining even better initial adhesive strength when the total content of the adhesive resin (P1) and the adhesive resin (P2) is 100% by mass.
  • it is 95% by mass or less, and more preferably 93% by mass or less.
  • the content of (meth) acrylonitrile in the adhesive resin layer 20 can be quantified by, for example, 1 H-NMR and 13 C-NMR analysis.
  • 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) containing the structural unit derived from (meth) acrylonitrile in the adhesive resin layer 20 according to this embodiment is an adhesive from the viewpoint of the balance between the initial adhesive force and the suppression of adhesive residue. 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass, based on 100% by mass of the entire resin layer 20. More preferably, it is 85 mass% or more and 97 mass% or less.
  • the adhesive resin layer 20 in addition to the adhesive resin (P) containing a structural unit derived from (meth) acrylonitrile, It is preferable to further include a cross-linking agent having two or more cross-linkable functional groups in one molecule.
  • Such 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 further includes a surfactant in addition to the adhesive resin (P) containing a structural unit derived from (meth) acrylonitrile. It is preferable to include.
  • the 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 11 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 ).
  • the adhesive laminated film of the Example provided with the adhesive resin layer containing the structural unit derived from (meth) acrylonitrile has suppressed the adhesive residue on the ITO film when the heat treatment is performed in a state of being attached to the ITO film. It was.
  • the adhesive laminated film of the comparative example provided with an adhesive resin layer not containing a structural unit derived from (meth) acrylonitrile is peeled off when the ITO film side is subjected to a heat treatment in a state of being attached to the ITO film. Adhesive residue was observed on the entire surface.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne un film stratifié adhésif (50) destiné à protéger la surface d'un film d'oxyde d'indium-étain (ITO), ledit film (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), et la couche de résine adhésive (20) comprenant des unités structurales issues de (méth)acrylonitrile.
PCT/JP2018/012700 2017-03-29 2018-03-28 Film stratifié adhésif et structure associée WO2018181452A1 (fr)

Applications Claiming Priority (2)

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JP2017-066127 2017-03-29
JP2017066127A JP2020111622A (ja) 2017-03-29 2017-03-29 粘着性積層フィルムおよび構造体

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004027070A (ja) * 2002-06-27 2004-01-29 Nitto Denko Corp 保護フィルム
JP2013072068A (ja) * 2011-09-29 2013-04-22 Nitto Denko Corp 表面保護フィルム
JP2013127012A (ja) * 2011-12-16 2013-06-27 Toyo Ink Sc Holdings Co Ltd 粘着剤、粘着シートおよびディスプレイ
JP2016037557A (ja) * 2014-08-07 2016-03-22 藤森工業株式会社 透明導電性フィルム用表面保護フィルム及びそれを用いた透明導電性フィルム
JP2016186062A (ja) * 2015-03-27 2016-10-27 東洋インキＳｃホールディングス株式会社 再剥離型粘着剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004027070A (ja) * 2002-06-27 2004-01-29 Nitto Denko Corp 保護フィルム
JP2013072068A (ja) * 2011-09-29 2013-04-22 Nitto Denko Corp 表面保護フィルム
JP2013127012A (ja) * 2011-12-16 2013-06-27 Toyo Ink Sc Holdings Co Ltd 粘着剤、粘着シートおよびディスプレイ
JP2016037557A (ja) * 2014-08-07 2016-03-22 藤森工業株式会社 透明導電性フィルム用表面保護フィルム及びそれを用いた透明導電性フィルム
JP2016186062A (ja) * 2015-03-27 2016-10-27 東洋インキＳｃホールディングス株式会社 再剥離型粘着剤

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