WO2016088697A1 - Stratifié de feuilles adhésives autocollantes et stratifié d'élément constitutif de dispositif d'affichage d'image - Google Patents

Stratifié de feuilles adhésives autocollantes et stratifié d'élément constitutif de dispositif d'affichage d'image Download PDF

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WO2016088697A1
WO2016088697A1 PCT/JP2015/083531 JP2015083531W WO2016088697A1 WO 2016088697 A1 WO2016088697 A1 WO 2016088697A1 JP 2015083531 W JP2015083531 W JP 2015083531W WO 2016088697 A1 WO2016088697 A1 WO 2016088697A1
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Prior art keywords
layer
meth
sensitive adhesive
pressure
photocurable
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PCT/JP2015/083531
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English (en)
Japanese (ja)
Inventor
かほる 新美
内田　貴久
福田　晋也
亮太 山本
誠 稲永
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三菱樹脂株式会社
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Priority to JP2016562434A priority Critical patent/JP6772837B2/ja
Publication of WO2016088697A1 publication Critical patent/WO2016088697A1/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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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

Definitions

  • the present invention relates to an adhesive sheet laminate comprising an adhesive resin layer and a release layer, an image display device component laminate using the adhesive sheet laminate, and a method for producing them.
  • the pressure-sensitive adhesive sheet is distributed as a pressure-sensitive adhesive sheet laminate by laminating a protective film (also referred to as “release film”) that can be peeled off the pressure-sensitive adhesive surface from the viewpoint of ensuring handling properties and preventing adhesion of foreign matters to the pressure-sensitive adhesive surface.
  • a protective film also referred to as “release film”
  • release film also referred to as “release film”
  • the transparent pressure-sensitive adhesive sheet itself is used from the viewpoint of ensuring optical properties and flexibility. Since it is preferably thin and flexible, many have been used as pressure-sensitive adhesive sheet laminates obtained by laminating a release film on a transparent pressure-sensitive adhesive sheet.
  • Patent Document 1 Japanese Patent Laid-Open No. 2009-102467
  • an ABA type triblock copolymer composed of an acrylic ester and a methacrylic ester and a hydroxyl group-containing resin are polymerized.
  • a pressure-sensitive adhesive sheet obtained by hot-melt molding a blended acrylic transparent pressure-sensitive adhesive composition between release sheets is disclosed.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2010-185037 is an adhesive sheet comprising an adhesive layer on at least one surface of a release film, and the adhesive layer is crosslinked, and the crosslinked adhesive layer includes: A pressure-sensitive adhesive sheet characterized by having a temperature range of 50,000 Pa to 1 million Pa in any temperature range of 25 ° C. to 120 ° C. when measuring the temperature dispersion behavior of the tensile storage modulus at a frequency of 1 Hz is disclosed. ing.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2013-1818878 discloses a transparent double-sided pressure-sensitive adhesive sheet used for bonding two constituent members for an image display device facing each other. It is the first feature that it is used by being cured by heat or ultraviolet rays while being bonded to a member, and obtained with a laser interferometer in a state where release films are laminated on the front and back surfaces of a transparent double-sided PSA sheet.
  • a transparent double-sided pressure-sensitive adhesive sheet characterized by having a surface shape that satisfies a predetermined condition when the average roughness Ra obtained by analysis is (Y) is disclosed.
  • a release agent is applied by applying a silicone release agent or the like to the surface of a film substrate such as a PET film for ease of adjustment of peelability. What was processed was used.
  • the release film formed by releasing the surface of the film substrate with a silicone release agent tends to increase the production cost, and the release agent is transferred to the surface of the adhesive layer. There was a possibility of deteriorating the quality stability.
  • a foreign material etc. may mix between a film base material and an adhesive resin layer.
  • Patent Document 4 Japanese Patent Laid-Open No. 2011-256319
  • Patent Document 5 Patent Document 5 (WO 2014/007137)
  • Patent Document 4 Japanese Patent Laid-Open No. 2011-256319
  • Patent Document 5 WO 2014/007137
  • [Peeling layer containing polyolefin resin] / [Adhesive layer made of acrylic resin] / [ A pressure-sensitive adhesive sheet laminate formed by coextrusion molding and integration so that three layers of a base material layer made of an acrylic resin] is obtained is disclosed.
  • the conventionally proposed pressure-sensitive adhesive sheet laminate does not have sufficient durability to be used for bonding image display device constituent members.
  • the present invention can suppress foreign matter contamination at the interface between the pressure-sensitive adhesive layer and the release layer and transfer transfer of the release agent to the pressure-sensitive adhesive layer, and is excellent in durability after bonding, and is an image display device constituent member It is intended to provide a new pressure-sensitive adhesive sheet laminate that can be suitably used for bonding.
  • the present invention is a pressure-sensitive adhesive sheet comprising a base material layer (III layer) on one or both sides of a photocurable pressure-sensitive adhesive resin layer (I layer) containing a photocurable pressure-sensitive adhesive resin via a release layer (II layer).
  • a laminate, The photocurable pressure-sensitive adhesive resin layer (I layer) was formed from a resin composition containing a (meth) acrylic acid ester copolymer (A), a crosslinking agent (B) and a photopolymerization initiator (C).
  • the release layer (II layer) is a layer formed from a resin composition containing an olefin polymer (D), and
  • the present invention proposes a pressure-sensitive adhesive sheet laminate in which the photocurable pressure-sensitive adhesive resin layer (I layer) and the release layer (II layer) are formed by coextrusion.
  • a layer (I layer) based on a (meth) acrylate copolymer and a layer (II layer) based on an olefin polymer are optical
  • the interlayer strength is weak and delamination easily occurs, so that one layer (II layer) can be used as a release layer.
  • the photocurable adhesive resin layer (I layer) is a photocurable resin composition containing a (meth) acrylate copolymer (A), a crosslinking agent (B) and a photopolymerization initiator (C).
  • the photocurable adhesive resin layer (I layer) is laminated after being laminated on the adherend, the photocurable adhesive resin layer (I layer) after bonding is made durable. It can be excellent. Therefore, for example, it can be used suitably for pasting of an image display device constituent member.
  • the photo-curable pressure-sensitive adhesive resin layer (I layer) and the release layer (II layer) are formed by coextrusion, so that the photo-curable pressure-sensitive adhesive resin layer (I Layer) and the release layer (II layer) can reduce the possibility of foreign matter entering the interface.
  • the release layer (II layer) is not a layer formed from a silicone resin, but is formed from a resin composition containing a polyolefin resin, the release agent is a photocurable adhesive resin layer (I It is also possible to prevent defects that transfer and transfer to the layer) and contaminate the adherend.
  • the pressure-sensitive adhesive sheet laminate can be provided at a lower cost.
  • the pressure-sensitive adhesive sheet laminate (referred to as “the present pressure-sensitive adhesive sheet laminate”) according to an example of the present embodiment is released on one side or both sides of a photocurable pressure-sensitive adhesive resin layer (I layer) containing a photocurable pressure-sensitive adhesive resin. It is an adhesive sheet laminate comprising a base material layer (III layer) through a layer (II layer).
  • the photocurable adhesive resin layer (I layer) is a layer formed from a resin composition containing a (meth) acrylic acid ester copolymer (A), a crosslinking agent (B) and a photopolymerization initiator (C). And it is preferable that it is a state before photocuring, ie, an uncured state.
  • the photocurable pressure-sensitive adhesive resin layer (I layer) is “the state before photocuring” and is cured by irradiating light with the intention of curing the photocurable pressure-sensitive adhesive resin layer (I layer). Means not in a state. For example, a state that is naturally photocured by the influence of room light, sunlight, or the like is a “state before photocuring”.
  • Such a photocurable adhesive resin layer (I layer) can form a photocurable adhesive resin layer (I layer) from the adhesive composition ⁇ or the adhesive composition ⁇ described below, for example.
  • the adhesive compositions ⁇ and ⁇ are preferable examples as the resin composition for forming the photocurable adhesive resin layer (I layer), and are not intended to be limited thereto. If a photocurable pressure-sensitive adhesive resin layer (I layer) is formed from the pressure-sensitive adhesive composition ⁇ or ⁇ , the sheet shape can be maintained even in an uncrosslinked state before photocuring.
  • the photocurable pressure-sensitive adhesive resin layer (I layer) and the release layer (II layer) can be coextruded by adjusting the 130 ° C. melt viscosity of the pressure-sensitive adhesive composition ⁇ or ⁇ .
  • the release layer (II layer) based on an olefin polymer is difficult to adhere to each other. Can function as. Further, if a photocurable pressure-sensitive adhesive resin layer (I layer) is formed from the pressure-sensitive adhesive composition ⁇ or ⁇ , the adhesiveness can be sufficiently enhanced by finally photocrosslinking.
  • Adhesive composition ⁇ As the adhesive composition ⁇ , a (meth) acrylic acid ester copolymer (A1) comprising a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B1), and a photopolymerization initiator (C1)
  • A1 acrylic acid ester copolymer
  • B1 crosslinking agent
  • C1 photopolymerization initiator
  • the (meth) acrylic acid ester copolymer (A1) as a base polymer in the pressure-sensitive adhesive composition ⁇ is a graft copolymer having a macromonomer as a branch component.
  • the “base polymer” means a resin that forms the main component of the adhesive composition ⁇ .
  • the specific content is not specified.
  • it is a resin that occupies 50% by mass or more of the resin contained in the adhesive composition ⁇ , particularly 80% by mass or more, of which 90% by mass (including 100% by mass) or more (in addition, a base polymer) In the case where two or more types are present, the total amount thereof corresponds to the content).
  • the trunk component of the (meth) acrylic acid ester copolymer (A1) is preferably composed of a copolymer component containing a repeating unit derived from (meth) acrylic acid ester.
  • the glass transition temperature of the copolymer constituting the trunk component of the (meth) acrylic acid ester copolymer (A1) is preferably ⁇ 70 to 0 ° C.
  • the glass transition temperature of the copolymer component constituting the trunk component is a polymer glass obtained by copolymerizing only the monomer component constituting the trunk component of the (meth) acrylic acid ester copolymer (A1).
  • the transition temperature Specifically, it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
  • the glass transition temperature of the copolymer component constituting the trunk component of the (meth) acrylic acid ester copolymer (A1) is the flexibility of the adhesive composition ⁇ at room temperature and the adhesive composition to the adherend.
  • the glass transition temperature is ⁇ 70 ° C. to 0 ° C. in order for the pressure-sensitive adhesive composition ⁇ to have appropriate adhesiveness (tackiness) at room temperature because it affects the wettability of ⁇ , that is, the adhesiveness.
  • ⁇ 65 ° C. or higher or ⁇ 5 ° C. or lower is preferable, and among them, ⁇ 60 ° C. or higher or ⁇ 10 ° C. or lower is particularly preferable.
  • the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.
  • Examples of the (meth) acrylic acid ester monomer contained in the main component of the (meth) acrylic acid ester copolymer (A1) include 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and isooctyl (meth). Examples thereof include acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, and the like.
  • hydroxyethyl (meth) acrylate hydroxypropyl (meth) acrylate, acrylic acid, methacrylic acid, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) having hydrophilic groups and organic functional groups.
  • Acrylamide, (meth) acrylonitrile, etc. can also be used.
  • Various vinyl monomers such as vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether that can be copolymerized with the acrylic monomer or methacryl monomer can also be used as appropriate.
  • the main component of the (meth) acrylic acid ester copolymer (A1) preferably contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units. Since the hydrophobic (meth) acrylate monomer can suppress water absorption of the acrylic copolymer (A) or adjust electrical characteristics such as the relative dielectric constant of the acrylic copolymer (A), preferable. On the other hand, if the main component of the (meth) acrylic acid ester copolymer (A1) is composed of only a hydrophobic monomer, a tendency to whiten by heat and heat is recognized. It is preferable to prevent this.
  • the main component of the (meth) acrylic acid ester copolymer (A1) a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and the polymerizability at the end of the macromonomer.
  • a copolymer component formed by random copolymerization with a functional group can be exemplified.
  • hydrophobic (meth) acrylic acid ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl (meth).
  • examples thereof include (meth) acrylic acid esters having an alicyclic structure such as ethyl (meth) acrylate, terpene acrylate and derivatives thereof, hydrogenated rosin acrylate and derivatives thereof, and styrene.
  • monomers having a long-chain alkyl group structure such as 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate, and monomers having a cyclic structure are acrylic polymers (A) It can be used effectively when adjusting the relative dielectric constant of the.
  • hydrophilic (meth) acrylate monomer examples include hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate.
  • (Meth) acrylic acid ester (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyl Oki Carboxylic group-containing monomers such as propyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconic acid, and amino group content such as dimethylaminoethyl (meth) acrylate and diethylaminoethy
  • monomers having a cyclic ether structure such as tetrahydrofurfuryl (meth) acrylate and (meth) acryloylmorpholine, and alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Examples include alkyl esters and methyl acrylate.
  • the (meth) acrylic acid ester copolymer (A1) preferably contains a macromonomer-derived repeating unit as a branch component of the graft copolymer.
  • the macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.
  • the glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the (meth) acrylic acid ester copolymer (A1). Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the pressure-sensitive adhesive composition ⁇ , the glass transition temperature (Tg) of the macromonomer is 30 ° C. to 120 ° C. Among them, it is preferable to be 40 ° C or higher or 110 ° C or lower, and it is more preferable to be 50 ° C or higher or 100 ° C or lower.
  • the glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC).
  • the macromonomer is preferably contained in the (meth) acrylic acid ester copolymer (A1) in a proportion of 5% by mass to 30% by mass, of which 6% by mass or more and 25% by mass or less. Among them, the content is preferably 8% by mass or more or 20% by mass or less.
  • the component constituting the high molecular weight skeleton of the macromonomer is preferably composed of an acrylic monomer or a vinyl monomer, and more preferably a hydrophobic monomer.
  • Examples of the component constituting the high molecular weight skeleton of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid.
  • (meth) acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid esters such as 4-hydroxybutyl (meth) acrylate and glycerol (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( (Meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxy Propyl maleic acid, 2- ( A) acrylic acid alkoxy
  • a monomer having a glass transition temperature of 30 ° C. to 120 ° C. when the component constituting the high molecular weight skeleton of the macromonomer is a homopolymer is more preferable.
  • examples of the monomer include methyl methacrylate, 3,5,5-trimethylcyclohexane acrylate, isobornyl acrylate, dicyclopentanyl acrylate, and cyclohexyl methacrylate.
  • the monomer when the component constituting the high molecular weight skeleton of the macromonomer has crystallinity, the monomer has a crystal melting temperature of 30 ° C. to 120 ° C. when the component is a homopolymer.
  • examples of the monomer include stearyl acrylate, stearyl methacrylate, cetyl acrylate, cetyl methacrylate, behenyl acrylate, and behenyl methacrylate.
  • one of these monomers may be polymerized and used alone, or a plurality of these monomers may be copolymerized and used.
  • Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
  • the (meth) acrylic acid ester copolymer (A1) preferably has a complex viscosity of 100 to 800 Pa ⁇ s, more preferably 150 to 700 Pa ⁇ s, and more preferably 170 to 600 Pa at a temperature of 130 ° C. and a frequency of 0.02 Hz. -S is more preferable.
  • the complex viscosity at a temperature of 130 ° C. of the (meth) acrylic acid ester copolymer (A1) affects the fluidity of the pressure-sensitive adhesive composition ⁇ when the transparent double-sided pressure-sensitive adhesive material is used by hot-melting. When the viscosity is 100 to 800 Pa ⁇ s, excellent hot melt suitability can be obtained.
  • the complex viscosity of the (meth) acrylic acid ester copolymer (A1) for example, a glass of a copolymer component constituting the trunk component of the (meth) acrylic acid ester copolymer (A1).
  • examples include adjusting the transition temperature.
  • the viscosity is adjusted to ⁇ 70 ° C. to 0 ° C., particularly ⁇ 65 ° C. or higher or ⁇ 5 ° C. or lower, and in particular, ⁇ 60 ° C. or higher or ⁇ 10 ° C. or lower, and the molecular weight of the copolymer component is adjusted to improve viscoelasticity.
  • the method of adjusting can be mentioned. However, it is not limited to this method.
  • the molecular weight of the (meth) acrylic acid ester copolymer (A1) is preferably 100,000 to 1,000,000, particularly 150,000 or more or 800,000 from the viewpoint of adjusting the 130 ° C. melt viscosity to a predetermined range. In the following, it is particularly preferable that it is 200,000 or more or 700,000 or less.
  • Crosslinking agent (B1)) for example, an epoxy crosslinking agent, an isocyanate crosslinking agent, an oxetane compound, a silane compound, an acrylic compound, or the like can be appropriately selected. Especially, it is preferable that it is the polyfunctional (meth) acrylic acid ester monomer which has two or more (meth) acryloyl groups at the point of the reactivity or the intensity
  • the crosslinking agent (B1) contained in the photocurable adhesive resin layer (I layer) is subjected to a crosslinking reaction.
  • the photocurable pressure-sensitive adhesive resin layer (I layer) can exhibit a high cohesive force in a high-temperature environment instead of losing hot melt properties, and can obtain excellent foaming reliability.
  • polyfunctional (meth) acrylic acid ester monomers examples include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin glycidyl ether di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy Di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trio Cyethyl (meth) acrylate, ⁇ -caprolact
  • polyester (meth) acrylate epoxy (meth) acrylate, urethane (meth) acrylate, and polyether (meth) acrylate
  • Acrylic oligomers can be mentioned.
  • the polyfunctional (meth) acrylate monomer is a polyfunctional monomer containing a polar functional group such as a hydroxyl group or Oligomers are preferred.
  • a polar functional group such as a hydroxyl group or Oligomers are preferred.
  • polyfunctional (meth) acrylic acid ester having a hydroxyl group it is preferable to use polyfunctional (meth) acrylic acid ester having a hydroxyl group. Therefore, from the viewpoint of preventing wet heat whitening, the methacrylic acid ester copolymer (A1), that is, the graft copolymer contains a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a trunk component.
  • the content of the crosslinking agent (B1) is not particularly limited. As a guideline, 0.5 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A1), in particular 1 to 15 parts by mass, among which 2 to 10 parts by mass The ratio is preferably less than or equal to parts.
  • the crosslinking agent (B1) in the above range, the shape stability of the photocurable adhesive resin layer (I layer) in an uncrosslinked state and the antifoaming in the photocurable adhesive resin layer (I layer) after crosslinking It is possible to achieve both reliability. However, this range may be exceeded in balance with other elements.
  • the photopolymerization initiator (C1) functions as a reaction initiation assistant in the crosslinking reaction of the aforementioned crosslinking agent (B1).
  • the photopolymerization initiator those currently known can be used as appropriate.
  • a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
  • the crosslinking reaction is likely to proceed.
  • the photocurable resin layer (I layer) is preferable at the point which can be hardened.
  • Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself, and a photoexcited initiator. And a hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
  • the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
  • a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. This is useful in that damage to the body can be reduced.
  • cleavage type photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1.
  • Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, and 2-benzoylbenzoic acid.
  • examples include 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, and derivatives thereof.
  • the photopolymerization initiator is not limited to the substances listed above. Any one of a cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator may be used, or both may be used in combination.
  • the content of the photopolymerization initiator (C1) is not particularly limited. As a guideline, 0.1 to 10 parts by weight, especially 0.5 parts by weight or more or 5 parts by weight or less, more preferably 1 part by weight or more, with respect to 100 parts by weight of the (meth) acrylic ester copolymer (A1) It is preferable to contain in the ratio of 3 mass parts or less. By setting the content of the photopolymerization initiator (C1) in the above range, an appropriate reaction sensitivity with respect to the active energy ray can be obtained.
  • the adhesive composition ⁇ may contain a known component blended in a normal adhesive composition as a component other than the above.
  • various additives such as tackifier resins, antioxidants, light stabilizers, metal deactivators, rust preventives, anti-aging agents, hygroscopic agents, rust preventives and hydrolysis inhibitors are contained as appropriate. It is possible to make it.
  • you may contain a reaction catalyst (A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.) suitably as needed.
  • a (meth) acrylic acid ester copolymer having a weight average molecular weight of 50,000 to 400,000, which is copolymerized with a monomer a3 at a molar ratio of a1: a2: a3 10-40: 90-35: 0-25
  • a resin composition containing (A2), a crosslinking agent (B2), and a photopolymerization initiator (C2) can be mentioned.
  • the (meth) acrylic acid ester copolymer (A2) as a base polymer is 130 from the viewpoint of achieving both shape retention at room temperature and hot melt properties, as described later.
  • the weight average molecular weight is preferably 50000 to 400000, more preferably 60000 or more and 350,000 or less, and particularly preferably 70000 or more and 300000 or less.
  • the (meth) acrylic acid ester copolymer (A2) has a glass transition temperature (Tg) by appropriately selecting the type, composition ratio, polymerization conditions, and the like of the acrylic monomer and methacrylic monomer used to adjust this. And physical properties such as molecular weight can be appropriately adjusted.
  • the acrylic monomer constituting the acrylic ester copolymer include 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-butyl (meth) acrylate, ethyl (Meth) acrylate and the like can be mentioned as the main raw material.
  • a (meth) acrylic monomer having various functional groups may be copolymerized with the acrylic monomer according to the purpose of imparting cohesive force or imparting polarity.
  • the (meth) acrylic monomer having the functional group include methyl methacrylate, methyl acrylate, hydroxyethyl acrylate, acrylic acid, glycidyl (meth) acrylate, N-substituted (meth) acrylamide, acrylonitrile, methacrylonitrile, and fluorine-containing alkyl.
  • (Meth) acrylate, organosiloxy group-containing (meth) acrylate and the like can be mentioned.
  • the (meth) acrylic acid ester copolymer (A2) includes a monomer a1 having a glass transition temperature (Tg) of less than 0 ° C., a monomer a2 having a glass transition temperature (Tg) of from 0 ° C. to less than 80 ° C., and a glass transition.
  • a (meth) acrylic acid ester copolymer obtained by copolymerizing a monomer a3 having a temperature (Tg) of 80 ° C. or more and a molar ratio of a1: a2: a3 10-40: 90-35: 0-25
  • the glass transition temperatures (Tg) of the monomers a1, a2, and a3 are the meanings of the glass transition temperatures (Tg) when a polymer is produced from the monomer (homogenization).
  • the monomer a1 is preferably a (meth) acrylic acid ester monomer having an alkyl group structure having a side chain having 4 or more carbon atoms, for example.
  • the side chain having 4 or more carbon atoms may be a straight chain or a branched carbon chain.
  • the monomer a1 is a (meth) acrylate monomer having a linear alkyl group structure having 4 to 10 carbon atoms, or a branched alkyl group structure having 6 to 18 carbon atoms ( It is preferably a (meth) acrylic acid ester monomer.
  • (meth) acrylic acid ester monomer having a linear alkyl group structure having 4 to 10 carbon atoms includes n-butyl acrylate, n-hexyl acrylate, n-octyl (meth) acrylate, n-nonyl ( Examples include meth) acrylate and n-decyl (meth) acrylate.
  • (meth) acrylic acid ester monomer having a branched alkyl group structure having 6 to 18 carbon atoms includes 2-ethylhexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (Meth) acrylate, isodecyl (meth) acrylate, etc. can be mentioned.
  • the monomer a2 has a (meth) acrylic acid ester monomer having 4 or less carbon atoms, a (meth) acrylic acid ester monomer having a cyclic skeleton in the side chain, a vinyl monomer having 4 or less carbon atoms, or a cyclic skeleton in the side chain.
  • a vinyl monomer is preferred.
  • the monomer a2 is particularly preferably a vinyl monomer having 4 or less carbon atoms in the side chain.
  • the “(meth) acrylic acid ester monomer having 4 or less carbon atoms” includes methyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl methacrylate, t- Examples thereof include butyl acrylate, isobutyl acrylate, and isobutyl methacrylate.
  • “(Meth) acrylic acid ester monomer having a cyclic skeleton in the side chain” includes isobornyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, tetrahydrofurfuryl methacrylate, benzyl acrylate, benzyl methacrylate , Phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, cyclic trimethylolpropane formal acrylate, 4-ethoxylated cumylphenol acrylate, dicyclopentenyl Oxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate - it can be mentioned, such as theft.
  • Examples of the “vinyl monomer having 4 or less carbon atoms” include vinyl acetate, vinyl propionate, vinyl butyrate, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and the like.
  • Examples of the “vinyl monomer having a cyclic skeleton in the side chain” include styrene, cyclohexyl vinyl ether, norbornyl vinyl ether, norbornenyl vinyl ether and the like. Among these, a vinyl monomer having 4 or less carbon atoms in the side chain or an acrylate monomer having 4 or less carbon atoms in the side chain is particularly suitable.
  • the monomer a3 is preferably a (meth) acrylic acid ester monomer having a side chain having 1 or less carbon atoms or a (meth) acrylic acid ester monomer having a cyclic skeleton in the side chain.
  • examples of the “(meth) acrylic acid ester monomer having a side chain having 1 or less carbon atoms” include methyl methacrylate, acrylic acid, and methacrylic acid.
  • Examples of the (meth) acrylate monomer having a cyclic skeleton in the side chain include isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, And cyclopentenyl methacrylate.
  • the tan ⁇ peak can be adjusted to 0 to 20 ° C., and the sheet-like shape can be maintained in a normal state, that is, a room temperature state.
  • tackiness a peelable adhesiveness
  • the molar ratio of the monomer a1, the monomer a2, and the monomer a3 in the (meth) acrylic acid ester copolymer constituting the (meth) acrylic acid ester copolymer (A2) is a1: a2.
  • A3 10 to 40:90 to 35: 0 to 25, preferably 13 to 40:87 to 35: 0 to 23, more preferably 15 to 40:85 to 38: 2 to 20 preferable.
  • the molar ratio is preferably a2> a1> a3.
  • Cross-linking agent (B2) When the cross-linking agent (B2) undergoes a cross-linking reaction, the pressure-sensitive adhesive composition ⁇ exhibits a high cohesive force in a high temperature environment and can obtain excellent foaming reliability.
  • a crosslinking agent (B2) for example, a crosslinking agent comprising an epoxy crosslinking agent, an isocyanate crosslinking agent, an oxetane compound, a silane compound, an acrylic compound, or the like can be appropriately selected.
  • polyfunctional (meth) acrylic acid ester monomers examples include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, neopentyl glycol di (Meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ⁇ -caprolactone modified tris (2-hydroxyethyl) isocyanurate Li (meth) acrylate, pentaerythritol tri (meth)
  • a polyfunctional monomer or oligomer containing a polar functional group is preferable from the viewpoint of improving adhesion to the adherend, heat resistance, and wet heat whitening suppression effect.
  • the content of the crosslinking agent (B2) is not particularly limited.
  • the ratio is preferably less than or equal to parts.
  • the photopolymerization initiator (C2) functions as a reaction initiation aid in the crosslinking reaction of the aforementioned crosslinking agent (B2).
  • An organic peroxide that generates radicals using an active energy ray as a trigger, a photopolymerization initiator, or the like can be used as appropriate.
  • a photopolymerization initiator particularly a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less, is preferable from the viewpoint of easy control of the crosslinking reaction.
  • the photocurable resin layer (I layer) is preferable at the point which can be hardened.
  • Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself, and a photoexcited initiator. And a hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
  • the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive sheet after the cross-linking reaction is completed, and there is no possibility of causing unexpected light degradation or the like to the pressure-sensitive adhesive sheet, which is preferable.
  • a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product like a cleavage type photopolymerization initiator during radical generation reaction by irradiation with active energy rays such as ultraviolet rays, so it is difficult to become a volatile component after the reaction is completed. This is useful in that damage to the body can be reduced.
  • cleavage type photopolymerization initiator examples include benzoin butyl ether, benzyl dimethyl ketal, 2-hydroxyacetophenone, diphenyl-2,4,6-trimethylbenzoylphosphine oxide and derivatives thereof.
  • hydrogen abstraction type photopolymerization initiator examples include benzophenone, Michler's ketone, 2-ethylanthraquinone, thioxanthone and derivatives thereof.
  • the photopolymerization initiator is not limited to the substances listed above.
  • the adhesive composition ⁇ either one of a cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator may be used, or a combination of both may be used.
  • the content of the photopolymerization initiator (C2) is not particularly limited. As a standard, 0.1 to 10 parts by weight, particularly 0.5 parts by weight or more or 5 parts by weight or less, more preferably 1 part by weight or more, with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer (A2) It is preferable to contain in the ratio of 3 mass parts or less. By setting the content of the photopolymerization initiator (C2) in the above range, an appropriate reaction sensitivity with respect to active energy rays can be obtained.
  • the pressure-sensitive adhesive composition ⁇ may contain known components blended in a normal pressure-sensitive adhesive composition as components other than those described above. For example, if necessary, various additives such as tackifier resins, antioxidants, light stabilizers, metal deactivators, rust inhibitors, anti-aging agents, and hygroscopic agents can be appropriately contained. It is. Moreover, you may contain reaction catalyst (A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.) suitably as needed.
  • reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
  • the release layer (II layer) is preferably a layer formed from a resin composition containing the olefin polymer (D) as a base polymer.
  • olefin polymer (D) examples include ethylene- ⁇ -olefin copolymers, styrene elastomers, polyisobutylene resins, polybutene resins, polybutadiene resins, polyisoprene resins, and ethylene / cyclic olefin copolymers. It is preferable to use one or a combination of two or more of these.
  • the “ethylene- ⁇ -olefin copolymer” may be a copolymer of ethylene and ⁇ -olefin.
  • the type of ⁇ -olefin copolymerized with ethylene is not particularly limited.
  • ⁇ -olefins having 3 to 20 carbon atoms can be suitably used.
  • propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-butene-1, 4-methyl-pentene-1, etc. Can be mentioned.
  • a copolymer having 1-butene, 1-hexene, or 1-octene as a copolymer component as the ⁇ -olefin is preferable.
  • only one ⁇ -olefin copolymerized with ethylene may be used alone, or two or more types may be used in combination at any ratio.
  • the content of ⁇ -olefin copolymerized with ethylene is not particularly limited. For example, it is preferably 2 mol% to 40 mol%, more preferably 3 mol% or more or 30 mol% or less, and more preferably 5 mol% or more or 25 mol% or less, based on the entire monomer used for copolymerization. preferable. If the content of the ⁇ -olefin copolymerized with ethylene is within the above range, it is preferable because crystallinity is reduced by the copolymer component and transparency (for example, total light transmittance, haze, etc.) is improved.
  • the content of the ⁇ -olefin copolymerized with ethylene is in the above-mentioned range since the generation of blocking is suppressed when producing raw material pellets.
  • the type and content of ⁇ -olefin copolymerized with ethylene can be analyzed by a known method, for example, a nuclear magnetic resonance (NMR) measuring device or other instrumental analyzer.
  • the ethylene- ⁇ -olefin copolymer may contain monomer units based on monomers other than ⁇ -olefin.
  • the monomer unit include cyclic olefins, vinyl aromatic compounds (such as styrene), polyene compounds, and the like.
  • the content of the monomer units is preferably 20 mol% or less, more preferably 15 mol% or less, based on 100 mol% of all monomer units in the ethylene- ⁇ -olefin copolymer. is there.
  • the steric structure, branching, branching degree distribution, molecular weight distribution and copolymerization form (random, block, etc.) of the ethylene- ⁇ -olefin copolymer are not particularly limited, but have, for example, long chain branching.
  • Copolymers that is, copolymers having a branch in the main chain itself, generally have good mechanical properties, and the melt tension (melt tension) at the time of forming a film increases, so that the moldability is improved. There are advantages.
  • the ethylene- ⁇ -olefin copolymer may or may not have a crystal melting peak.
  • the upper limit of the crystal melting peak temperature is not particularly limited. In consideration of transparency and low temperature flexibility, the temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 65 ° C. or lower. Further, the lower limit of the crystal melting peak temperature is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 40 ° C. in consideration of blocking prevention of raw material pellets, handling property of the adhesive, shape retention performance at room temperature, and the like. It is above °C. There may be a plurality of crystal melting peak temperatures.
  • the heat of crystal melting of the ethylene- ⁇ -olefin copolymer is not particularly limited. Preferably, it is 0 to 100 J / g, especially 5 J / g or more or 80 J / g or less, and more preferably 10 J / g or more or 65 J / g or less. If it is in the said range, since a softness
  • the crystal melting peak temperature and the crystal melting calorie can be measured using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min according to JIS K-7121.
  • the MFR of the above ethylene- ⁇ -olefin copolymer in JIS K-7210 is preferably from 1 to 80 g / 10 min, especially 5 g / 10 min or more or 60 g / 10 min or less, and more preferably 8 g / 10 min or more or 50 g / min. It is particularly preferable that it is 10 min or less.
  • the ethylene- ⁇ -olefin copolymer is preferably an ethylene- ⁇ -olefin copolymer having a density of 0.850 to 0.900 g / cm 3 in order to impart excellent transparency and low temperature characteristics.
  • An ethylene- ⁇ -olefin copolymer (linear low density polyethylene) of 0.860 to 0.885 g / cm 3 is more preferred.
  • ethylene- ⁇ -olefin copolymers an ethylene- ⁇ -olefin random copolymer is more preferable from the viewpoint of low crystallinity and excellent light transmittance and flexibility. These may be used alone or in a combination of two or more.
  • the method for producing the ethylene- ⁇ -olefin copolymer is not particularly limited, and a known polymerization method using a known ethylene polymerization catalyst can be employed.
  • Known polymerization methods include, for example, a slurry polymerization method, a solution polymerization method, a gas polymerization method using a multi-site catalyst typified by a Ziegler-Natta type catalyst, or a single-site catalyst typified by a metallocene catalyst or a post metallocene catalyst. Examples thereof include a phase polymerization method and a bulk polymerization method using a radical initiator.
  • polystyrene elastomer examples include SBR (styrene-butadiene rubber), SIB (styrene-isobutylene rubber), SBS (styrene-butylene-styrene block copolymer), and SIS (styrene-isobutylene-styrene block copolymer).
  • SBR styrene-butadiene rubber
  • SIB styrene-isobutylene rubber
  • SBS styrene-butylene-styrene block copolymer
  • SIS styrene-isobutylene-styrene block copolymer
  • Polymer SEBS (styrene-ethylene-butylene-styrene block copolymer), SEBC (styrene-ethylene-butylene-ethylene block copolymer), SIB (styrene-isobutylene block copolymer), HS
  • the styrene content in the styrene elastomer is not particularly limited.
  • 20 mol% or less is preferable with respect to all monomer components constituting the elastomer.
  • the MFR (JIS K7210: temperature 190 ° C., load 21.18 N) of the above styrene elastomer is not particularly limited. It is preferably 5 g / 10 min to 100 g / 10 min, particularly 8 g / 10 min or more or 80 g / 10 min or less, and more preferably 10 g / 10 min or more or 50 g / 10 min or less.
  • polyisobutylene resin may be a resin having a polyisobutylene skeleton in the main chain or side chain.
  • examples thereof include homopolymers of isobutylene monomers, copolymers of isobutylene and a small amount of isoprene, copolymers of isobutylene and n-butane or butadiene.
  • the viscosity average molecular weight (Mv) of the polyisobutylene resin is not particularly limited. It is preferably 50,000 to 400,000, more preferably 70,000 or more and 300,000 or less, and more preferably 100,000 or more or 200,000 or less. By setting the viscosity average molecular weight (Mv) in the above range, it becomes easy to improve all of workability, shape stability after processing, and practical heat resistance.
  • the olefin polymer (D) may have a functional group.
  • compatibility with an additive such as an antioxidant described later can be enhanced, and a photocurable resin layer (I layer) or a base material layer (III layer) ) And the adhesive strength can be adjusted.
  • these may be used alone or in combination with an olefin polymer having no functional group, but in consideration of molding processability, economy, etc. when forming into a sheet, the functional group is It is preferable to use it together with an olefin polymer which does not exist.
  • olefin polymers having functional groups include silane-modified olefin polymers, acid-modified olefin polymers, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), and ethylene-methyl. It is at least one resin selected from the group consisting of a methacrylate copolymer (E-MMA), an ethylene-ethyl acrylate copolymer (E-EAA), and an ethylene-glycidyl methacrylate copolymer (E-GMA). It is preferable.
  • E-MMA methacrylate copolymer
  • E-EAA ethylene-ethyl acrylate copolymer
  • E-GMA ethylene-glycidyl methacrylate copolymer
  • the molecular weight of the olefin polymer (D) is preferably 50,000 to 400,000 from the viewpoint of adjusting the 130 ° C. melt viscosity to a predetermined range, more preferably 60,000 or more and 300,000 or less, of which 70,000. It is particularly preferable that it is more than or less than 200,000.
  • ⁇ Other resins> In addition to the olefin polymer (D), various additives can be added to the release layer (II layer) as necessary.
  • the additive include a silane coupling agent, an antioxidant, a weathering stabilizer, a processing aid, a nucleating agent, an ultraviolet absorber, a flame retardant, and a discoloration preventing agent. These additives may be used alone or in combination of two or more.
  • the said base material layer (III layer) should just function as a base material for making it easy to peel a mold release layer (II layer). Therefore, it has a certain degree of hardness and stiffness, and at least the adhesive strength with the photocurable pressure-sensitive adhesive resin layer (I layer) based on the (meth) acrylic acid ester copolymer (A), What has a higher adhesive strength with the release layer (II layer) which uses olefin polymer (D) as a base resin is preferable.
  • the base material layer (III layer) is preferably a layer containing, as a base resin, one or more thermoplastic resins selected from the group consisting of polyester, polyolefin, polycarbonate, and acrylic resin. . Among them, it is preferable to use a polyolefin-based resin in order to improve the adhesive strength with the release layer (II layer).
  • additives can be added to the base material layer (III layer) as necessary.
  • the additive include a silane coupling agent, an antioxidant, a weathering stabilizer, a processing aid, a nucleating agent, an ultraviolet absorber, a flame retardant, and a discoloration preventing agent. These additives may be used alone or in combination of two or more.
  • the pressure-sensitive adhesive sheet laminate comprises a base material layer (III layer) on one side of a photo-curable pressure-sensitive adhesive resin layer (I layer) via a release layer (II layer), while a photo-curable pressure-sensitive adhesive resin layer ( The structure provided with the mold release layer (IV layer) and the base material layer (V layer) on the other side of I layer) may be sufficient. At this time, it is preferable that the photocurable adhesive resin layer (I layer) and the release layers (II layer) on both sides are coextruded into two types and two layers.
  • the release layer (IV layer) and the base material layer (V layer) laminated on the other side of the photocurable pressure-sensitive adhesive resin layer (I layer) are, for example, known in that the film surface is subjected to a release treatment.
  • the release film can be used.
  • the photocurable pressure-sensitive adhesive resin layer (I layer) and the one-side release layer (II layer) may be coextruded into two types and three layers.
  • transparent inorganic oxide film layers such as SiO 2 and Al 2 O 3 , barrier film layers, retardation films for displays, and antistatic layers. it can.
  • the thickness of this pressure-sensitive adhesive sheet laminate can meet the demand for thinning by reducing the sheet thickness, but if the thickness is too thin, for example, if there is an uneven part on the surface of the bonding member In addition, there is a possibility that bubbles are generated around the step. From this viewpoint, the thickness of the pressure-sensitive adhesive sheet laminate is preferably 80 to 2000 ⁇ m, more preferably 100 ⁇ m or more and 1500 ⁇ m or less, and particularly preferably 150 ⁇ m or more and 1000 ⁇ m or less.
  • the photocurable pressure-sensitive adhesive resin layer (I layer) has a thickness of 50 ⁇ m to 1000 ⁇ m, preferably 70 ⁇ m or more and 500 ⁇ m or less, more preferably 100 ⁇ m or more and 350 ⁇ m or less.
  • the thickness of the release layer (II layer) Is preferably 5 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m or more and 350 ⁇ m or less, and particularly preferably 18 ⁇ m or more or 250 ⁇ m or less, and the thickness of the base layer (III layer) is 25 ⁇ m to 500 ⁇ m, especially 38 ⁇ m or more or 350 ⁇ m or less. Among these, it is preferable that it is 50 micrometers or more or 250 micrometers or less.
  • the pressure-sensitive adhesive sheet laminate can obtain the following physical properties.
  • ⁇ Melt viscosity> In this pressure-sensitive adhesive sheet laminate, a 130 ° C. I-layer melt viscosity ⁇ I of the resin composition constituting the photocurable adhesive resin layer (I layer) and a resin composition constituting the release layer (II layer)
  • the 130 ° C. II layer melt viscosity ⁇ II is in the range of 1 ⁇ 10 1 to 5 ⁇ 10 3 Pa ⁇ s, and the I layer melt viscosity ⁇ I and the II layer melt viscosity ⁇ II
  • the ratio ⁇ II / ⁇ I is preferably 0.05-30.
  • the II layer melt viscosity ⁇ II of the resin composition constituting the release layer (II layer) contained as the base resin within a predetermined range, the same viscosity characteristics will be exhibited at the same temperature.
  • the co-extrusion can enhance the adhesion between the layers when integrated by co-extrusion, so that the interfacial adhesion between the two layers can be enhanced.
  • both the I layer melt viscosity ⁇ I of the resin composition constituting the photocurable adhesive resin layer (I layer) and the II layer melt viscosity ⁇ II of the resin composition constituting the release layer (II layer) are both It is preferably 1 ⁇ 10 1 to 5 ⁇ 10 3 Pa ⁇ s. If both are 1 ⁇ 10 1 Pa ⁇ s or more, it is easy to form a sheet while heating, and if it is 5 ⁇ 10 3 Pa ⁇ s or less, adhesion between layers can be maintained, and the layers can be integrated. Since it becomes easy, it is preferable. Among them, the 130 ° C.
  • melt viscosity ⁇ is 2 ⁇ 10 1 Pa ⁇ s or more or 3 ⁇ 10 3 Pa ⁇ s or less, and more preferably 3 ⁇ 10 1 Pa ⁇ s or more or 1 ⁇ 10 3 Pa ⁇ s or less. Is particularly preferred.
  • the ⁇ II / ⁇ I of the I layer melt viscosity ⁇ I and the II layer melt viscosity ⁇ II is preferably 0.05 to 30, more preferably 0.1 or more, and 25 or less, of which 0 .2 or more and 20 or less, more preferably 0.3 or more and 15 or less.
  • a resin that is a main component of each resin composition that is, a (meth) acrylic acid ester copolymer (A) and an olefin
  • Mw weight average molecular weight of the (meth) acrylic acid ester copolymer (A) is 100,000 to 800,000, particularly 150,000 or more and 550,000 or less, and more preferably 200,000 or more or 500,000 or less. Is particularly preferred.
  • the weight average molecular weight (Mw) of the olefin polymer (D) is 50,000 to 400,000, particularly 60,000 or more and 200,000 or less, and particularly preferably 70,000 or more and 150,000 or less.
  • the melt viscosity may be adjusted by increasing or decreasing the amount of additive components such as a crosslinking agent and a photocrosslinking initiator.
  • the Si abundance ratio of the surface of the photocurable adhesive resin layer (I layer) is preferably less than 2.0 atom%. If the Si abundance ratio on the surface of the photocurable pressure-sensitive adhesive resin layer (I layer) is less than 2.0 atom%, the adhesive force of the photocurable pressure-sensitive adhesive resin layer due to the migration of Si is reduced or the adherend is contaminated. This is preferable. From this point of view, the Si abundance ratio of the surface of the photocurable pressure-sensitive adhesive resin layer (I layer) is preferably less than 2.0 atom%, more preferably less than 1.5 atom%, and more preferably 1.0 atom%. It is particularly preferred that it is less than.
  • the migratory component applied to the release layer (II layer) should not be mixed. However, it is not limited to such a method.
  • the peeling force when the release layer (II layer) is peeled 180 ° from the photocurable adhesive resin layer (I layer) at a peeling speed of 300 mm / min is 0.3 N / cm or less. If the said peeling force is 0.3 N / cm or less, since there is little peeling resistance and it is excellent in workability
  • the peeling force is preferably 0.3 N / cm or less, more preferably 0.01 N / cm or more or 0.25 N / cm or less, and particularly 0.02 N / cm. More preferably, it is not less than cm or not more than 0.2 N / cm.
  • the peel force between the base layer (III layer) and the release layer (II layer) is greater than the peel force between the photocurable adhesive resin layer (I layer) and the release layer (II layer). Is preferably large.
  • the peel force between the base layer (III layer) and the release layer (II layer) is greater than the peel force between the photocurable adhesive resin layer (I layer) and the release layer (II layer).
  • the pressure-sensitive adhesive sheet laminate comprises a base material layer (III layer) on one side of a photo-curable pressure-sensitive adhesive resin layer (I layer) via a release layer (II layer).
  • the release layer (IV layer) and the base material layer (V layer) are provided on the other side of the resin layer (I layer)
  • the photocurable adhesive resin layer (I layer) and the release layer (II Layer) and the peeling force between the photocurable adhesive resin layer (I layer) and the release layer (IV layer) can be made different.
  • the peeling force between the photocurable adhesive resin layer (I layer) and the release layer (II layer) and the peeling force between the photocurable adhesive resin layer (I layer) and the release layer (IV layer).
  • the adhesive force of the photocurable adhesive resin layer (I layer) is preferably 3 N / cm to 30 N / cm.
  • the adhesive strength of the photocurable adhesive resin layer (I layer) is 3 N / cm to 30 N / cm, more preferably 4 N / cm or more or 25 N / cm or less, and more preferably 5 N / cm. It is particularly preferable that the density is 20 N / cm or less.
  • the composition of the (meth) acrylate copolymer (A) constituting the (I layer) In addition to adjusting the molecular weight and the crosslinking agent (B), it is preferable to appropriately add an additive that contributes to improving the adhesive strength, such as a silane coupling agent. However, it is not limited to such a method.
  • This pressure-sensitive adhesive sheet laminate is, for example, a resin composition forming a photocurable pressure-sensitive adhesive resin layer (I layer), that is, a (meth) acrylic acid ester copolymer (A), a crosslinking agent (B), and photopolymerization initiation.
  • a photocurable pressure-sensitive adhesive resin layer that is, a (meth) acrylic acid ester copolymer (A), a crosslinking agent (B), and photopolymerization initiation.
  • a resin composition containing an olefin polymer D
  • a pressure-sensitive adhesive sheet laminate comprising a base material layer (III layer) on one side or both sides of a photocurable pressure-sensitive adhesive resin layer (I layer) containing a photocurable pressure-sensitive adhesive resin via a release layer (II layer) The body can be manufactured.
  • the resin composition which forms a photocurable adhesive resin layer (I layer), the resin composition which forms a mold release layer (II layer), and the resin composition which forms a base material layer (III layer) further
  • the pressure-sensitive adhesive sheet laminate can also be produced by co-extrusion.
  • the image display device constituting member laminate is, for example, a release layer from the photocurable pressure-sensitive adhesive resin layer (I layer) of the pressure-sensitive adhesive sheet laminate using the pressure-sensitive adhesive sheet laminate produced as described above. (II layer) and base material layer (III layer) are peeled off together, and then two image display device constituent members are laminated via the photocurable adhesive resin layer (I layer), and one or both of the images
  • the image display device constituent member laminate can be manufactured by irradiating the photocurable adhesive resin layer (I layer) with light through the display device constituent member and curing it.
  • ⁇ Shaping process> The surface shape identical to the uneven shape of the bonding surface of the image display device constituent member is formed on the pressure-sensitive adhesive sheet laminate, and the image display device configuration is formed using the pressure-sensitive adhesive sheet laminate as described above.
  • a member laminated body can also be manufactured.
  • an appropriate shaping method such as shaping with a press mold, shaping with a mold, shaping with a roll, shaping with lamination, etc. is appropriately performed on the pressure-sensitive adhesive sheet laminate. can do.
  • the forming method using a press mold or a roll is preferable from the viewpoints of productivity, accuracy of forming process, and the like. That is, as a method of shaping the same surface shape as the uneven shape of the bonding surface of the image display device constituting member, a mold simulating the uneven shape of the bonding surface of the image display device forming member is used as a photocurable adhesive. Press against the release layer (II layer) and the base layer (III layer) against at least one side of the resin layer (I layer), that is, apply together with the release layer (II layer) and base layer (III layer). A method of forming can be preferably exemplified.
  • an unstretched film As the release film of the release layer (II layer).
  • an unstretched film it is possible to easily form a surface shape that is substantially the same as the concave and convex shape of the original mold when a shaping process is performed by a press process or the like.
  • unstretched films it is more preferable to use any one of unstretched polypropylene film, unstretched polyethylene film, and unstretched polyester film from the viewpoint of mechanical strength, flexibility, and chemical resistance of the film itself.
  • Forming with a press mold may include a method of pressing at least one side of a photocurable adhesive resin layer (I layer) through a release layer (II layer) and a base material layer (III layer). it can. Also, the release layer (II layer) and the base material layer (III layer) are pressed by a press mold and shaped, and an adhesive composition is applied to the release layer (II layer) and the base material layer (III layer).
  • the present pressure-sensitive adhesive sheet laminate that has been shaped can also be produced by applying or pouring an object. Under the present circumstances, the shaping using a metal mold
  • Forming with a roll is performed by passing a pressure-sensitive adhesive sheet laminate comprising a photocurable pressure-sensitive adhesive resin layer (I layer), a release layer (II layer) and a base material layer (III layer) between the rolls.
  • a pressure-sensitive adhesive sheet laminate comprising a photocurable pressure-sensitive adhesive resin layer (I layer), a release layer (II layer) and a base material layer (III layer) between the rolls.
  • Forming by lamination can produce a two-sided pressure-sensitive adhesive sheet 1 that is shaped by preparing two flat pressure-sensitive adhesive sheets having different sizes and superposing them.
  • each structural member for image display apparatuses such as a surface protection panel and a touch panel, can be bonded without gap.
  • a specific shaping method will be described below. However, it is not limited to these methods.
  • the pressure-sensitive adhesive sheet laminate provided with the photocurable pressure-sensitive adhesive resin layer (I layer), release layer (II layer) and base material layer (III layer) was appropriately slit and slit. While feeding and feeding the pressure-sensitive adhesive sheet laminate, the release layer (II layer) is peeled off, and a photocurable pressure-sensitive adhesive is used by using a press mold along the surface irregularity shape of the adherend, that is, the surface shape of the adherend surface 2a. The resin layer (I layer) is directly hot pressed to form the surface.
  • the pressure-sensitive adhesive sheet laminate is produced by cutting pieces into a handleable shape.
  • the material of the press mold is not particularly limited, but a silicone resin having excellent releasability and a fluorine resin can also be used. Moreover, even if it is a material without mold release property, such as stainless steel and aluminum, it can use suitably by apply
  • the temperature of hot pressing is, for example, room temperature or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher.
  • a press pressure, a press depth, and press time suitably with a dimension, a shape, and a shaping state.
  • the cutting method by a Thomson blade and a rotary blade can be mentioned, for example.
  • a pressure-sensitive adhesive sheet that has been surface-shaped by applying a pressure-sensitive adhesive to at least one surface of a release film that has been previously shaped into a surface irregularity shape of the adherend, that is, a surface shape substantially the same as the surface shape of the adherend surface. That is, an original sheet of a photocurable adhesive resin layer (I layer) is formed.
  • the release adhesive film on the one side is peeled off in the next step, and the exposed adhesive sheet surface is cut along the outer shape, After removing unnecessary adhesive ears on the outer periphery of the sheet, a new release film wider than the outer cut size is pasted again.
  • the pressure-sensitive adhesive sheet laminate is produced by cutting pieces into a handleable shape.
  • Adhesive is applied or injected into a mold that imitates the surface irregularity of the adherend, that is, the surface shape of the adherend surface, to form a surface-shaped adhesive sheet, that is, a photocurable adhesive resin layer (I layer).
  • a surface-shaped adhesive sheet that is, a photocurable adhesive resin layer (I layer).
  • a release film is pasted on the opposite side, and a rubber roll or the like is adhered to the release film. After solidifying the pressure-sensitive adhesive, the pressure-sensitive adhesive sheet laminate is pulled away from the mold by pulling the release film.
  • the material of the mold is not particularly limited, but a silicone resin having excellent releasability and a fluorine resin can also be used. Moreover, even if it is a metal mold
  • Shapeing method by roll After applying a pressure-sensitive adhesive, that is, a photocurable pressure-sensitive adhesive resin layer (I layer), between two flat release films, the surface irregularity shape of the adherend, that is, the surface shape of the adherend surface, was simulated on at least one side.
  • a shaping roll is arranged, sandwiched between the rolls on the other side and passed, and the surface is shaped to form an adhesive sheet, that is, a photocurable adhesive resin layer (I layer) original sheet.
  • the release adhesive film on the one side is peeled off in the next step, and the exposed adhesive sheet is cut along the shape of the shaped shape Then, after removing unnecessary adhesive ears on the outer periphery of the outer shape, a new release film wider than the outer cut size is reapplied.
  • the pressure-sensitive adhesive sheet laminate is produced by cutting pieces into a handleable shape.
  • the temperature at which the shaping roll is arranged and sandwiched between the rolls on the other side and passed through is preferably room temperature or higher, more preferably 80 ° C. or higher, more preferably 100 ° C. That's it.
  • a flat first pressure-sensitive adhesive sheet in which release films are laminated on both sides that is, an original sheet of a photocurable pressure-sensitive adhesive resin layer (I layer) is appropriately slit, Then, a flat second pressure-sensitive adhesive sheet having a different size cut into the shape of the surface of the stepped portion is prepared. Thereafter, the release film on each one surface side is peeled off, and the exposed adhesive surfaces are laminated together to produce the present adhesive sheet laminate having a desired surface shaping.
  • sheet is a thin product as defined by JIS and generally has a thickness that is small and flat instead of length and width.
  • film refers to length and width.
  • a thin flat product whose thickness is extremely small in comparison with the maximum thickness is arbitrarily limited and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900).
  • a film having a thickness of 100 ⁇ m or more is sometimes referred to as a sheet, and a film having a thickness of less than 100 ⁇ m is sometimes referred to as a film.
  • [I-layer resin composition 1] Acrylic acid obtained by random copolymerization of 15 parts by weight of a polymethyl methacrylate macromonomer having a number average molecular weight of 2400, 81 parts by weight of butyl acrylate and 4 parts by weight of acrylic acid as the (meth) acrylic acid ester copolymer (A) 1 kg of ester copolymer (A-1) (weight average molecular weight: 230,000), 100 g of glycerin dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: G101P) (B-1) as a crosslinking agent (B), light A mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as a polymerization initiator (C) (product name: Ezacure TZT, manufactured by Lanberti) (C-1) 15 g (C-1) is uniformly mixed to obtain a resin for I layer A composition (I-1) was produced.
  • the (meth) acrylic acid ester copolymer (A) a vinyl copolymer (A-) obtained by random copolymerization of 55 parts by mass of 2-ethylhexyl acrylate, 40 parts by mass of vinyl acetate, and 5 parts by mass of acrylic acid.
  • I-layer resin composition 3 As a resin composition 3 for I layer, a block copolymer of methyl methacrylate and butyl acrylate (manufactured by Kuraray Co., Ltd., product name: Clarity LA2140e, density: 1080 kg / m 3 , melting point: 55 ° C., weight average molecular weight (Mw): 100,000, MFR (190 ° C., 21.18 N): 35 g / 10 min) was prepared as a resin composition for I layer (I-3). The 130 ° C. melt viscosity ⁇ I of the resin composition for I layer (I-3) was 1.7 ⁇ 10 5 Pa ⁇ s.
  • II-layer resin composition 1 As the olefin polymer (D), an ethylene-butene random copolymer (d-1) (density: 870 kg / m 3 , melting point: 55 ° C., weight average molecular weight (Mw): 100,000, MFR (190 ° C., 21 .18N): 35 g / 10 min) was designated as II-layer resin composition (II-1). The 130 ° C. melt viscosity ⁇ II of the II-layer resin composition (II-1) was 7.3 ⁇ 10 2 Pa ⁇ s.
  • silane-modified ethylene-octene random copolymer (d-2) (density: 870 kg / m 3 , melting point: 1 kg of ethylene-butene random copolymer (d-1) 50 g, MFR (190 ° C., 21.18 N): 36 g / 10 min, weight average molecular weight (Mw): 250,000) were mixed to give a II-layer resin composition (II-2). 130 ° C.
  • the melt viscosity eta II of II layer resin composition (II-2) was 7.5 ⁇ 10 2 Pa ⁇ s.
  • the olefin polymer (D) is an ethylene-butene random copolymer (d-1) (density: 870 kg / m 3 , melting point: 55 ° C., weight average molecular weight (Mw): 100,000, MFR (190 ° C.
  • Example 1 Resin composition as a release layer (II layer) on a polyethylene terephthalate film (III-1: manufactured by Mitsubishi Plastics, product name: Diafoil T-100, thickness 50 ⁇ m) as a base layer (III layer)
  • the extrusion temperature is such that the product (II-1) (thickness: 38 ⁇ m) and the resin composition (I-1) (thickness: 150 ⁇ m) as the photocurable adhesive resin layer (I layer) are laminated in this order.
  • Polyethylene terephthalate film manufactured by Mitsubishi Plastics, product name: Diafoil MRA, thickness: 100 ⁇ m, co-extruded at 130 ° C. and formed into a sheet shape, indicated as “release PET” in the table ) was overlaid and coated on the photocurable adhesive resin layer (I layer) to prepare an adhesive sheet laminate 1.
  • Example 2 A pressure-sensitive adhesive sheet laminate 2 was prepared in the same manner as in Example 1 except that the resin composition (I-2) was used instead of the resin composition (I-1).
  • Example 3 A pressure-sensitive adhesive sheet laminate 3 was prepared in the same manner as in Example 1 except that the resin composition (II-2) was used instead of the resin composition (II-1).
  • Example 4 A pressure-sensitive adhesive sheet laminate 4 was prepared in the same manner as in Example 1 except that the resin composition (II-3) was used instead of the resin composition (II-1).
  • Example 5 Resin composition (II-2) (thickness: 50 ⁇ m) as a release layer (II layer) on a biaxially stretched polypropylene film (III-2: thickness 38 ⁇ m) as a base material layer (III layer) Then, the resin composition (I-1) (thickness: 100 ⁇ m) as a photocurable pressure-sensitive adhesive resin layer (I layer) was laminated in the order, and was coextruded at an extrusion temperature of 130 ° C. to form a sheet.
  • a release-treated polyethylene terephthalate film manufactured by Mitsubishi Plastics, product name: Diafoil MRF, thickness: 75 ⁇ m
  • a release-treated polyethylene terephthalate film manufactured by Mitsubishi Plastics, product name: Diafoil MRF, thickness: 75 ⁇ m
  • an adhesive sheet laminate 5 was created.
  • Example 2 Example 1 except that the resin composition for the I layer (I-3) was coextruded at an extrusion temperature of 160 ° C. to form a sheet instead of the resin composition for the I layer (I-1)
  • the pressure-sensitive adhesive sheet laminate 7 was prepared.
  • the base material layer (III layer) / release layer (II layer) of the above sample was peeled off from the photocurable pressure-sensitive adhesive resin layer (I layer) at a peel angle of 180 ° and a peel angle of 300 mm / min, and the release layer (II
  • the peel strength (N / cm) from the photocurable adhesive resin layer (I layer) of the layer) was measured and indicated as “II layer peel strength” in the table.
  • the adhesive sheet laminated body 8 of the comparative example 3 peels only a mold release layer (II layer) from a photocurable adhesive resin layer (I layer). It was.
  • the polyethylene terephthalate film (Mitsubishi resin company make, product name: Diafoil MRA, thickness: 100 micrometers) side was bonded to the support substrate, and the polyethylene terephthalate which carried out the mold release process was carried out.
  • the release layer (II layer) was peeled from the photocurable pressure-sensitive adhesive resin layer (I layer), and the exposed adhesive surface was covered with a 100 ⁇ m PET film ( Toyobo Co., Ltd., product name: Cosmo Shine A4300, thickness: 100 ⁇ m) was bonded to produce a laminated product. After cutting this laminated product into a width of 10 mm and a length of 150 mm, the remaining release film was peeled off, and the exposed adhesive surface was roll-bonded to soda lime glass using a hand roller.
  • a 100 ⁇ m PET film Toyobo Co., Ltd., product name: Cosmo Shine A4300, thickness: 100 ⁇ m
  • the bonded product thus obtained was subjected to autoclave treatment (80 ° C., gauge pressure: 0.2 MPa, 30 minutes) and finished and bonded, and then 365 nm from the backing PET film side using a high-pressure mercury lamp.
  • the pressure-sensitive adhesive sheet was cured by irradiating the ultraviolet ray with an integrated light amount of 2000 mJ / cm 2 .
  • the sample was cured at 23 ° C. and 50% RH for 15 hours to prepare a sample for measuring adhesive strength.
  • the peel strength measurement sample was peeled off at a peel angle of 180 ° and a peel rate of 60 mm / min in an environment of 23 ° C. and 40% RH, and the adhesive strength (N / cm) of the I layer to the glass was measured. It was shown as “I layer adhesion”.
  • the photocurable adhesive resin layer (I layer) which peeled and exposed the polyethylene terephthalate film (the Mitsubishi resin company make, product name: Diafoil MRF, thickness: 75 micrometers). ) was measured.
  • the pressure-sensitive adhesive sheet laminates 1 to 8 produced in the examples and comparative examples were cut using a Thomson punching machine with a 50 mm ⁇ 80 mm Thomson blade, and the release layer (II layer) or the release film was lifted It was confirmed. Those with 10 or more floats at the end were judged as “ ⁇ (poor)”, and those with less than 10 floats were judged as “good”.
  • An evaluation glass substrate having a printing step of 20 ⁇ m on the peripheral portion was produced by printing black on the peripheral portion of 5 mm on a peripheral portion 5 mm of soda lime glass (82 mm ⁇ 53 mm ⁇ thickness 0.5 mm).
  • a polarizing plate (“HLC2-5618” manufactured by Sanlitz) was previously bonded to the entire surface of a glass plate (83 ⁇ 52 mm ⁇ t0.5 mm). Things were made.
  • the adhesive sheet laminates 1 to 8 produced in Examples and Comparative Examples were cut into 80 mm ⁇ 50 mm.
  • the photo-curing adhesive resin layer (I layer) exposed by peeling off the release layer (II layer) is pasted on the surface having the printing step of the glass substrate for evaluation with a hand roller so as to cover the printing step portion. I wore it.
  • the remaining release film is peeled off, and the polarizing plate surface of the adherend for evaluation is press bonded under reduced pressure (absolute pressure: 5 kPa) to the exposed adhesive surface, and autoclaved (80 ° C., gauge pressure: 0.2 MPa, 30 minutes) was applied and finished to prepare a laminate for evaluation.
  • an ultraviolet-ray is irradiated so that the integrated light quantity of 365 nm may become 2000 mJ / cm ⁇ 2 >, and an adhesive sheet is hardened, 23 degreeC and 50% RH
  • the sample was cured for 15 hours and used as a sample for evaluation of foaming reliability.
  • the foam resistance test sample prepared in this way was stored for 100 hours in an environment of 85 ° C. and 85% RH, the appearance was visually observed, and deformation, foaming, and peeling of the adhesive material occurred after the environmental test. was determined as “ ⁇ (poor)”, and those that did not occur were determined as “good”.
  • Each of the pressure-sensitive adhesive sheet laminates prepared in Examples 1 to 5 was excellent in peelability between the release layer (II layer) and the photocurable pressure-sensitive adhesive resin layer (I layer), and was co-extruded. Therefore, there was no floating due to the cutting process, and the processability was excellent. In addition, no migration component such as silicone release agent is observed on the surface of the photocurable adhesive resin layer (I layer) on the surface in contact with the release layer (II layer), and the adherend is excellent in stain resistance. It was a thing. Furthermore, since the photocurable adhesive resin layer has photocurability, the foaming reliability after bonding the adhesive sheet was also excellent.
  • the pressure-sensitive adhesive sheet laminate of Comparative Example 1 has a structure in which release treatment films are laminated on both surfaces of the photo-curable pressure-sensitive adhesive resin layer (I layer), and therefore, the release layer is released on the surface of the I layer.
  • the agent adhered, and transfer of the release agent to the adherend during bonding was observed.
  • the release film tends to float at the time of cutting, which is inferior in workability as compared with the above examples. It was.
  • the pressure-sensitive adhesive sheet laminate of Comparative Example 2 was excellent in workability as a result of using a resin having no photo-curing property as the pressure-sensitive adhesive resin layer, but it was difficult to adapt to uneven surfaces and foamed in a high-temperature and high-humidity environment. Occurred, and the quality as an adhesive sheet was inferior. Since the pressure-sensitive adhesive sheet laminate of Comparative Example 3 does not have a base material layer (III layer), the exposed release layer (II layer) and the peeled-off film placed on each other cause partial sticking (blocking) over time. The storage stability was inferior.
  • the base material layer (III layer) was more than the peeling force between the photocurable pressure-sensitive adhesive resin layer (I layer) and the release layer (II layer). ) And the release layer (II layer).
  • ⁇ I and ⁇ II are 1 ⁇ 10 1 to 5 ⁇ 10 3 Pa ⁇ s
  • the ratio ⁇ II / ⁇ I to the 130 ° C. melt viscosity ⁇ II of the resin composition constituting the mold layer (II layer) is preferably in the range of 0.05 to 30.
  • the thickness of the photocurable adhesive resin layer (I layer) is 50 ⁇ m to 1000 ⁇ m, particularly 70 ⁇ m or more or 500 ⁇ m or less, of which 100 ⁇ m or more.
  • the thickness of the release layer (II layer) is preferably 5 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m or more and 350 ⁇ m or less, and particularly preferably 18 ⁇ m or more or 250 ⁇ m or less.
  • the thickness of the layer (III layer) is 25 ⁇ m to 500 ⁇ m, more preferably 38 ⁇ m or more and 350 ⁇ m or less, and particularly preferably 50 ⁇ m or more and 250 ⁇ m or less.

Landscapes

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

Abstract

L'invention concerne un nouveau stratifié de feuilles adhésives autocollantes permettant de minimaliser une contamination, par des matières étrangères, de l'interface entre une couche adhésive et une couche de démoulage et/ou le transfert par migration d'un agent de démoulage vers la couche adhésive lors de la fixation d'un élément constitutif d'un dispositif d'affichage d'image, et qui présente une excellente durabilité après la fixation. Dans le stratifié de feuilles adhésives autocollantes, une couche de substrat (couche III) est prévue par l'intermédiaire d'une couche de démoulage (couche II) sur une face ou sur les deux faces d'une couche de résine adhésive photodurcissable (couche I) contenant une résine adhésive photodurcissable. La couche de résine adhésive photodurcissable (couche I), dans son état non durci, est formée à partir d'une composition de résine contenant un copolymère d'ester d'acide (méth)acrylique (A), un agent de réticulation (B) et un photo-initiateur (C); la couche de démoulage (couche II) est formée à partir d'une composition de résine contenant un polymère d'oléfine (D); et la couche de résine adhésive photodurcissable (couche I) et la couche de démoulage (couche II) sont formées par coextrusion.
PCT/JP2015/083531 2014-12-03 2015-11-30 Stratifié de feuilles adhésives autocollantes et stratifié d'élément constitutif de dispositif d'affichage d'image WO2016088697A1 (fr)

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JP2018002756A (ja) * 2016-06-27 2018-01-11 日東電工株式会社 光学用粘着シート、粘着剤層付偏光フィルム、および液晶表示装置
WO2018051857A1 (fr) * 2016-09-15 2018-03-22 三菱ケミカル株式会社 Stratifié de feuille adhésive, stratifié façonné de feuille adhésive et procédé pour sa production
JP2018048317A (ja) * 2016-09-15 2018-03-29 三菱ケミカル株式会社 粘着シート積層体、賦形粘着シート積層体及びその製造方法
WO2018101252A1 (fr) * 2016-12-02 2018-06-07 三菱ケミカル株式会社 Composition photodurcissable, feuille d'adhésif sensible à la pression, stratifié de feuilles d'adhésif sensible à la pression, produit durci, stratifié pour former un dispositif d'affichage d'image et dispositif d'affichage d'image
JP2018115310A (ja) * 2017-01-19 2018-07-26 三菱ケミカル株式会社 賦形粘着シート積層体の製造方法
JP2018144381A (ja) * 2017-03-07 2018-09-20 三菱ケミカル株式会社 塗布フィルムおよび粘着シート積層体
KR102072660B1 (ko) * 2018-08-27 2020-02-03 닛토덴코 가부시키가이샤 보강 필름
JP2020100073A (ja) * 2018-12-21 2020-07-02 味の素株式会社 積層配線板の製造方法
CN113242790A (zh) * 2018-12-14 2021-08-10 三菱化学株式会社 粘合剂树脂组合物、粘合剂树脂固化物、粘合片及图像显示装置层叠体
CN115279589A (zh) * 2020-03-27 2022-11-01 东洋纺株式会社 脱模薄膜和其制造方法

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JP2018002756A (ja) * 2016-06-27 2018-01-11 日東電工株式会社 光学用粘着シート、粘着剤層付偏光フィルム、および液晶表示装置
KR102457647B1 (ko) 2016-09-15 2022-10-24 미쯔비시 케미컬 주식회사 점착 시트 적층체, 부형 점착 시트 적층체 및 그 제조방법
WO2018051857A1 (fr) * 2016-09-15 2018-03-22 三菱ケミカル株式会社 Stratifié de feuille adhésive, stratifié façonné de feuille adhésive et procédé pour sa production
JP2018048317A (ja) * 2016-09-15 2018-03-29 三菱ケミカル株式会社 粘着シート積層体、賦形粘着シート積層体及びその製造方法
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KR20220025251A (ko) * 2016-09-15 2022-03-03 미쯔비시 케미컬 주식회사 점착 시트 적층체, 부형 점착 시트 적층체 및 그 제조방법
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KR102426469B1 (ko) 2016-09-15 2022-07-29 미쯔비시 케미컬 주식회사 점착 시트 적층체, 부형 점착 시트 적층체 및 그 제조방법
WO2018101252A1 (fr) * 2016-12-02 2018-06-07 三菱ケミカル株式会社 Composition photodurcissable, feuille d'adhésif sensible à la pression, stratifié de feuilles d'adhésif sensible à la pression, produit durci, stratifié pour former un dispositif d'affichage d'image et dispositif d'affichage d'image
JPWO2018101252A1 (ja) * 2016-12-02 2019-10-24 三菱ケミカル株式会社 光硬化性組成物、粘着シート、粘着シート積層体、硬化物、画像表示装置構成用積層体及び画像表示装置
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JP2018115310A (ja) * 2017-01-19 2018-07-26 三菱ケミカル株式会社 賦形粘着シート積層体の製造方法
JP2018144381A (ja) * 2017-03-07 2018-09-20 三菱ケミカル株式会社 塗布フィルムおよび粘着シート積層体
CN112601796A (zh) * 2018-08-27 2021-04-02 日东电工株式会社 增强薄膜
CN112601796B (zh) * 2018-08-27 2022-05-06 日东电工株式会社 增强薄膜
KR102072660B1 (ko) * 2018-08-27 2020-02-03 닛토덴코 가부시키가이샤 보강 필름
CN113242790A (zh) * 2018-12-14 2021-08-10 三菱化学株式会社 粘合剂树脂组合物、粘合剂树脂固化物、粘合片及图像显示装置层叠体
JP7047750B2 (ja) 2018-12-21 2022-04-05 味の素株式会社 積層配線板の製造方法
JP2020100073A (ja) * 2018-12-21 2020-07-02 味の素株式会社 積層配線板の製造方法
CN115279589A (zh) * 2020-03-27 2022-11-01 东洋纺株式会社 脱模薄膜和其制造方法

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