WO2020054146A1 - Feuille adhésive - Google Patents

Feuille adhésive Download PDF

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Publication number
WO2020054146A1
WO2020054146A1 PCT/JP2019/022107 JP2019022107W WO2020054146A1 WO 2020054146 A1 WO2020054146 A1 WO 2020054146A1 JP 2019022107 W JP2019022107 W JP 2019022107W WO 2020054146 A1 WO2020054146 A1 WO 2020054146A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
resin
meth
Prior art date
Application number
PCT/JP2019/022107
Other languages
English (en)
Japanese (ja)
Inventor
耕治 直田
中西　健一
一博 佐々木
達宏 池谷
Original Assignee
昭和電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to JP2020546693A priority Critical patent/JPWO2020054146A1/ja
Priority to KR1020217001506A priority patent/KR20210021063A/ko
Priority to CN201980044971.7A priority patent/CN112424308A/zh
Publication of WO2020054146A1 publication Critical patent/WO2020054146A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • 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 relates to an adhesive sheet.
  • Priority is claimed on Japanese Patent Application No. 2018-168735, filed on September 10, 2018, the content of which is incorporated herein by reference.
  • MLCC multilayer ceramic capacitors
  • MLCC is a process of printing electrodes on a pre-fired sheet (green sheet), a process of laminating and pressing several tens to several hundreds of these to obtain a laminate, and a process of cutting (cutting) the laminate into small pieces. It is manufactured through a step of heating and baking the fragmented laminate. In the step of cutting the laminate, cutting is performed in a state where the pressure-sensitive adhesive sheet is stuck to the laminate.
  • the pressure-sensitive adhesive sheet is required to have an adhesive property that does not peel off from the laminate when the laminate is cut, and an easy peelability that can be easily peeled off from the laminate that has been cut into small pieces after cutting.
  • Patent Document 1 discloses an adhesive structure in which an adhesive tape including a base material and an adhesive layer is adhered to an adherend.
  • Patent Literature 1 discloses a pressure-sensitive adhesive layer of a pressure-sensitive adhesive tape, which includes an adhesive substance containing a pressure-sensitive adhesive resin as a main component and a gas generating agent that generates a gas when stimulated.
  • the adhesive structure described in Patent Document 1 can be peeled off without damaging the adherend by giving a stimulus and releasing gas when peeling, and thus is suitable for recycling applications. Is described.
  • Patent Document 2 discloses an adhesive tape for processing electronic components having high adhesive strength and releasability.
  • the adhesive layer has a two-layer structure of an inner layer and an outer layer, the inner layer contains a gas generating agent that generates a gas by stimulation, and the outer layer is crosslinked by light and / or heat stimulation.
  • An adhesive tape containing a hydrophilic adhesive is disclosed.
  • an adhesive sheet has been used in a process of manufacturing an electronic component, such as a process of dividing a member on which a plurality of electronic components are formed into small pieces.
  • This pressure-sensitive adhesive sheet is attached to an adherend such as a green sheet on which a plurality of electronic components are formed, and is peeled off from the adherend after predetermined processing is completed.
  • the pressure-sensitive adhesive sheet used for the above-mentioned applications when performing a predetermined processing step, the pressure-sensitive adhesive sheet has a sufficient adhesive force to the adherend, and after the predetermined processing step is completed, It is required that it can be easily peeled off.
  • the conventional pressure-sensitive adhesive sheet has not sufficiently satisfied the above conditions.
  • the present invention has been made in view of the above circumstances, and provides an adhesive sheet having a sufficiently high adhesive force to an adherend and an adhesive force capable of easily peeling off from the adherend by irradiating light. As an issue.
  • the first adhesive containing at least the resin (A) having no ethylenically unsaturated bond (hereinafter, sometimes referred to as “saturated resin (A)”) and the gas generating agent on the base material.
  • saturated resin (A) a resin having no ethylenically unsaturated bond
  • unsaturated resin (B) a resin having an ethylenically unsaturated bond having an unsaturated group equivalent of 500 to 1200
  • the second pressure-sensitive adhesive layer to be formed may be a pressure-sensitive adhesive sheet laminated in this order.
  • the pressure-sensitive adhesive sheet When the pressure-sensitive adhesive sheet is irradiated with light such as ultraviolet (UV) light, the unsaturated bonds in the unsaturated resin (B) contained in the second pressure-sensitive adhesive layer form a three-dimensional crosslinked structure and are cured, and the pressure-sensitive adhesive strength is increased. Changes. Specifically, when the second pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is brought into close contact with the adherend, sufficient adhesive force is obtained on the adherend before light irradiation, and after the light irradiation, a sufficient adhesive force is obtained. Power drops. Moreover, in the above-mentioned pressure-sensitive adhesive sheet, the first pressure-sensitive adhesive layer contains a gas generating agent that generates gas by light irradiation.
  • UV ultraviolet
  • the pressure-sensitive adhesive sheet when the pressure-sensitive adhesive sheet is irradiated with light, gas is generated from the gas generating agent.
  • the gas generated in the first pressure-sensitive adhesive layer pushes up the second pressure-sensitive adhesive layer which has been heated and softened by light irradiation, and forms irregularities on the surface of the second pressure-sensitive adhesive layer.
  • the contact area between the adherend and the second pressure-sensitive adhesive layer that is in close contact with the adherend decreases.
  • the surface of the second pressure-sensitive adhesive layer has an adhesive force that can be easily peeled from the adherend.
  • the present inventors have conceived the present invention based on such findings. That is, the pressure-sensitive adhesive sheet according to one embodiment of the present invention relates to the following matters.
  • the first pressure-sensitive adhesive layer contains at least a saturated resin (A) and a gas generating agent that generates a gas by light irradiation,
  • the ethylenically unsaturated group-containing (meth) acrylic resin contains 10 to 30% by mass of a structural unit derived from a hydroxy group-containing (meth) acrylate,
  • the constitutional unit according to [6], wherein a constitutional unit derived from an ethylenically unsaturated compound containing a group reactive with a hydroxy group is added to 65 to 95 mol% of the constitutional units derived from the hydroxy group-containing (meth) acrylate.
  • Adhesive sheet [8] The pressure-sensitive adhesive sheet according to [7], wherein the ethylenically unsaturated compound containing a group reactive with a hydroxy group is an isocyanato group-containing (meth) acrylate.
  • the second pressure-sensitive adhesive layer according to any one of [1] to [8], wherein the second adhesive layer has a glass transition temperature (Tg) of 10 to 70 ° C. after being photocured at a UV irradiation dose of 3000 mJ / cm 2 .
  • Tg glass transition temperature
  • the pressure-sensitive adhesive sheet of the present invention has a sufficiently high adhesive strength to the adherend by bringing the second pressure-sensitive adhesive layer into close contact with the adherend, and irradiates light to the pressure-sensitive adhesive sheet adhered to the adherend. By doing so, it can be easily separated from the adherend.
  • the pressure-sensitive adhesive sheet of the present invention is obtained by laminating a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on a substrate in this order.
  • the pressure-sensitive adhesive sheet of the present embodiment has a sheet-like base material.
  • a known material can be appropriately selected and used. Since the adhesive sheet is irradiated with light from the substrate side, it is preferable to use a resin sheet made of a transparent resin material as the substrate.
  • the resin material examples include polyolefins such as polyethylene (PE) and polypropylene (PP); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate; polyvinyl chloride (PVC); polyimide (PI); Examples include polyphenylene sulfide (PPS); ethylene vinyl acetate (EVA); and polytetrafluoroethylene (PTFE).
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PI polyethylene naphthalate
  • PVC polyvinyl chloride
  • PI polyimide
  • Examples include polyphenylene sulfide (PPS); ethylene vinyl acetate (EVA); and polytetrafluoroethylene (PTFE).
  • an adhesive sheet having appropriate flexibility can be obtained, and therefore, it is preferable to use at least one selected from PE, PP, and PET
  • the resin sheet When a resin sheet is used as the base material, the resin sheet may have a single-layer structure or a multilayer structure having two or more layers (for example, a three-layer structure).
  • the resin material constituting each layer may be a resin material containing only one type or a resin material containing two or more types.
  • the resin sheet can be produced by appropriately employing a conventionally known general sheet forming method (eg, extrusion molding, T-die molding, inflation molding, or uniaxial or biaxial stretching molding).
  • a conventionally known general sheet forming method eg, extrusion molding, T-die molding, inflation molding, or uniaxial or biaxial stretching molding.
  • the thickness of the substrate can be appropriately selected according to the use of the pressure-sensitive adhesive sheet, the material of the substrate, and the like.
  • the thickness of the substrate is preferably from 10 to 1000 ⁇ m, more preferably from 50 to 300 ⁇ m.
  • the rigidity (stiffness) of the pressure-sensitive adhesive sheet increases. Therefore, when the pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive sheet tends to be less likely to wrinkle or to float between the pressure-sensitive adhesive sheet and the adherend.
  • the pressure-sensitive adhesive sheet attached to the adherend is easily peeled off from the adherend, and workability (handling property, handling) is improved.
  • the thickness of the base material is 1000 ⁇ m or less, the pressure-sensitive adhesive sheet has appropriate flexibility and workability is improved.
  • the surface of the substrate on the side of the first pressure-sensitive adhesive layer may be subjected to a surface treatment in order to improve the adhesion between the substrate and the first pressure-sensitive adhesive layer.
  • a surface treatment include corona discharge treatment, acid treatment, ultraviolet irradiation treatment, plasma treatment, and application of a primer (primer).
  • the pressure-sensitive adhesive sheet of the present embodiment has a first pressure-sensitive adhesive layer on a substrate.
  • the first pressure-sensitive adhesive layer contains at least a saturated resin (A) and a gas generating agent that generates a gas by light irradiation.
  • the first pressure-sensitive adhesive layer may further contain a photosensitizer and / or a curing agent in addition to the saturated resin (A) and the gas generating agent.
  • the thickness of the first pressure-sensitive adhesive layer is preferably 1 to 100 ⁇ m, more preferably 5 to 80 ⁇ m, and further preferably 30 to 70 ⁇ m.
  • the thickness of the first pressure-sensitive adhesive layer is 1 ⁇ m or more, the uniformity of the thickness of the first pressure-sensitive adhesive layer is improved.
  • the thickness of the first pressure-sensitive adhesive layer is 100 ⁇ m or less, the solvent can be easily removed when the first pressure-sensitive adhesive layer is formed using a solvent, which is preferable.
  • the glass transition temperature (Tg) of the saturated resin (A) contained in the first pressure-sensitive adhesive layer is preferably ⁇ 80 to 0 ° C., more preferably ⁇ 70 to ⁇ 5 ° C., and further preferably ⁇ 60. ⁇ -10 ° C.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the saturated resin (A) is -80 ° C or more, the adhesion between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is further improved.
  • the glass transition temperature (Tg) of the saturated resin (A) is 0 ° C. or less, peeling at the interface between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer hardly occurs.
  • the glass transition temperature (Tg) of the saturated resin (A) indicates a value determined by the following method. Take 10 mg of the saturated resin (A) as a sample. Using a differential scanning calorimeter (DSC), the temperature of the sample was changed from ⁇ 80 ° C. to 200 ° C. at a heating rate of 10 ° C./min, and the differential scanning calorimetry was performed. Let the temperature be Tg. When two Tg are observed, the average value of the two Tg is used.
  • DSC differential scanning calorimeter
  • the weight average molecular weight of the saturated resin (A) is preferably from 200,000 to 2,000,000, more preferably from 300,000 to 1,500,000, and further preferably from 400,000 to 1,000,000.
  • weight average molecular weight of the saturated resin (A) is 200,000 or more, cohesive failure of the first pressure-sensitive adhesive layer hardly occurs.
  • weight-average molecular weight of the saturated resin (A) is 2,000,000 or less, the viscosity of the saturated resin (A) does not become too high, and the effect that the workability in forming the first pressure-sensitive adhesive layer is good.
  • the weight average molecular weight of the saturated resin (A) was measured at room temperature under the following conditions using gel permeation chromatography (Showdex (registered trademark) GPC-101) and converted to polystyrene. Is calculated.
  • saturated resin (A) contained in the first pressure-sensitive adhesive layer examples include (meth) acrylic resin, rubber, urethane resin, and silicone resin. Among these, it is preferable to use a (meth) acrylic resin as the saturated resin (A) from the viewpoints of physical properties and economy as an adhesive.
  • (meth) acryl refers to at least one selected from “methacryl” and “acryl”.
  • the saturated resin (A) preferably contains a (meth) acrylic resin containing a structural unit derived from a monomer having a reactive functional group, and particularly contains a hydroxy group-containing (meth) acrylate. ) It is preferable to include a (meth) acrylic resin containing a constituent unit derived from acrylate.
  • the ratio of the structural unit derived from the monomer having a reactive functional group in the (meth) acrylic resin is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass.
  • the (meth) acrylic resin sufficiently contains structural units derived from the reactive functional group-containing monomer that reacts with the curing agent.
  • a first pressure-sensitive adhesive layer having good adhesion to the substrate and the second pressure-sensitive adhesive layer is obtained, and a pressure-sensitive adhesive sheet having good adhesion to an adherend is obtained.
  • the proportion of the constituent unit derived from the reactive functional group-containing monomer is 20% by mass or less, the adhesive strength is not easily reduced by the reaction with the curing agent, and the adhesive strength between the base material and the second adhesive layer is good.
  • One adhesive layer is obtained.
  • the saturated resin (A) is obtained, for example, by copolymerizing a raw material monomer including a (meth) acrylic monomer by a known polymerization method.
  • the raw material monomer of the saturated resin (A) may include only one type of monomer alone, or may include two or more types of monomers.
  • Examples of the polymerization method for polymerizing the raw material monomers include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and an alternating copolymerization method. Among these, it is preferable to use a solution polymerization method from the viewpoint of the transparency and cost of the (meth) acrylic resin obtained after the polymerization.
  • Examples of the (meth) acrylic monomer used as a raw material monomer of the saturated resin (A) include a (meth) acrylic monomer and a (meth) acrylamide monomer.
  • Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, Examples include tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylic acid, and 2-hydroxyethyl (meth) acrylate.
  • Examples of the (meth) acrylamide monomer include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, and (meth) Acrylamide and the like can be mentioned.
  • N-vinylpyrrolidone N-vinylcaprolactam
  • N-vinylacetamide N-acryloylmorpholine
  • acrylonitrile etc.
  • a first pressure-sensitive adhesive layer having good adhesion to the substrate and the second pressure-sensitive adhesive layer can be obtained. It is preferable to use at least one selected from acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and N, N-dimethyl (meth) acrylamide.
  • the first pressure-sensitive adhesive layer contains a curing agent
  • a monomer having a reactive functional group is contained in the raw material monomer of the saturated resin (A).
  • the reactive functional group contained in the reactive functional group-containing monomer include a hydroxy group, a carboxy group, and an epoxy group.
  • a hydroxy group is preferable because of high reactivity with a curing agent.
  • the reactive functional group-containing monomer is selected from the group consisting of hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, and glycidyl (meth) acrylate. Species or two or more can be used.
  • the content of the reactive functional group-containing monomer in the raw material monomer is preferably 0.5 to 20% by mass. And more preferably 1 to 10% by mass.
  • the saturated resin (A) preferably contains 0.5 to 20% by mass of a structural unit derived from a monomer having a reactive functional group.
  • the adhesive force of the first pressure-sensitive adhesive layer hardly decreases due to the reaction between the reactive functional group-containing monomer and the curing agent, and And a first pressure-sensitive adhesive layer having good adhesion to the second pressure-sensitive adhesive layer.
  • the (meth) acrylic resin used as the saturated resin (A) is produced by a solution polymerization method, a polymerization initiator and / or a solvent are used as necessary together with the raw material monomers.
  • the polymerization initiator is not particularly limited and can be appropriately selected from known ones.
  • polymerization initiator examples include, for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4- Azo polymerization initiators such as trimethylpentane), dimethyl-2,2'-azobis (2-methylpropionate); benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl Peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butyl An oil-soluble polymerization initiator such as a peroxide-based polymerization initiator
  • the amount of the polymerization initiator to be used is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, based on 100 parts by mass of the raw material monomer of the saturated resin (A). More preferably, the amount is 0.03 to 3 parts by mass.
  • the solvent various general solvents can be used.
  • the solvent include esters such as ethyl acetate, n-propyl acetate and n-butyl acetate, aromatic hydrocarbons such as toluene and benzene, aliphatic hydrocarbons such as n-hexane and n-heptane, and cyclohexane.
  • organic solvents such as alicyclic hydrocarbons such as methylcyclohexane and ketones such as methyl ethyl ketone and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more.
  • Gas generator The gas generating agent contained in the first pressure-sensitive adhesive layer generates a gas by light irradiation.
  • a gas generating agent For example, an azo compound, an azide compound, etc. can be used suitably. Azo compounds and azide compounds generate nitrogen gas when stimulated by light, heat, or the like.
  • azo compound for example, 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis (2-methylpropionate) , 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis [2- (2-imidazoyl-2-yl) Propane] dihydrochloride, 2,2′-azobis [2- (2-imidazoyl-2-yl) propane], 2,2′-azobis (2-methylpropio Amidain) hydrochloride, 2,2'-azobis ⁇ 2- [N- (2- carboxyethyl) Amidain] propane ⁇ , and the like
  • azo compounds in particular, from the viewpoint of the stability of the compounds, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), , 2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [N- ( 2-propenyl) -2-methylpropionamide].
  • azide compound for example, azide such as glycidyl azide polymer obtained by ring-opening polymerization of 3-azidomethyl-3-methyloxetane, terephthalazide, p-tert-butylbenzazide, 3-azidomethyl-3-methyloxetane And a polymer having a group.
  • azide compounds it is particularly preferable to use a glycidyl azide polymer from the viewpoint of compatibility with the (meth) acrylic resin.
  • the content of the gas generating agent in the first pressure-sensitive adhesive layer is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the saturated resin (A).
  • the content of the gas generating agent is 5 parts by mass or more, a sufficient amount of gas is generated by irradiating the pressure-sensitive adhesive sheet with light.
  • the ratio of the area where the irregularities are formed on the surface of the second pressure-sensitive adhesive layer is sufficiently large, and the contact area between the surface of the second pressure-sensitive adhesive layer and the adherend is significantly reduced, and the adherend is reduced.
  • the content of the gas generating agent is 50 parts by mass or less, deposition of the gas generating agent in the first pressure-sensitive adhesive layer can be prevented.
  • the first pressure-sensitive adhesive layer may contain a curing agent.
  • the curing agent reacts with the functional group of the saturated resin (A) and crosslinks to improve the cohesive force of the first pressure-sensitive adhesive layer.
  • the curing reaction is performed by heating the first pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive composition may be cured by heating for drying.
  • the curing reaction temperature is preferably 60 to 120 ° C., although it depends on the type of the curing agent to be used, the type of functional group that reacts with the curing agent, and the thickness of the first pressure-sensitive adhesive layer.
  • the reaction time (heating time) is preferably 1 to 60 minutes.
  • the curing agent is not particularly limited as long as it has two or more reactive functional groups having reactivity to a hydroxy group, a carboxy group, or an epoxy group, and those that restrict reaction with other functional groups. is not.
  • an isocyanate compound, an epoxy compound, an aziridine compound, a melamine compound and the like can be used as the curing agent.
  • isocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and diphenylmethane-4,4.
  • -Diisocyanate isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalenediisocyanate, tolylene diisocyanate adduct of trimethylolpropane, xylylene diisocyanate adduct of trimethylolpropane , Triphenylmethane triisocyanate, methylene bis (4-phenylmethane) triisocyanate, and the like.
  • Examples of the epoxy compound include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, and trimethylol.
  • Examples thereof include propane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, and diglycerol polyglycidyl ether.
  • the aziridine compound for example, tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), N, N'-hexamethylene-1,6-bis (1-aziridinecarboxamide) and the like.
  • the melamine compound include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexaptoxymethylmelamine, hexapentyloxymethylmelamine, and hexahexyloxymethylmelamine.
  • curing agents may be used alone or in combination of two or more.
  • an isocyanate compound as a curing agent from the viewpoint of reactivity with the hydroxy group.
  • the content of the curing agent is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the saturated resin (A).
  • the content of the curing agent is 0.05 parts by mass or more, a three-dimensional crosslinked structure is sufficiently formed in the saturated resin (A).
  • the content of the curing agent is 10 parts by mass or less, the first pressure-sensitive adhesive layer has good adhesion to the substrate and the second pressure-sensitive adhesive layer.
  • the content of the curing agent is preferably such that the amount of the reactive functional group contained in the curing agent is 0.1 to 300 mol% based on the amount of the hydroxy group, carboxy group or epoxy group of the saturated resin (A). , More preferably 1 to 200 mol%.
  • the amount of the reactive functional group contained in the curing agent is 0.1 mol% or more, a sufficient cohesive force can be obtained.
  • the amount of the reactive functional group contained in the curing agent is 300 mol% or less, there is no adverse effect even if an unreacted curing agent remains in the first pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer may contain a photosensitizer.
  • the photosensitizer has an effect of amplifying light stimulation to the gas generating agent. Therefore, since the first pressure-sensitive adhesive layer contains a photosensitizer, the irradiation amount of light used when releasing gas from the gas generating agent is reduced, or light having a wider wavelength range is used as irradiation light. It becomes possible.
  • the photosensitizer is not particularly limited, and a known photosensitizer can be used.
  • the photosensitizer include a thioxanthone compound and an anthracene compound.
  • Specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
  • anthracene compound examples include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dibenzyloxyanthracene, and 9,10-di- ⁇ -methylbenzyl.
  • Oxyanthracene 9,10-di (octanoyloxy) anthracene, 9,10-di (2-hydroxyethoxy) anthracene, 9,10-di (glycidyloxy) anthracene, 9,10-di (2-vinyloxyethoxy) anthracene , 9,10-di (p-epoxyphenylmethoxy) anthracene, 2-ethyl-9,10-di (p-epoxyphenylmethoxy) anthracene, 9,10-di (p-vinylphenylmethoxy) anthracene and the like. .
  • a (meth) acrylic resin is used as the saturated resin (A) among these photosensitizers, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, It is preferable to use one or more selected from 9,10-dibutoxyanthracene, 9,10-di (octanoyloxy) anthracene, and 9,10-di (2-hydroxyethoxy) anthracene.
  • the content of the photosensitizer is preferably from 0.03 to 5 parts by mass, more preferably from 0.05 to 3 parts by mass, per 100 parts by mass of the saturated resin (A).
  • the mass ratio between the gas generator and the photosensitizer is preferably from 200: 1 to 1: 1 and more preferably from 100: 1 to 5: 1. .
  • gas can be efficiently generated from the gas generating agent even if the amount of light irradiation on the pressure-sensitive adhesive sheet is small.
  • the pressure-sensitive adhesive sheet of the present embodiment has a second pressure-sensitive adhesive layer on the surface of the first pressure-sensitive adhesive layer opposite to the substrate.
  • the second pressure-sensitive adhesive layer contains at least an unsaturated resin (B) and a photopolymerization initiator.
  • the second pressure-sensitive adhesive layer may further contain a curing agent in addition to the unsaturated resin (B) and the photopolymerization initiator.
  • the second pressure-sensitive adhesive layer preferably has a glass transition temperature (Tg) of 10 to 70 ° C., more preferably 20 to 70 ° C. after UV irradiation at a UV irradiation amount of 3000 mJ / cm 2 and photocuring. .
  • Tg glass transition temperature
  • the pressure-sensitive adhesive sheet in which the glass transition temperature of the second pressure-sensitive adhesive layer after photocuring is 10 ° C. or more can be easily peeled from the adherend after UV irradiation. Further, the pressure-sensitive adhesive sheet in which the glass transition temperature of the second pressure-sensitive adhesive layer after photocuring is 70 ° C. or lower shows a good pressure-sensitive adhesive strength before UV irradiation.
  • the pressure-sensitive adhesive sheet in which the glass transition temperature of the second pressure-sensitive adhesive layer after photocuring is 70 ° C. or lower has a sufficiently large area ratio of the surface of the second pressure-sensitive adhesive layer after UV irradiation where irregularities are formed. Therefore, the adherend can be easily peeled.
  • the glass transition temperature (Tg) of the second pressure-sensitive adhesive layer refers to a value determined by the same method as the glass transition temperature (Tg) of the saturated resin (A) contained in the first pressure-sensitive adhesive layer.
  • the thickness of the second pressure-sensitive adhesive layer is preferably 1 to 80 ⁇ m, more preferably 2 to 60 ⁇ m, and still more preferably 5 to 30 ⁇ m.
  • the thickness of the second pressure-sensitive adhesive layer is 1 ⁇ m or more, the uniformity of the thickness of the second pressure-sensitive adhesive layer is improved.
  • the thickness of the second pressure-sensitive adhesive layer is 80 ⁇ m or less, the solvent can be easily removed when the second pressure-sensitive adhesive layer is formed using a solvent, which is preferable.
  • the thickness of the second pressure-sensitive adhesive layer is preferably smaller than the thickness of the first pressure-sensitive adhesive layer. In this case, by irradiating the pressure-sensitive adhesive sheet with light, the surface of the second pressure-sensitive adhesive layer is more likely to form irregularities.
  • the glass transition temperature (Tg) of the unsaturated resin (B) contained in the second pressure-sensitive adhesive layer is preferably ⁇ 50 to 0 ° C., more preferably ⁇ 40 to 0 ° C., and still more preferably ⁇ 35 to 0 ° C. -5 ° C.
  • Tg glass transition temperature
  • the second pressure-sensitive adhesive layer between when the pressure-sensitive adhesive sheet is attached to the adherend and when the pressure-sensitive adhesive sheet is irradiated with light has a better adhesive strength.
  • the glass transition temperature (Tg) of the unsaturated resin (B) contained in the second pressure-sensitive adhesive layer is determined in the same manner as the glass transition temperature (Tg) of the saturated resin (A) contained in the first pressure-sensitive adhesive layer. Points.
  • the weight average molecular weight of the unsaturated resin (B) is preferably from 200,000 to 2,000,000, more preferably from 200,000 to 1,500,000, further preferably from 400,000 to 1,000,000.
  • the weight average molecular weight of the unsaturated resin (B) is 200,000 or more, the second pressure-sensitive adhesive layer is less likely to remain on the adherend when the pressure-sensitive adhesive sheet is peeled off after being adhered to the adherend.
  • the weight average molecular weight of the unsaturated resin (B) is 2,000,000 or less, the viscosity of the unsaturated resin (B) does not become too high, and the effect of good workability is obtained.
  • the weight average molecular weight of the unsaturated resin (B) can be measured under the same conditions as for the saturated resin (A).
  • the unsaturated group equivalent of the unsaturated resin (B) is from 500 to 1200, preferably from 600 to 1,000.
  • the unsaturated group equivalent is 500 or more, irradiating the pressure-sensitive adhesive sheet with light ensures that irregularities are formed on the surface of the second pressure-sensitive adhesive layer.
  • the unsaturated group equivalent is less than 500, the elastic modulus of the photocured second pressure-sensitive adhesive layer becomes too high, and the ratio of the area of the surface of the second pressure-sensitive adhesive layer where irregularities are formed becomes small, so that the peelability is reduced. Run out.
  • the pressure-sensitive adhesive sheet When the unsaturated group equivalent is 1200 or less, the pressure-sensitive adhesive sheet is irradiated with light, whereby the adhesive strength of the second pressure-sensitive adhesive layer is sufficiently reduced, and the second pressure-sensitive adhesive layer is easily peeled.
  • the unsaturated group equivalent is more than 1200, the photocuring of the second pressure-sensitive adhesive layer becomes insufficient, the adhesion of the second pressure-sensitive adhesive layer to the adherend does not sufficiently decrease, and the releasability is insufficient. .
  • the unsaturated group equivalent of the unsaturated resin (B) in this specification is the mass of the unsaturated resin (B) per mole of ethylenically unsaturated bonds, and assuming that each raw material has reacted 100%. This is a calculated value calculated from the charged amount.
  • the unsaturated group equivalent of the unsaturated resin (B) may be calculated from the amount of halogen bonded to the unsaturated resin (B).
  • the amount of the halogen bonded to the unsaturated resin (B) can be evaluated according to JIS K 0070-1992. That is, chloroform is added to and dissolved in the dried unsaturated resin (B). An appropriate amount of Wies's solution is added thereto and stirred.
  • the container is closed with a stopper, and left at 23 ° C. for 1 hour in a dark place.
  • a potassium iodide solution and water are added to this solution and stirred.
  • This solution is titrated with a sodium thiosulfate solution, and when the solution turns slightly yellow, add a few drops of the starch solution and titrate until the blue color disappears.
  • the unsaturated groups in the unsaturated resin (B) react with halogen molecules at a ratio of 1: 1. Therefore, the unsaturated group equivalent of the unsaturated resin (B) is obtained by measuring the amount (mol) of the halogen molecule bound to the unsaturated resin (B) determined by this measurement by the mass of the unsaturated resin (B) used in the measurement. (g).
  • the unsaturated group equivalent of the unsaturated resin (B) obtained by this method can be considered to be the same as the above calculated value.
  • the unsaturated resin (B) contained in the second pressure-sensitive adhesive layer a resin having a radically polymerizable unsaturated bond in a molecule can be mentioned, and it is preferable to contain an ethylenically unsaturated group-containing (meth) acrylic resin.
  • the unsaturated resin (B) contains an ethylenically unsaturated group-containing (meth) acrylic resin, it preferably contains an ethylenically unsaturated group-containing (meth) acrylic resin containing a structural unit derived from a reactive functional group-containing monomer.
  • the ethylenically unsaturated group-containing (meth) acrylic resin containing a hydroxy group-containing (meth) acrylate-derived structural unit some of the hydroxy group-containing (meth) acrylate-derived structural units have reactivity with a hydroxy group. It is preferable to use those to which a structural unit derived from an ethylenically unsaturated compound having a group is added.
  • the unsaturated resin (B) contains an ethylenically unsaturated group-containing (meth) acrylic resin containing a structural unit derived from a hydroxy group-containing (meth) acrylate, and a part of the structural unit derived from the hydroxy group-containing (meth) acrylate.
  • the (meth) acrylic resin containing an ethylenically unsaturated group has a hydroxyl group-containing content of 10 to 30% by mass.
  • the ethylenically unsaturated compound preferably contains a structural unit derived from a (meth) acrylate, and 65 to 95 mol% of the structural unit derived from the hydroxy group-containing (meth) acrylate contains a group reactive with a hydroxy group. It is preferable that a structural unit derived from the polymer is added.
  • the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate in the ethylenically unsaturated group-containing (meth) acrylic resin in the unsaturated resin (B) is preferably from 10 to 30% by mass, and from 12 to 25% by mass. More preferably, it is mass%.
  • the resulting resin is a (meth) acrylic resin containing an ethylenically unsaturated group sufficiently containing structural units derived from an ethylenically unsaturated compound containing a group reactive with a hydroxy group.
  • the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate is 30% by mass or less, the second pressure-sensitive adhesive layer can be easily formed because the compatibility with the organic solvent is high and the handling is easy.
  • the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate in the unsaturated resin (B) to which the structural unit derived from the ethylenically unsaturated compound containing a group reactive with the hydroxy group is added is preferably from 65 to 95 mol%, more preferably from 70 to 90 mol%. When the above ratio is at least 65 mol%, a pressure-sensitive adhesive sheet having good adhesion to an adherend will be obtained.
  • the proportion of the structural unit derived from the ethylenically unsaturated compound containing a reactive group is 95 mol% or less
  • the ethylenically unsaturated group containing the structural unit derived from a hydroxy group-containing (meth) acrylate may be used. It is preferable because the synthesis of the group-containing (meth) acrylic resin is easy.
  • the ethylenically unsaturated compound containing a group reactive with a hydroxy group in the unsaturated resin (B) is preferably an isocyanato group-containing (meth) acrylate because of easy synthesis.
  • the unsaturated resin (B) is obtained, for example, by a method of adding a radical polymerizable unsaturated group-containing monomer to a resin precursor having a reactive functional group. Specifically, for example, a structural unit derived from an ethylenically unsaturated compound containing a group having a reactivity with a reactive functional group is added to a part of the structural unit derived from a (meth) acrylate containing a reactive functional group.
  • Unsaturated resin (B) comprising an ethylenically unsaturated group-containing (meth) acrylic resin can be produced by the following method.
  • a raw material monomer containing a (meth) acrylic monomer and a monomer having a reactive functional group is copolymerized by a known polymerization method. Thereby, a (meth) acrylic resin containing a structural unit derived from a monomer having a reactive functional group is obtained as a resin precursor.
  • Examples of the reactive functional group contained in the reactive functional group-containing monomer include a hydroxy group, a carboxy group, and an epoxy group.
  • a reactive functional group-containing monomer a hydroxy group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth)
  • a hydroxy group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate
  • (meth) acrylic acid glycidyl (meth)
  • glycidyl (meth) One or more selected from the group consisting of acrylates can be used.
  • the content of the reactive functional group-containing monomer in the raw material monomer used in the production of the precursor is such that the ratio of the constituent unit derived from the reactive functional group-containing monomer in the unsaturated resin (B) is 10 to 30% by mass. It is preferably in the range, more preferably from 12 to 25% by mass.
  • the content of the reactive functional group-containing monomer is 10% by mass or more, the radically polymerizable unsaturated group can be sufficiently imparted. Therefore, by irradiating the pressure-sensitive adhesive sheet with light, the second pressure-sensitive adhesive having sufficient peelability can be obtained. An agent layer is obtained.
  • the content of the reactive functional group-containing monomer is 30% by mass or less, the compatibility between the unsaturated resin (B) and the organic solvent is improved, and the handling is easy.
  • the same (meth) acrylic monomer that can be used as a raw material monomer of the (meth) acrylic resin used as the saturated resin (A) of the first pressure-sensitive adhesive layer can be appropriately selected and used.
  • the method of polymerizing the raw material monomer containing the (meth) acrylic monomer and the reactive functional group-containing monomer is the same as the method of polymerizing the raw material monomer of the (meth) acrylic resin used as the saturated resin (A) of the first pressure-sensitive adhesive layer.
  • the method can be appropriately selected and used.
  • a (meth) acrylic resin containing a constituent unit derived from a reactive functional group-containing monomer is produced by a solution polymerization method as a resin precursor
  • the saturated resin (A) of the first pressure-sensitive adhesive layer is prepared by a solution polymerization method.
  • the same polymerization initiator and / or solvent as in the case of producing by using the above can be used if necessary.
  • a monomer having a functional group reactive with the reactive functional group contained in the resin precursor and an ethylenically unsaturated group (monomer containing a radical polymerizable unsaturated group) is added to the resin precursor.
  • the monomer having a functional group reactive with the reactive functional group contained in the resin precursor and the ethylenically unsaturated group include (meth) acrylate containing an isocyanate group, (meth) acrylate containing an epoxy group, and carboxy.
  • Examples include a group-containing (meth) acrylate, which can be appropriately determined according to the reactive functional group contained in the resin precursor. Specifically, the following methods (1) to (3) are exemplified.
  • a method of adding an isocyanato group-containing (meth) acrylate to a resin precursor composed of a (meth) acrylic resin polymerized using at least a hydroxy group-containing (meth) acrylate as a reactive functional group-containing monomer isocyanato group-containing (meth) acrylate.
  • a resin precursor composed of a (meth) acrylic resin polymerized using at least a hydroxy group-containing (meth) acrylate as a reactive functional group-containing monomer.
  • the isocyanato group-containing (meth) acrylate 2-isocyanatoethyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate and the like can be suitably used.
  • a method of adding an epoxy group-containing (meth) acrylate to a resin precursor composed of a (meth) acrylic resin polymerized using at least a carboxy group-containing (meth) acrylate as a reactive functional group-containing monomer (2) A method of adding an epoxy group-containing (meth) acrylate to a resin precursor composed of a (meth) acrylic resin polymerized using at least a carboxy group-containing (meth) acrylate as a reactive functional group-containing monomer.
  • Functional groups having reactivity to the reactive functional groups contained in the resin precursor, and the amount of the monomer having an ethylenically unsaturated group added to the resin precursor is the amount of the structural unit derived from the reactive functional group-containing monomer. It is preferable that the ratio of the addition of the structural unit derived from the ethylenically unsaturated compound containing a group having a reactivity with the reactive functional group is in the range of 65 to 95 mol%, and 70 to 90 mol%. Is more preferable. When the amount added to the resin precursor is 65 mol% or more, an appropriate amount of the reactive functional group remains in the resin precursor, and a second adhesive layer having good adhesive strength to an adherend is obtained.
  • the constitutional unit derived from the monomer having a reactive functional group and the constitution derived from an ethylenically unsaturated compound containing a group having reactivity with the reactive functional group are included.
  • the reactivity with the unit is good and preferable.
  • an addition catalyst and / or a solvent are used as necessary.
  • the solvent the same solvent that can be used in producing the resin precursor can be appropriately selected and used.
  • the solvent used in producing the resin precursor may not be removed and may be used as it is in the addition reaction of the radical-polymerizable unsaturated group-containing monomer. .
  • a known catalyst can be appropriately selected and used depending on the type of the resin precursor and / or the monomer having a radical polymerizable unsaturated group.
  • dibutyltin dilaurate, titanium diisopropoxybis (ethylacetoacetate), tetrakis (2,4-pentanedionato) zirconium, bismuthtris (2-ethyl) may be used as an addition catalyst.
  • One or two or more urethane-forming catalysts such as hexanoate) can be used.
  • the amount of the addition catalyst used is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the radical polymerizable unsaturated group-containing monomer.
  • the second pressure-sensitive adhesive layer of the present embodiment contains a photopolymerization initiator.
  • the photopolymerization initiator include, for example, a carbonyl-based photopolymerization initiator, a sulfide-based photopolymerization initiator, an acylphosphine oxide, a quinone-based photopolymerization initiator, a sulfochloride-based photopolymerization initiator, and a thioxanthone-based photopolymerization initiator.
  • a photopolymerization initiator include, for example, a carbonyl-based photopolymerization initiator, a sulfide-based photopolymerization initiator, an acylphosphine oxide, a quinone-based photopolymerization initiator, a sulfochloride-based photopolymerization initiator, and a thioxanthone-based photopolymerization initiator.
  • Examples of the carbonyl-based photopolymerization initiator include benzophenone, benzyl, benzoin, ⁇ -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and p-dimethylamino.
  • Examples of the sulfide-based photopolymerization initiator include diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, tetramethylammonium monosulfide, and the like.
  • Examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.
  • Examples of the quinone-based photopolymerization initiator include benzoquinone and anthraquinone.
  • Examples of the thioxanthone-based photopolymerization initiator include thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.
  • photopolymerization initiators may be used alone, or two or more thereof may be used in combination.
  • photopolymerization initiators 1-hydroxycyclohexylphenyl ketone and / or 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferred from the viewpoint of solubility in an organic solvent and / or an unsaturated resin (B). Preferably, it is used.
  • the content of the photopolymerization initiator is preferably from 0.1 to 5 parts by mass, more preferably from 0.5 to 2.0 parts by mass, per 100 parts by mass of the unsaturated resin (B). .
  • the content of the photopolymerization initiator is 0.1 parts by mass or more, by irradiating light, the second pressure-sensitive adhesive layer is cured at a sufficiently high curing speed, and the second pressure-sensitive adhesive after light irradiation is cured.
  • the adhesive strength of the agent layer is sufficiently small, which is preferable.
  • the content of the photopolymerization initiator is 5 parts by mass or less, the second pressure-sensitive adhesive layer hardly remains on the adherend when the pressure-sensitive adhesive sheet is peeled off after being adhered to the adherend. Further, even if the content of the photopolymerization initiator exceeds 5 parts by mass, the effect corresponding to the content of the photopolymerization initiator is not obtained.
  • the second pressure-sensitive adhesive layer may contain a curing agent, similarly to the first pressure-sensitive adhesive layer.
  • the curing agent reacts with the functional group of the unsaturated resin (B) and crosslinks to improve the cohesive force of the second pressure-sensitive adhesive layer.
  • the curing reaction is performed by heating the second pressure-sensitive adhesive layer. After applying the second pressure-sensitive adhesive composition to the release sheet as described later, the second pressure-sensitive adhesive composition may be cured by heating for the purpose of drying.
  • the curing reaction temperature is preferably from 60 to 120 ° C., although it depends on the type of the curing agent used, the type of functional group that reacts with the curing agent, and the thickness of the second pressure-sensitive adhesive layer.
  • the reaction time (heating time) is preferably 1 to 60 minutes.
  • the curing agent for the second pressure-sensitive adhesive layer the same curing agent that can be used as the curing agent for the first pressure-sensitive adhesive layer can be used.
  • the content of the curing agent is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the unsaturated resin (B).
  • the content of the curing agent is 0.05 parts by mass or more, a three-dimensional crosslinked structure is sufficiently formed in the unsaturated resin (B), and the elastic modulus of the second pressure-sensitive adhesive layer after light irradiation is sufficiently high. Become smaller.
  • the content of the curing agent is 10 parts by mass or less, the adhesive strength of the second pressure-sensitive adhesive layer before light irradiation is improved.
  • the content of the curing agent is preferably such that the amount of the reactive functional group contained in the curing agent is 0.1 to 300 mol based on the amount of the hydroxy group, carboxy group or epoxy group of the unsaturated resin (B). %, More preferably 1 to 200 mol%.
  • the amount of the reactive functional group contained in the curing agent is 0.1 mol% or more, a sufficient cohesive force that does not leave glue is obtained.
  • the amount of the reactive functional group contained in the curing agent is 300 mol% or less, even if an unreacted curing agent is present, there is no adverse effect such as adhesive residue.
  • the pressure-sensitive adhesive sheet of this embodiment may have a release sheet (separator) on the surface of the second pressure-sensitive adhesive layer opposite to the first pressure-sensitive adhesive layer.
  • a release sheet separator
  • the pressure-sensitive adhesive surface (the surface of the second pressure-sensitive adhesive layer) of the pressure-sensitive adhesive sheet can be protected until immediately before the pressure-sensitive adhesive sheet is adhered to the adherend.
  • the operation of peeling the release sheet to expose the second pressure-sensitive adhesive layer (adhering surface) and efficiently pressing the pressure-sensitive adhesive to the adherend can be performed.
  • a material for the release sheet a known material can be appropriately selected and used.
  • a resin sheet used as a base material can be used as a material of the release sheet.
  • the thickness of the release sheet can be appropriately selected according to the use of the pressure-sensitive adhesive sheet, the material of the release sheet, and the like.
  • the thickness of the release sheet is preferably, for example, 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and further preferably 25 to 100 ⁇ m.
  • the release surface of the release sheet (the surface disposed in contact with the second pressure-sensitive adhesive layer) is subjected to a release treatment using a conventionally known release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent, if necessary. It may be.
  • a conventionally known release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent, if necessary. It may be.
  • the pressure-sensitive adhesive sheet is wound into a roll and used as a pressure-sensitive adhesive tape
  • the surface of the substrate opposite to the first pressure-sensitive adhesive layer may be subjected to a release treatment.
  • the substrate also functions as a release sheet.
  • the pressure-sensitive adhesive sheet of the present embodiment can be manufactured, for example, by the following method.
  • a first pressure-sensitive adhesive composition for forming a first pressure-sensitive adhesive layer is prepared.
  • the first pressure-sensitive adhesive composition is prepared by mixing a saturated resin (A), a gas generating agent, and a photosensitizer and / or a curing agent, if necessary, by using a conventionally known method.
  • the first pressure-sensitive adhesive composition may contain a diluting solvent for the purpose of adjusting the viscosity as necessary. As the diluting solvent, the solvent used when producing the saturated resin (A) can be used as it is.
  • the first pressure-sensitive adhesive composition is applied on the base material, and dried by heating to form a first pressure-sensitive adhesive layer.
  • heating and drying are performed at a temperature and for a time that are preferable for the curing reaction to proceed.
  • a known method can be used as a method for applying the first pressure-sensitive adhesive composition. Specifically, a method of applying using an applicator and a conventional coater, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, a direct coater, and the like. Is mentioned.
  • a second pressure-sensitive adhesive composition for forming the second pressure-sensitive adhesive layer is prepared.
  • the second pressure-sensitive adhesive composition can be produced by mixing the unsaturated resin (B), the photopolymerization initiator, and the curing agent contained as necessary with a conventionally known method and stirring the mixture. .
  • the second pressure-sensitive adhesive composition may contain a diluting solvent for the purpose of adjusting the viscosity, if necessary.
  • the diluting solvent the solvent used when producing the unsaturated resin (B) can be used as it is.
  • the second pressure-sensitive adhesive composition is applied to the release surface of the release sheet and dried by heating to form a second pressure-sensitive adhesive layer.
  • the second pressure-sensitive adhesive composition contains a curing agent, heating and drying are performed at a temperature and for a time that is preferable for the curing reaction to proceed.
  • a method of applying the second pressure-sensitive adhesive composition a method that can be used as a method of applying the first pressure-sensitive adhesive composition can be appropriately selected and used.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are bonded to face each other.
  • the second pressure-sensitive adhesive layer with the release sheet side facing up is laminated and bonded on the first pressure-sensitive adhesive layer placed with the substrate side down.
  • the pressure-sensitive adhesive sheet of this embodiment may have a predetermined shape according to the shape of the adherend by a punching method or the like. Further, the pressure-sensitive adhesive sheet of this embodiment may be wound and cut to be used as a roll-shaped pressure-sensitive adhesive tape.
  • the release sheet is peeled off during use to expose the second pressure-sensitive adhesive layer (adhering surface).
  • the exposed second pressure-sensitive adhesive layer is disposed so as to face an adherend (an electronic component such as an MLCC laminate sheet), and pressure-bonded.
  • adherend an electronic component such as an MLCC laminate sheet
  • the adhesive sheet and the adherend are brought into close contact with each other. In this state, for example, a step of cutting the adherend is performed.
  • the pressure-sensitive adhesive sheet becomes unnecessary, the pressure-sensitive adhesive sheet is irradiated with light, preferably from the substrate side, to reduce the pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive sheet is peeled from the adherend.
  • UV ultraviolet light
  • the light source used when performing UV irradiation include, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, and a black light. preferable.
  • Dose of UV for the pressure-sensitive adhesive sheet when used high-pressure mercury lamp or a metal halide lamp, preferably from 500 ⁇ 10000mJ / cm 2, and more preferably 1000 ⁇ 5000mJ / cm 2.
  • the amount of UV irradiation applied to the pressure-sensitive adhesive sheet is 500 mJ / cm 2 or more, the effect of lowering the adhesive strength of the pressure-sensitive adhesive sheet by UV irradiation is sufficiently obtained.
  • the second pressure-sensitive adhesive layer is light-cured at a sufficiently high curing speed to increase the elastic modulus, and the adhesive force of the second pressure-sensitive adhesive layer to the adherend is sufficiently small.
  • the second pressure-sensitive adhesive layer is heated by the UV irradiation, and the second pressure-sensitive adhesive layer is sufficiently softened.
  • a sufficient amount of gas is generated from the gas generating agent.
  • the surface of the softened second pressure-sensitive adhesive layer is pushed up, and irregularities are easily formed on the surface of the second pressure-sensitive adhesive layer.
  • the UV irradiation amount applied to the pressure-sensitive adhesive sheet is 10,000 mJ / cm 2 or more, the effect of reducing the adhesive strength of the second pressure-sensitive adhesive layer corresponding thereto cannot be obtained.
  • the pressure-sensitive adhesive sheet according to the present embodiment includes a first pressure-sensitive adhesive layer containing at least a saturated resin (A) and a gas generating agent that generates a gas by light irradiation on a substrate, and an unsaturated group having an unsaturated group equivalent of 500 to 1200.
  • a second pressure-sensitive adhesive layer containing at least a saturated resin (B) and a photopolymerization initiator is laminated in this order. Therefore, by bringing the second pressure-sensitive adhesive layer into close contact with the adherend, a high adhesive force to the adherend can be obtained. In addition, by irradiating the pressure-sensitive adhesive sheet adhered to the adherend with light, the adhesive force to the adherend is reduced. Therefore, the pressure-sensitive adhesive sheet of the present embodiment can be easily peeled from the adherend.
  • the pressure-sensitive adhesive sheet of the present embodiment can be suitably used for applications such as dicing of semiconductor chips which are generally performed widely.
  • the pressure-sensitive adhesive sheet of the present embodiment can be suitably used, for example, when cutting a laminate formed in a small MLCC manufacturing process into small pieces. Specifically, when cutting the laminate in which the pressure-sensitive adhesive sheet of the present embodiment is adhered, the laminate is fixed to the pressure-sensitive adhesive sheet by the high adhesive force of the pressure-sensitive adhesive sheet. Therefore, the laminate can be stably cut. In addition, by irradiating light after the cutting process, the pressure-sensitive adhesive sheet can be easily peeled from the fragmented laminate without applying force to the fragmented laminate.
  • the pressure-sensitive adhesive sheet of the present embodiment gas is generated by light irradiation. For this reason, it is possible to prevent the adherends from re-adhering to each other after the adherends are peeled off from the adhesive sheet, as compared with, for example, a case where an adhesive sheet that generates a gas by heat stimulation is used. From these facts, by using the pressure-sensitive adhesive sheet of this embodiment, a small MLCC can be manufactured with a high yield.
  • (Meth) acrylic resins (A-1) (B-1) to (B-5) were produced by the following method.
  • (A-1) is a saturated resin having no ethylenically unsaturated bond
  • (B-1) to (B-5) are unsaturated resins having an ethylenically unsaturated bond.
  • ⁇ (Meth) acrylic resin (A-1)> A reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer was charged with the types and ratios (parts by mass) of the polymerization monomers shown in Table 1 and 300 parts of ethyl acetate as a solvent. After heating and refluxing, 0.1 parts of azobisisobutyronitrile as a polymerization initiator was added, and the mixture was reacted at the reflux temperature of ethyl acetate for 3 hours.
  • ⁇ (Meth) acrylic resin (B-1)> In a reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer, polymerization monomers of the types and ratios (parts by mass) shown in Table 1 and 300 parts of ethyl acetate as a solvent were charged. After heating and refluxing, 0.1 parts of azobisisobutyronitrile as a polymerization initiator was added, and the mixture was reacted at the reflux temperature of ethyl acetate for 3 hours.
  • DMAA dimethylacrylamide
  • BuA butyl acrylate manufactured by KJ Chemical Co., Ltd.
  • EHA 2-ethylhexyl acrylate manufactured by Toa Gosei Co., Ltd.
  • MA methyl acrylate manufactured by Toa Gosei Co., Ltd.
  • HOA 2-hydroxyethyl acrylate manufactured by Toa Gosei Co., Ltd.
  • Aa acrylic acid manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • AOI 2-isocyanatoethyl acrylate manufactured by Nippon Shokubai Co., Ltd. manufactured by Showa Denko KK
  • the “number of HEA moles” described in Table 1 is the number of moles of 2-hydroxyethyl acrylate used when synthesizing each (meth) acrylic resin, and is a value calculated by the following formula.
  • HEA mole number HEA (parts by mass) / molecular weight of HEA
  • Molecular weight of HEA 116.1
  • AOI mole number is the mole number of 2-isocyanatoethyl acrylate used when each (meth) acrylic resin was synthesized, and is a value calculated by the following formula.
  • the “AOI addition rate” is a ratio of a structural unit derived from 2-hydroxyethyl acrylate to which a structural unit derived from 2-isocyanatoethyl acrylate is added, and is a value calculated by the following formula.
  • AOI addition ratio (mol%) (moles of AOI / moles of HEA) ⁇ 100
  • the weight average molecular weight (Mw), glass transition temperature (Tg), and unsaturated group equivalent of the (meth) acrylic resins (A-1) and (B-1) to (B-5) were measured by the following methods. . Table 1 shows the results.
  • Tg Glass transition temperature
  • DSC7000X differential scanning calorimeter
  • 1 g of each of the (meth) acrylic resin (A-1) and (B-1) to (B-5) solutions was collected and dried at 100 ° C. for 10 minutes to evaporate the ethyl acetate solvent.
  • a sample of 10 mg was collected from each solid content.
  • DSC differential scanning calorimeter
  • the onset temperature was the glass transition temperature (Tg).
  • Tg glass transition temperature
  • Unsaturated group equivalent was calculated from the charged amount of the raw materials by the following equation.
  • Unsaturated group equivalent (mol / g) [C / D]
  • C number of moles of AOI
  • D total weight (g) of all components used in the synthesis excluding the solvent
  • first pressure-sensitive adhesive compositions (a1) to (a3) In a room in which actinic radiation was blocked, a (meth) acrylic resin (A-1), a gas generating agent, a photosensitizer, and a curing agent shown in Table 2 were mixed in a plastic container in a ratio shown in Table 2. And agitated to produce first pressure-sensitive adhesive compositions (a1) to (a3).
  • the numerical values of the (meth) acrylic resins (A-1) (B-1) to (B-5) in Tables 2 and 3 are the values of the (meth) acrylic resin solution ((A-1) (B-1)) (B-5)) content (parts by mass), and the numerical value in parentheses is the value of the solid content of the (meth) acrylic resin (A-1) (B-1) to (B-5). It is the net content (% by mass).
  • the solid content was measured by the following method. The solid content of each resin solution was 35%.
  • the numerical values of the contents of the gas generating agent, the photosensitizer, and the curing agent described in Table 2 and the numerical values of the contents of the curing agent and the photopolymerization initiator described in Table 3 are respectively the solid values of the (meth) acrylic resin. Content (parts by mass) with respect to 100 parts by mass per minute.
  • the glass transition temperature (Tg) of the photo-cured product obtained by photo-curing the second pressure-sensitive adhesive compositions (b1) to (b5) shown in Table 3 by the method described below was measured using a (meth) acrylic resin (A- It was measured in the same manner as in the glass transition temperature (Tg) of 1).
  • Table 3 shows the results.
  • Each of the second pressure-sensitive adhesive compositions (b1) to (b5) was applied on the release surface of a release sheet using an applicator, and was heated and dried at 100 ° C. for 10 minutes to be cured. A second pressure-sensitive adhesive layer was obtained.
  • each second pressure-sensitive adhesive layer was irradiated with ultraviolet rays at a dose of 3000 mJ / cm 2 by using a conveyor type ultraviolet ray irradiation device (2KW lamp, 80 W / cm, manufactured by Eye Graphics Co., Ltd.), and photocured.
  • first pressure-sensitive adhesive compositions (a1) to (a3) shown in Table 2 and the second pressure-sensitive adhesive compositions (b1) to (b5) shown in Table 3 were used to prepare Examples according to the following methods.
  • Pressure-sensitive adhesive sheets 1 to 9 and Comparative Examples 1 to 6 were produced.
  • the first pressure-sensitive adhesive composition (a1) was applied to the treated surface side of a 50 ⁇ m-thick polyethylene terephthalate (PET) sheet that had been subjected to corona discharge treatment so that the film thickness after heating and drying was 15 ⁇ m.
  • the composition was applied using an applicator, dried by heating at 80 ° C. for 2 minutes, and cured to form a first pressure-sensitive adhesive layer having a film thickness shown in Table 2.
  • the thickness of the first pressure-sensitive adhesive layer is obtained by measuring the thickness of a PET sheet adhered on the first pressure-sensitive adhesive layer using a film thickness meter, and then subtracting the thickness of the PET sheet and the base material. I asked.
  • the second pressure-sensitive adhesive composition (b1) was coated on a release surface of a 50 ⁇ m-thick polyethylene terephthalate (PET) sheet coated with a release agent with an applicator so that the film thickness after heating and drying was 10 ⁇ m.
  • the coating was used, and dried by heating at 100 ° C. for 2 minutes to be cured to form a second pressure-sensitive adhesive layer having a film thickness shown in Table 3.
  • the thickness of the second pressure-sensitive adhesive layer is obtained by measuring the thickness of a PET sheet adhered on the second pressure-sensitive adhesive layer using a film thickness meter, and then subtracting the thickness of the PET sheet and the release sheet. I asked.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are disposed to face each other, and a 1 kg rubber roller (width: about 25 cm) is reciprocated once from the top of the release sheet and stuck together, so that the first pressure-sensitive adhesive layer is formed on the base material.
  • a pressure-sensitive adhesive sheet in which an agent layer, a second pressure-sensitive adhesive layer, and a release sheet were laminated in this order.
  • Examples 2 to 9, Comparative Examples 1 to 6 The first pressure-sensitive adhesive layer having the thickness shown in Table 2 was formed using the first pressure-sensitive adhesive composition shown in Tables 4 and 5, and the second pressure-sensitive adhesive composition shown in Tables 4 and 5 was used. Except that the second pressure-sensitive adhesive layer having the thickness shown in Table 3 was formed, pressure-sensitive adhesive sheets of Examples 2 to 9 and Comparative Examples 1 to 6 were produced in the same manner as in Example 1.
  • test pieces were prepared for the pressure-sensitive adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 6 by the following methods, respectively, and the adhesive strength before UV irradiation and the surface state of the photocured second pressure-sensitive adhesive layer were prepared. And the releasability were evaluated. The results are shown in Tables 4 and 5.
  • the pressure-sensitive adhesive sheet was cut into a size of 25 mm in length and 100 mm in width, and the release sheet was peeled off to expose the second pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet is attached to the glass plate so that the exposed second pressure-sensitive adhesive layer (measurement surface) is in contact with the glass plate, and a 2 kg rubber roller (width: about 50 mm) is reciprocated once, before UV irradiation. Samples were used.
  • UV irradiation was performed on the base material side of the sample before UV irradiation using a conveyor-type ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., 2 KW lamp, 80 W / cm) at a UV irradiation amount of 3000 mJ / cm 2 , After irradiation, a sample was obtained.
  • a conveyor-type ultraviolet irradiation device manufactured by Eye Graphics Co., Ltd., 2 KW lamp, 80 W / cm
  • the pressure-sensitive adhesive sheets of Examples 1 to 9 had an adhesive strength before UV irradiation of 0.7 N / 25 mm or more, and had sufficiently high adhesive strength before UV irradiation. Further, in the pressure-sensitive adhesive sheets of Examples 1 to 9, irregularities occur (“B” or “A”) in 40% or more of the surface area of the photo-cured second pressure-sensitive adhesive layer after UV irradiation, and The evaluation was "A”.
  • the pressure-sensitive adhesive sheet of the present invention has a sufficiently high adhesive strength to the adherend by bringing the second pressure-sensitive adhesive layer into close contact with the adherend, and irradiates light to the pressure-sensitive adhesive sheet adhered to the adherend. By doing so, it can be easily separated from the adherend. Therefore, the pressure-sensitive adhesive sheet of the present invention is suitable for the production of MLCC and the like that require extremely high precision processing technology.

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

Abstract

Cette feuille adhésive est obtenue par superposition séquentielle d'une première couche adhésive et d'une seconde couche adhésive sur un matériau de base dans cet ordre; la première couche adhésive contient au moins une résine saturée (A) et un générateur de gaz qui génère un gaz lorsqu'il est irradié avec de la lumière; et la seconde couche adhésive contient au moins une résine insaturée (B) qui a un équivalent de groupe insaturé de 500-1 200 et un initiateur de photopolymérisation.
PCT/JP2019/022107 2018-09-10 2019-06-04 Feuille adhésive WO2020054146A1 (fr)

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WO2021124854A1 (fr) * 2019-12-20 2021-06-24 日東電工株式会社 Feuille adhésive
WO2021124855A1 (fr) * 2019-12-20 2021-06-24 日東電工株式会社 Feuille adhésive
WO2022168785A1 (fr) * 2021-02-04 2022-08-11 パナソニックＩｐマネジメント株式会社 Composition de résine pour cosmétique, composition de résine pour ongles, agent de base de vernis pour ongles en gel, et adhésif pour allongement des cils

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JP2010153774A (ja) * 2008-11-26 2010-07-08 Nitto Denko Corp ダイシング・ダイボンドフィルム及び半導体装置の製造方法
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WO2022168785A1 (fr) * 2021-02-04 2022-08-11 パナソニックＩｐマネジメント株式会社 Composition de résine pour cosmétique, composition de résine pour ongles, agent de base de vernis pour ongles en gel, et adhésif pour allongement des cils

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