WO2018181518A1 - Feuille adhésive et procédé de production d'un corps stratifié - Google Patents

Feuille adhésive et procédé de production d'un corps stratifié Download PDF

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Publication number
WO2018181518A1
WO2018181518A1 PCT/JP2018/012848 JP2018012848W WO2018181518A1 WO 2018181518 A1 WO2018181518 A1 WO 2018181518A1 JP 2018012848 W JP2018012848 W JP 2018012848W WO 2018181518 A1 WO2018181518 A1 WO 2018181518A1
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WIPO (PCT)
Prior art keywords
group
adhesive sheet
resin
molecular
reactive
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Application number
PCT/JP2018/012848
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English (en)
Japanese (ja)
Inventor
秀一 中山
和恵 上村
Original Assignee
リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201880021870.3A priority Critical patent/CN110461975B/zh
Priority to JP2019510002A priority patent/JP6605779B2/ja
Priority to KR1020197029138A priority patent/KR102314239B1/ko
Publication of WO2018181518A1 publication Critical patent/WO2018181518A1/fr

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Classifications

    • 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
    • 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
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • 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
    • C09J2301/312—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 parameters being the characterizing feature

Definitions

  • the present invention includes a resin layer, a molecular adhesive layer (referred to as a layer formed using a molecular adhesive; hereinafter the same), and a protective film, and an adhesive sheet excellent in adhesiveness to an adherend, and this
  • the present invention relates to a method for manufacturing a laminate using an adhesive sheet.
  • Patent Document 1 discloses a laminate in which an entropy elastic molecular adhesive layer is formed between two substrates, and the entropy elastic molecular adhesive layer is an entropy elastic body. What is characterized by comprising a layer and a molecular adhesive layer is described.
  • a protective film (release film) is usually provided on the adhesive layer for long-term storage and transport.
  • release film a protective film
  • an adhesive sheet provided with a protective film on a molecular adhesive layer may not sufficiently develop the inherent adhesive strength of the molecular adhesive.
  • the present invention aims to solve this problem, and includes an adhesive sheet having a resin layer, a molecular adhesive layer, and a protective film, and having excellent adhesion to an adherend, and the adhesive sheet. It aims at providing the manufacturing method of the laminated body to be used.
  • the present inventors have intensively studied an adhesive sheet having a resin layer, a molecular adhesive layer, and a protective film.
  • the decrease in the adhesive strength of the molecular adhesive layer is caused by a chemical bond caused by contact between the molecular adhesive layer and the protective film; and
  • a protective film having an embossed surface in which at least one or more convex portions are present on the surface in contact with the molecular adhesive layer it is possible to suppress a decrease in the adhesive strength of the molecular adhesive layer; As a result, the present invention has been completed.
  • the resin (S) has a reactive partial structure (Z ⁇ ) capable of forming a chemical bond with the reactive group (Z ⁇ ) of the molecular adhesive
  • the protective film comprises: An adhesive sheet having an embossed surface in which at least one or more convex portions are present on the surface in contact with the molecular adhesive layer.
  • the molecular adhesive layer is formed by a chemical bond between a reactive group (Z ⁇ ) of the molecular adhesive and a reactive partial structure (Z ⁇ ) of the resin (S).
  • the reactive group (Z ⁇ ) of the molecular adhesive is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group
  • the resin (S) is The adhesive sheet according to [1] or [2], wherein the reactive partial structure (Z ⁇ ) is at least one selected from the group consisting of a hydroxy group, a carboxy group, an aldehyde group, and an amino group.
  • the reactive group (Z ⁇ ) of the molecular adhesive is an azide group
  • the reactive partial structure (Z ⁇ ) of the resin (S) is a carbon-carbon single bond, carbon-carbon double bond.
  • R 1 is a reactive group (Z ⁇ ) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group and an epoxy group, or a monovalent group having one or more of these reactive groups.
  • A represents a divalent organic group
  • X represents a hydroxy group
  • Y represents a hydrocarbon group having 1 to 20 carbon atoms
  • a represents an integer of 1 to 3.
  • the protective film has no reactive group (Z ⁇ ) selected from the group consisting of a silanol group and a group that generates a silanol group by a hydrolysis reaction.
  • the hydrocarbon resin is at least one selected from the group consisting of polyethylene, polypropylene, poly (4-methyl-1-pentene), and polycycloolefin having an alicyclic structure having 4 to 10 carbon atoms.
  • [15] Obtained by a method for producing an adhesive sheet comprising the steps of forming the molecular adhesive layer on the resin layer and then overlaying the protective film on the formed molecular adhesive layer.
  • [16] A resin layer / molecule characterized in that the protective film constituting the adhesive sheet according to any one of [1] to [15] is peeled off and the exposed molecular adhesive layer is pressure-bonded to an adherend.
  • the method for producing a laminate according to [16] wherein the temperature T p (° C.) during the pressure bonding satisfies the following formula (I).
  • T g represents the glass transition temperature (° C.) of the resin layer
  • T s represents the softening point (° C.) of the resin layer.
  • H is 40.
  • the Young's modulus at a temperature T p (° C.) at the time of pressure bonding of at least one of the resin layer or the adherend is 1 ⁇ 10 6 to 1 ⁇ 10 9 Pa, [16] or [17] The manufacturing method of the laminated body of description.
  • an adhesive sheet having a resin layer, a molecular adhesive layer, and a protective film and having excellent adhesion to an adherend, and a method for producing a laminate using the adhesive sheet.
  • Adhesive sheet The adhesive sheet of the present invention comprises at least one reactive group selected from the group consisting of a resin layer containing a resin (S), an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group.
  • a molecular adhesive layer comprising a molecular adhesive having (Z ⁇ ) and at least one reactive group (Z ⁇ ) selected from the group consisting of a silanol group and a group that generates a silanol group by a hydrolysis reaction; and The protective film is directly laminated in this order.
  • the resin (S) has a reactive partial structure (Z ⁇ ) capable of forming a chemical bond with the reactive group (Z ⁇ ) of the molecular adhesive.
  • the protective film has an embossed surface in which at least one convex portion is present on the surface in contact with the molecular adhesive layer.
  • “including molecular adhesive” in “molecular adhesive layer including molecular adhesive” means “molecular adhesive and / or compound derived from molecular adhesive (for example, through reaction, Including a compound having a changed structure).
  • “The resin (S) has a reactive partial structure (Z ⁇ ) capable of forming a chemical bond with the reactive group (Z ⁇ ) of the molecular adhesive” means that a molecular adhesive layer is formed on the resin layer. It shows the state before it is done. In the resin layer after the molecular adhesive layer is formed, the resin (S) has a structure derived from the reactive partial structure (Z ⁇ ) and / or the reactive partial structure (Z ⁇ ).
  • the resin layer which comprises the adhesive sheet of this invention is a layer containing resin (S).
  • the resin layer plays a role of fixing the molecular adhesive.
  • the resin layer plays a role of fixing the molecular adhesive.
  • the resin (S) has a reactive partial structure (Z ⁇ ) that can form a chemical bond with the reactive group (Z ⁇ ) of the molecular adhesive. Since the resin (S) has the reactive partial structure (Z ⁇ ), the molecular adhesive layer can be efficiently formed.
  • Examples of the reactive partial structure (Z ⁇ ) of the resin (S) include a hydroxy group, a carboxy group, an aldehyde group, an amino group, a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. . These can be appropriately selected according to the reactive group (Z ⁇ ) in the molecular adhesive.
  • the reactive group (Z ⁇ ) of the molecular adhesive is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group
  • the reactive partial structure (Z ⁇ ) As for, at least 1 sort (s) chosen from the group which consists of a hydroxy group, a carboxy group, an aldehyde group, and an amino group is used preferably.
  • the reactive partial structure (Z ⁇ ) includes a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. At least one selected from the group consisting of bonds is preferably used.
  • the resin (S) is not particularly limited as long as it can form a resin layer for fixing the molecular adhesive.
  • the resin (S) include polyolefin resins such as polyethylene, polypropylene, polybutene, and poly-4-methyl-1-pentene; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyvinyl chloride, polyvinylidene chloride, Vinyl resins such as polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; polystyrene; acrylonitrile-butadiene-styrene (ABS) resin; polycarbonate; polysulfone; polyether ether ketone; polyether sulfone; Polysulfide; Polyetherimide; Polyimide; Polyamide; Acrylic resin; Cycloolefin resin; Fluororesin; Urethane resin; Resin (S) can
  • the resin (S) preferably has a Young's modulus at 23 ° C. of 1 ⁇ 10 8 to 1 ⁇ 10 10 Pa.
  • a resin (S) By using such a resin (S), an adhesive sheet that is more excellent in adhesiveness can be easily obtained.
  • the resin (S) is a resin (S ′) having a functional group such as a hydroxy group, a carboxy group, an aldehyde group, and an amino group as a reactive partial structure (Z ⁇ )
  • the crystalline partial structure (Zr ′) can be formed by a known method. For example, when performing a polymerization reaction, a monomer having a functional group such as a hydroxy group, a carboxy group, an aldehyde group, or an amino group is used, or a polymer obtained by performing a polymerization reaction is modified with maleic anhydride.
  • the reactive partial structure (Z ⁇ ′) can be formed by performing a modification treatment such as the above.
  • the resin (S ′) may be generated on the surface of the layer (s1).
  • the surface treatment is not particularly limited as long as it generates a hydroxy group or a carboxy group.
  • Examples of the surface treatment include corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, and base treatment. These surface treatments can be performed according to known methods.
  • the resin layer may contain components other than the resin (S).
  • a component other than the resin (S) an appropriate component may be used as long as it is a component and a content that do not inhibit the adhesion with the molecular adhesive layer. Examples thereof include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.
  • the content of the resin (S) in the resin layer is preferably 20% by mass or more, more preferably 30% by mass or more and 100% by mass or less, and more preferably 50% by mass or more and 100% based on the entire resin layer. More preferably, it is at most mass%.
  • the thickness of the resin layer is not particularly limited.
  • the thickness of the resin layer is usually 2 to 4000 ⁇ m, preferably 5 to 1000 ⁇ m, more preferably 10 to 600 ⁇ m, still more preferably 15 to 400 ⁇ m.
  • the method for forming the resin layer is not particularly limited.
  • the resin (S) contained in the resin layer is a resin (S ′′) having a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond as a reactive partial structure (Z ⁇ )
  • a commercially available resin film can be used as it is as the resin layer.
  • the resin (S ′′) is diluted with an appropriate organic solvent to prepare a coating solution, which is applied to the surface of a support, a process sheet, a release sheet, and the resulting coating film is dried.
  • the resin layer can also be formed by performing a curing treatment.
  • the resin layer can be formed by any of the following methods (a) to (d).
  • A) By using a commercially available resin film or resin sheet as the layer (s1) containing the resin that is the precursor of the resin (S ′), the layer (s1) is subjected to the above-described surface treatment to thereby form the resin (S ′ ) Is formed.
  • B) A resin, which is a precursor of the resin (S ′), was diluted with an appropriate organic solvent to prepare a coating solution, which was applied to the surface of a support, a process sheet, a release sheet, and the like.
  • a layer (s1) is formed by performing a drying process and a hardening process with respect to a coating film. Next, the surface treatment is performed on the layer (s1) to form a resin layer containing the resin (S ′).
  • C) A commercially available resin film or resin sheet containing the resin (S ′) is used as it is as the resin layer.
  • D) The resin (S ′) is diluted with an appropriate organic solvent to prepare a coating solution, which is applied to the surface of a support, a process sheet, a release sheet, etc., and dried on the resulting coating film.
  • a resin layer is formed by performing a treatment or a curing treatment.
  • the molecular adhesive layer constituting the adhesive sheet of the present invention comprises at least one reactive group (Z ⁇ ) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group and an epoxy group, and a silanol. And a molecular adhesive having at least one reactive group (Z ⁇ ) selected from the group consisting of a group and a group that generates a silanol group by a hydrolysis reaction.
  • the reactive group (Z ⁇ ) in the molecular adhesive is capable of forming a chemical bond with the reactive partial structure (Z ⁇ ) of the resin (S) in the resin layer.
  • the molecular adhesive is chemically fixed to the surface of the resin layer by this chemical bond.
  • the chemical bond at this time include a covalent bond, a hydrogen bond, an ionic bond, and an intermolecular force, and a covalent bond is preferable.
  • Examples of the group that generates a silanol group by a hydrolysis reaction include a group having a partial structure represented by Si—X 1 .
  • X 1 includes an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom.
  • the reactive group (Z ⁇ ) in the molecular adhesive is mainly used when a chemical bond is formed with the adherend when the adhesive sheet of the present invention is adhered to the adherend. Therefore, the adhesive sheet of the present invention is preferably used for an adherend having a group having high reactivity with these groups on the surface.
  • molecular adhesives examples include compounds represented by the following formula (1).
  • R 1 represents a reactive group (Z ⁇ ) or a monovalent group having one or more reactive groups (Z ⁇ ) (excluding the reactive group (Z ⁇ ) itself), and A is a divalent group.
  • X represents a hydroxy group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom
  • Y represents a hydrocarbon group having 1 to 20 carbon atoms
  • a represents an integer of 1 to 3 .
  • Examples of the monovalent group having one or more reactive groups (Z ⁇ ) for R 1 include groups represented by the following formulas (2) to (4).
  • R 2 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms.
  • Examples of the divalent hydrocarbon group for R 2 include alkylene groups such as ethylene group, trimethylene group and propylene group; and arylene groups such as o-phenylene group, m-phenylene group and p-phenylene group.
  • R 3 and R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrocarbon group for R 3 and R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, n Alkyl groups such as -hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3-butenyl group, Alkenyl groups such as 4-pentenyl group and 5-hexenyl group; alkynyl groups such as ethynyl group, propargyl group and butynyl group;
  • Z represents a single bond or a divalent group represented by —N (R 7 ) —.
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group for R 7 include the same as those shown as the hydrocarbon groups for R 3 and R 4 .
  • R 5 and R 6 each independently represent a reactive group (Z ⁇ ) or a group represented by the formula (2).
  • Examples of the divalent organic group for A include an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, and a substituent.
  • Examples of the alkylene group having 1 to 20 carbon atoms of A include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
  • Examples of the alkenylene group having 2 to 20 carbon atoms of A include a vinylene group, a propenylene group, a butenylene group and a pentenylene group.
  • Examples of the alkynylene group having 2 to 20 carbon atoms of A include an ethynylene group and a propynylene group.
  • Examples of the arylene group having 6 to 20 carbon atoms of A include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 2,6-naphthylene group, and a 1,5-naphthylene group.
  • Examples of the substituent for the alkylene group, alkenylene group, and alkynylene group include a halogen atom such as a fluorine atom and a chlorine atom; an alkoxy group such as a methoxy group and an ethoxy group; an alkylthio group such as a methylthio group and an ethylthio group; a methoxycarbonyl group; An alkoxycarbonyl group such as an ethoxycarbonyl group; and the like.
  • substituents for the arylene group include: a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; And alkylthio groups such as ethylthio group; and the like.
  • substituents may be bonded at arbitrary positions in groups such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, and a plurality of them may be bonded in the same or different manner.
  • Examples of the alkoxy group having 1 to 10 carbon atoms of X include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.
  • Examples of the halogen atom for X include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms for Y include the same as those shown as the hydrocarbon groups for R 3 and R 4 .
  • Examples of molecular adhesives in which R 1 is an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3- ( N, N-dimethylamino) propyl] trimethoxysilane, [3- (phenylamino) propyl] trimethoxysilane, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride etc. are mentioned.
  • Examples of molecular adhesives in which R 1 is an azide group include (11-azidoundecyl) trimethoxysilane, (11-azidoundecyl) triethoxysilane, and the like.
  • Examples of the molecular adhesive in which R 1 is a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.
  • Examples of the molecular adhesive in which R 1 is an isocyanate group include 3- (trimethoxysilyl) propyl isocyanate and 3- (triethoxysilyl) propyl isocyanate.
  • Examples of the molecular adhesive in which R 1 is a ureido group include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane.
  • Examples of molecular adhesives in which R 1 is an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Examples include diethoxysilane.
  • Examples of molecular adhesives in which R 1 is a monovalent group having one or more reactive groups (Z ⁇ ) include 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) Examples thereof include propyltriethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and compounds represented by the following formulas (5) to (13). .
  • the compound represented by the formula (1) is preferably a compound in which R 1 is a group represented by the formula (4), more preferably the compounds represented by the formulas (5) to (13).
  • Compounds represented by formulas (5) to (10) are more preferable.
  • R 1 has a triazine ring. Molecular adhesives having a triazine ring tend to be more efficiently fixed on the resin layer.
  • the molecular adhesive to be used can be appropriately selected in consideration of the combination of the reactive group (Z ⁇ ) and the reactive partial structure (Z ⁇ ) of the resin (S).
  • the reactive group (Z ⁇ ) is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group
  • the reactive partial structure (Z ⁇ ) includes a hydroxy group
  • At least one selected from the group consisting of a carboxy group, an aldehyde group, and an amino group is preferably used.
  • preferred combinations of the reactive group (Z ⁇ ) and the reactive partial structure (Z ⁇ ) [reactive group (Z ⁇ ) / reactive partial structure (Z ⁇ )] include (amino group / hydroxy group), (amino group / (Carboxy group), (isocyanate group / hydroxy group), (isocyanate group / carboxy group), (hydroxy group / carboxy group) and the like.
  • the molecular adhesive has an azide group as a reactive group (Z ⁇ )
  • the azide group is activated by irradiation with light as described later.
  • nitrene as a reaction intermediate can react with a carbon-carbon single bond, a carbon-carbon double bond, or a carbon-hydrogen single bond. Therefore, when a molecular adhesive having an azide group is used, the resin (S) The type is not particularly limited.
  • the method for forming the molecular adhesive layer is not particularly limited.
  • a molecular adhesive solution containing a molecular adhesive can be prepared, and a molecular adhesive layer can be formed on the resin layer by a known method using this solution.
  • the solvent used when preparing the molecular adhesive solution is not particularly limited.
  • the solvent include alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and butyl acetate; halogen-containing compound solvents such as methylene chloride; Aliphatic hydrocarbon solvents such as butane and hexane; Ether solvents such as tetrahydrofuran and butyl ether; Aromatic solvents such as benzene and toluene; Amides such as N, N-dimethylformamide and methylpyrrolidone; Water; Is mentioned. These can be used alone or in combination of two or more.
  • the concentration of the molecular adhesive in the molecular adhesive solution is not particularly limited.
  • the concentration is preferably 0.005 to 1.000 mol / L, more preferably 0.050 to 0.500 mol / L.
  • concentration of the molecular adhesive By setting the concentration of the molecular adhesive to 0.005 mol / L or more, the molecular adhesive can be efficiently formed on the object to be coated.
  • the reaction which the molecular adhesive solution does not intend can be suppressed by setting it as 1.000 mol / L or less, and it is excellent in stability of a solution.
  • Examples of the method for forming the molecular adhesive layer include an immersion method, a coating method, and a spraying method. Among these, a coating method is preferable from the viewpoint of productivity.
  • Examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, dip coating, curtain coating, die coating, and gravure coating.
  • the bar coating method, the dip coating method, and the gravure coating method are preferable.
  • a drying process is required by natural drying or by feeding into a drying mechanism, but it is preferable to perform a drying process by loading into a drying mechanism from the viewpoint of improving productivity.
  • a drying mechanism for example, a batch-type drying mechanism such as an air oven, a heat roll, a hot air through mechanism (a drying target moves and passes through an open drying furnace, and is heated and dried while receiving air.
  • a continuous drying mechanism, etc. An apparatus that can also be used as a part of these drying mechanisms, for example, a heating medium circulating heater such as high-frequency heating or an oil heater, and a heater such as a far-infrared heater itself can be used as the drying mechanism.
  • the drying temperature adjusted by the drying mechanism is usually 20 to 250 ° C., preferably 50 to 200 ° C., more preferably 65 to 150 ° C., and particularly preferably 80 to 120 ° C.
  • the drying time is usually 1 second to 120 minutes, preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 20 seconds to 3 minutes.
  • the molecular adhesive layer it is considered that the molecular adhesive is fixed to the resin layer by a chemical bond between the reactive group (Z ⁇ ) of the molecular adhesive and the reactive partial structure (Z ⁇ ) of the resin (S). . Therefore, when forming the molecular adhesive layer, usually, a process of fixing the molecular adhesive to the resin layer (hereinafter sometimes referred to as a fixing process) is performed.
  • the fixing treatment can be appropriately selected according to the characteristics of the reactive group (Z ⁇ ) of the molecular adhesive.
  • a chemical bond is generated by applying a molecular adhesive on the resin layer, and generation of a chemical bond is promoted by heating. Therefore, heat treatment is preferable from the viewpoint of improving productivity.
  • the heating temperature is usually 40 to 250 ° C, preferably 60 to 200 ° C, more preferably 80 to 120 ° C.
  • the heating time is usually 1 second to 120 minutes, preferably 1 to 60 minutes, more preferably 1 to 30 minutes.
  • the heating method is not particularly limited, and the same mechanism and apparatus as the above-described drying mechanism can be used.
  • a light irradiation process is performed as the fixing process.
  • the irradiation light ultraviolet rays are usually used.
  • Ultraviolet irradiation can be performed using an ultraviolet irradiation device using a light source such as a mercury lamp, a metal halide lamp, an ultraviolet LED, or an electrodeless lamp.
  • the coating, drying treatment and fixing treatment may be repeated a plurality of times.
  • the molecular adhesive layer may contain components other than the molecular adhesive in an amount that does not impair each performance described below.
  • components other than the molecular adhesive include a catalyst.
  • the content of the molecular adhesive in the molecular adhesive layer is preferably 50% by mass or more on the basis of the entire molecular adhesive layer because the adhesive force is reduced when a component not involved in adhesion is included. More preferably, it is 70 mass% or more and 100 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less, Especially preferably, it is 100 mass%.
  • the thickness of the molecular adhesive layer is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less.
  • the thickness of the molecular adhesive layer is preferably 1 nm or more.
  • the protective film constituting the adhesive sheet of the present invention is provided on the molecular adhesive layer.
  • the protective film has a role of protecting the molecular adhesive layer until it is used after the production of the adhesive sheet of the present invention.
  • the protective film used in the present invention has an embossed surface in which at least one convex portion is present on the surface in contact with the molecular adhesive layer.
  • an adhesive sheet having a smooth protective film hereinafter sometimes referred to as “smooth protective film” that does not have such an embossed surface
  • contact between the smooth protective film and the molecular adhesive layer can occur entirely. Therefore, the reactive group (Z ⁇ ) of the molecular adhesive is in a state where it easily reacts with the compound constituting the smooth protective film, and many reactive groups (Z ⁇ ) are deactivated during storage of the adhesive sheet.
  • the adhesive strength of the layer may be reduced.
  • the contact between the protective film and the molecular adhesive layer can be made only partially, and in many parts, between the protective film and the molecular adhesive layer. It is possible to create a gap. As a result, the amount of the reactive group (Z ⁇ ) deactivated during storage of the adhesive sheet can be reduced, and a decrease in the adhesive strength of the molecular adhesive layer can be suppressed.
  • the protective film having the target embossed surface can be formed by a known method.
  • a film hereinafter sometimes referred to as “film (A)” that is a material for the protective film is passed between the embossing roll and the elastic roll, and the shape of the embossing roll peripheral surface is reflected in the film (A).
  • film (A) a film that is a material for the protective film is passed between the embossing roll and the elastic roll, and the shape of the embossing roll peripheral surface is reflected in the film (A).
  • the protective film which has the target embossed surface can be manufactured.
  • a protective film having a target embossed surface is produced by providing a convex portion made of the same material as or different from the film (A) on the film (A) using a printing technique such as a screen printing method. be able to.
  • Examples of the embossed surface on which the convex portions exist are those in which a large number of protrusions such as hemisphere, columnar shape, triangular prism shape, quadrangular prism shape, conical shape, triangular pyramid shape, quadrangular pyramid shape, stripe shape, etc. are formed on a plane. It is done.
  • the height of the convex portion is not particularly limited, but is usually 10 to 200 ⁇ m, preferably 30 to 100 ⁇ m.
  • the ratio of the total area of the protrusions to the entire protective film is not particularly limited, but is usually 3 to 50%, preferably 5 to 30%.
  • the thickness of the protective film is not particularly limited.
  • the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 60 ⁇ m, and particularly preferably 10 to 45 ⁇ m.
  • the adhesive sheet of the present invention is formed by directly laminating the resin layer, the molecular adhesive layer, and the protective film in this order.
  • the adhesive sheet of the present invention may have a molecular adhesive layer only on one side of the resin layer, or may have a molecular adhesive layer on both sides of the resin layer.
  • the adhesive sheet of the present invention may have a layer other than a resin layer, a molecular adhesive layer, and a protective film.
  • the layer other than the resin layer, the molecular adhesive layer, and the protective film include a support. That is, when the resin layer has a certain thickness, the resin layer also has a function as a support, but when the resin layer is too thin, it is preferable to provide a separate support.
  • paper base materials such as fine paper, art paper, coated paper, kraft paper, glassine paper; laminated base materials obtained by laminating these paper base materials with a thermoplastic resin such as polyethylene; polyethylene film, Polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin Film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, Imide film, a resin substrate such as a fluorine resin film; metal foil; and the like.
  • a thermoplastic resin such as polyethylene; polyethylene film, Polypropylene film, polybutene film, polybutadiene film, polymethylpen
  • Examples of the adhesive sheet of the present invention include those having the following layer structure. Resin layer / molecular adhesive layer / protective film support / resin layer / molecular adhesive layer / protective film support / molecular adhesive layer / resin layer / molecular adhesive layer / protective film molecular adhesive layer / resin layer / support Body / resin layer / molecular adhesive layer / protective film
  • the method for producing the adhesive sheet of the present invention is not particularly limited.
  • a molecular adhesive layer is formed on the resin layer, and then a protective film is formed on the formed molecular adhesive layer, and the molecular adhesive layer and the surface having the embossed surface of the protective film face each other. It is preferable to manufacture by overlapping.
  • the method for producing a laminate of the present invention is characterized in that the protective film constituting the adhesive sheet of the present invention is peeled off and the exposed molecular adhesive layer is pressure-bonded to an adherend.
  • This is a method for producing a laminate having a layer structure of: / molecular adhesive layer / adhered body.
  • a reactive group (Z ⁇ ) in the molecular adhesive usually reacts with a functional group in the compound constituting the adherend to form a chemical bond. Is done. Therefore, as the adherend, one having a group having reactivity with the reactive group (Z ⁇ ) on its surface is usually used. Examples of such an adherend include glass, inorganic oxide, silicone resin, and the like. Moreover, even if it does not contain these components on the surface, it is used as an adherend by applying a surface treatment and providing a layer containing a group having reactivity with the reactive group (Z ⁇ ) on the surface. be able to.
  • the molecular adhesive layer and the adherend are sufficiently adhered.
  • the temperature T p (° C.) when the molecular adhesive layer is pressure-bonded to the adherend is not particularly limited, but preferably satisfies the following formula (I).
  • T g represents the glass transition temperature (° C.) of the resin layer
  • T s represents the softening point (° C.) of the resin layer.
  • H is 40.
  • the value of H is preferably 30, more preferably 20, and even more preferably 0.
  • the pressure at the time of pressure bonding is usually 0.1 to 3.0 MPa, preferably 0.5 to 1.5 MPa.
  • the Young's modulus at a temperature T p (° C.) during pressure bonding of at least one of the resin layer or the adherend is preferably 1 ⁇ 10 6 to 1 ⁇ 10 9 Pa, more preferably 1 ⁇ 10 7 to 9 ⁇ 10 8 Pa, more preferably 1 ⁇ 10 8 to 8 ⁇ 10 8 Pa.
  • the molecular adhesive layer and the adherend can be sufficiently adhered by pressing the molecular adhesive layer to the adherend under conditions that satisfy these requirements.
  • the above polyisobutylene resin solution is applied with a screen printer so that a plurality of cylindrical convex portions having a diameter of 500 ⁇ m and a height of 50 ⁇ m are formed, Subsequently, this thing was dried at 100 degreeC for 2 minute (s), and the protective film (1) whose total area of a convex part is 10% of the whole was obtained.
  • an ultraviolet irradiation device manufactured by Heraeus Co., Ltd., product name “ Using a light hammer 10 MARK II ”, light source: mercury lamp
  • ultraviolet rays were irradiated under the following conditions to form a release agent layer having a thickness of 0.1 ⁇ m to obtain a protective film (3).
  • the total area of the convex portions is 15% of the whole.
  • UV irradiation conditions The ultraviolet irradiation conditions were an illuminance of 84 mW / cm 2 and an amount of light of 100 mJ / cm 2 , and the illuminance and the amount of light were determined using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT) and The amount of light was measured.
  • Production Example 6 In Production Example 3, a protective film (4) was obtained in the same manner as in Production Example 3, except that the polyisobutylene resin solution was applied to the entire surface of the polyethylene terephthalate film.
  • Example 1 The molecular adhesive solution (1) was dip coated on the resin layer (1) by dipping for 5 seconds, and the resulting coating film was dried at 100 ° C. for 30 seconds. Next, using an ultraviolet irradiation device (product name “Light Hammer 10 MARK II” manufactured by Heraeus Co., Ltd., light source: mercury lamp), this coating film is irradiated with ultraviolet rays to perform fixing treatment, and the resin layer (1) And a laminate comprising molecular adhesive layers was obtained.
  • an ultraviolet irradiation device product name “Light Hammer 10 MARK II” manufactured by Heraeus Co., Ltd., light source: mercury lamp
  • the ultraviolet irradiation conditions are an illuminance of 84 mW / cm 2 and an amount of light of 29 mJ / cm 2 , and the illuminance and the amount of light are measured in the UVC region using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT). Illuminance and light intensity were measured.
  • the protective film (1) was overlaid on the molecular adhesive layer of the obtained laminate to obtain an adhesive sheet.
  • Example 2 and 3 Comparative Examples 1 and 2
  • An adhesive sheet was obtained in the same manner as in Example 1 except that the resin layer, molecular adhesive solution, and protective film were those listed in Table 1.

Landscapes

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

Abstract

La présente invention concerne : une feuille adhésive obtenue par stratification directe d'une couche de résine contenant une résine (S), d'une couche d'adhésif moléculaire et d'un film protecteur dans l'ordre indiqué, où ladite couche d'adhésif moléculaire contient un adhésif moléculaire ayant au moins un groupe réactif (Zα) choisi dans le groupe constitué par les groupes amino, les groupes azoture, les groupes mercapto, les groupes isocyanate, les groupes uréido et les groupes époxy, et au moins un groupe réactif (Zβ) choisi dans le groupe constitué par les groupes silanol et les groupes qui génèrent un groupe silanol par une réaction d'hydrolyse, où la résine (S) a une sous-structure réactive (Zγ) qui peut former une liaison chimique avec le groupe réactif (Zα) de l'adhésif moléculaire, et le film protecteur a une surface embossée où au moins une protubérance est présente du côté qui est en contact avec la couche d'adhésif moléculaire ; et un procédé de production d'un corps stratifié utilisant ladite feuille adhésive. Une feuille adhésive comportant une couche de résine, une couche d'adhésif moléculaire et un film protecteur, où ladite feuille adhésive a une adhésivité exceptionnelle à une surface à coller ; et un procédé de production d'un corps stratifié utilisant ladite feuille adhésive sont en outre décrits.
PCT/JP2018/012848 2017-03-30 2018-03-28 Feuille adhésive et procédé de production d'un corps stratifié WO2018181518A1 (fr)

Priority Applications (3)

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CN201880021870.3A CN110461975B (zh) 2017-03-30 2018-03-28 粘接片、和层叠体的制造方法
JP2019510002A JP6605779B2 (ja) 2017-03-30 2018-03-28 接着シート、及び積層体の製造方法
KR1020197029138A KR102314239B1 (ko) 2017-03-30 2018-03-28 접착 시트, 및 적층체의 제조 방법

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JP7508626B2 (ja) 2022-04-18 2024-07-01 輝能科技股▲分▼有限公司 補助フィルム

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JP7508626B2 (ja) 2022-04-18 2024-07-01 輝能科技股▲分▼有限公司 補助フィルム

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KR20190129066A (ko) 2019-11-19
KR102314239B1 (ko) 2021-10-18
TWI758450B (zh) 2022-03-21
JPWO2018181518A1 (ja) 2019-12-12
JP6605779B2 (ja) 2019-11-20
CN110461975A (zh) 2019-11-15
CN110461975B (zh) 2021-12-24

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