WO2012165368A1 - Pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive sheet Download PDF

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Publication number
WO2012165368A1
WO2012165368A1 PCT/JP2012/063607 JP2012063607W WO2012165368A1 WO 2012165368 A1 WO2012165368 A1 WO 2012165368A1 JP 2012063607 W JP2012063607 W JP 2012063607W WO 2012165368 A1 WO2012165368 A1 WO 2012165368A1
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WO
WIPO (PCT)
Prior art keywords
meth
sensitive adhesive
pressure
acrylic acid
acid ester
Prior art date
Application number
PCT/JP2012/063607
Other languages
French (fr)
Japanese (ja)
Inventor
和典 鹿野
齋藤　岳史
Original Assignee
電気化学工業株式会社
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 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2013518074A priority Critical patent/JP5961610B2/en
Publication of WO2012165368A1 publication Critical patent/WO2012165368A1/en

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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
    • 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
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

Definitions

  • This invention relates to the adhesive sheet used for manufacture of an electronic component.
  • the adhesive sheet is usually bonded after the circuit is formed, and then cut into element pieces (dicing), washed, dried, stretched (expanded) the adhesive sheet, and peeled off the element pieces from the adhesive sheet. (Pickup), mounting and other processes.
  • the pressure-sensitive adhesive sheet there is one in which a pressure-sensitive adhesive layer that undergoes a polymerization and curing reaction with ultraviolet light or the like is coated on a base material that is transparent to active rays such as ultraviolet light and / or electron beams.
  • the adherend can be easily peeled off from the pressure-sensitive adhesive sheet after the pressure-sensitive adhesive layer is irradiated with ultraviolet rays or the like to polymerize and cure the pressure-sensitive adhesive layer to reduce the pressure-sensitive adhesive force.
  • Patent Document 1 and Patent Document 2 contain a compound (polyfunctional oligomer) having a photopolymerizable unsaturated double bond in the molecule, which can be three-dimensionally reticulated by, for example, actinic rays.
  • a pressure-sensitive adhesive sheet having a base material surface coated with a pressure-sensitive adhesive is disclosed. In such a pressure-sensitive adhesive sheet, as described in the cited document 3 or 4, the balance of the holding power of the pressure-sensitive adhesive sheet, the releasability at the time of pick-up, and the reflow resistance is a very important factor.
  • the adhesive sheet may be placed under a high temperature condition such as 260 ° C. (for example, a reflow process). Under high temperature conditions, the volatilized component may form bubbles in the pressure-sensitive adhesive layer or the substrate may melt. When bubbles are generated in the pressure-sensitive adhesive layer or the base material is melted, the adhesive force of the pressure-sensitive adhesive layer cannot be sufficiently reduced by light irradiation, and it becomes difficult to peel the adherend from the pressure-sensitive adhesive sheet.
  • a high temperature condition such as 260 ° C.
  • the main object of the present invention is to provide a pressure-sensitive adhesive sheet that does not generate bubbles from the pressure-sensitive adhesive or melt the substrate even under high temperature conditions.
  • the present invention is a pressure-sensitive adhesive sheet comprising a base material and a photocurable pressure-sensitive adhesive layer laminated on one side of the base material, the pressure-sensitive adhesive constituting the photocurable pressure-sensitive adhesive layer Contains a (meth) acrylic acid ester copolymer (A), a photopolymerizable compound (B), a polyfunctional isocyanate curing agent (C) and a photopolymerization initiator (D), and a (meth) acrylic acid ester copolymer.
  • A acrylic acid ester copolymer
  • B photopolymerizable compound
  • C polyfunctional isocyanate curing agent
  • D photopolymerization initiator
  • the polymer (A) is a copolymer of a (meth) acrylic acid ester monomer having a weight average molecular weight of 1,000,000 to 2,000,000, or a (meth) acrylic acid ester monomer and a vinyl compound monomer
  • a pressure-sensitive adhesive sheet that is any one of copolymers is provided. Since this pressure-sensitive adhesive sheet does not contain a low molecular weight component (a component having a polymerization average molecular weight of less than 1 million) that easily volatilizes as a component of the (meth) acrylic acid ester copolymer (A), Air bubbles are unlikely to occur.
  • the polyfunctional isocyanate curing agent (C) has a trifunctional or higher functional isocyanate group, and its blending amount is 1 to 5 masses per 100 mass parts of the (meth) acrylic acid ester copolymer (A).
  • the photopolymerizable compound (B) is preferably a bisphenol A type epoxy acrylate, and the substrate is preferably a light transmissive polyimide film.
  • the present invention provides a pressure-sensitive adhesive sheet that does not generate bubbles from the pressure-sensitive adhesive or melt the substrate even under high temperature conditions.
  • the pressure-sensitive adhesive sheet according to the present invention comprises a base material and a photocurable pressure-sensitive adhesive layer laminated on one side of the base material.
  • the base material is made of a material that is transparent to actinic rays such as ultraviolet rays and / or electron beams (hereinafter also simply referred to as “light”) and has heat resistance that does not melt even at a high temperature of about 260 ° C. .
  • the material include polyimide, and a transparent polyimide film having a total light transmittance of 80% or more is preferably used.
  • the thickness of the substrate is 10 to 150 ⁇ m, preferably 20 to 100 ⁇ m. By making the thickness of the substrate within this range, good handling properties can be obtained.
  • the photocurable pressure-sensitive adhesive layer contains a (meth) acrylic acid ester copolymer (A), a photopolymerizable compound (B), a polyfunctional isocyanate curing agent (C), and a photopolymerization initiator (D). It can form with the adhesive formed.
  • A acrylic acid ester copolymer
  • B photopolymerizable compound
  • C polyfunctional isocyanate curing agent
  • D photopolymerization initiator
  • the (meth) acrylic acid ester copolymer (A) is a copolymer of only a monomer of (meth) acrylic acid ester, or a monomer of (meth) acrylic acid ester and a vinyl compound monomer. A copolymer is preferred.
  • the (meth) acrylic acid ester copolymer (A) preferably has a polymerization average molecular weight (Mw) of 1,000,000 to 2,000,000. Prevents the generation of bubbles from pressure-sensitive adhesives under high-temperature conditions by not containing low-molecular components that easily volatilize (components with a polymerization average molecular weight of less than 1 million) as components of (meth) acrylic acid ester copolymer (A) it can. Moreover, sufficient adhesiveness can be obtained by setting the polymerization average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (A) to 2 million or less.
  • Examples of the (meth) acrylic acid ester monomer include butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, tridecyl (meth) acrylate, myristyl ( (Meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acryl
  • vinyl compound monomers copolymerizable with (meth) acrylic acid ester monomers include vinyl acetate, vinyl alcohol, (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, Examples include acrylamide N-glycolic acid and cinnamic acid.
  • the photopolymerizable compound (B) is preferably a bisphenol A type epoxy acrylate represented by the following general formula.
  • R represents a hydrogen atom or a (meth) acrylate group.
  • N represents an integer of 1 or more.
  • epoxy acrylate for the photopolymerizable compound (B), it is preferable to use epoxy acrylate in order to suppress the generation of bubbles under high temperature conditions.
  • epoxy acrylate for example, in the case of urethane acrylate, there is a possibility that bubbles are generated during heating.
  • the photopolymerizable compound (B) is preferably a tri- to tetra-functional acrylate. If it is less than trifunctional, the peelability from the adherend after light irradiation tends to decrease. On the other hand, if it is pentafunctional or higher, the pressure-sensitive adhesive layer tends to crack when the adherend is peeled off after light irradiation.
  • the photopolymerizable compound (B) preferably has a molecular weight of 1000 to 2000.
  • the molecular weight is less than 1000, the pressure-sensitive adhesive layer tends to crack when the adherend is peeled off.
  • the molecular weight is larger than 2000, the peelability from the adherend tends to decrease.
  • the blending amount of the photopolymerizable compound (B) is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). If the blending amount is less than 20 parts by mass, the pickup property tends to be lowered. On the other hand, when the blending amount exceeds 200 parts by mass, the pressure-sensitive adhesive layer is scraped up in the dicing process, and the scraped pressure-sensitive adhesive layer may cause a decrease in accuracy in the pickup process.
  • the polyfunctional isocyanate curing agent (C) is preferably a trimer (trifunctional) such as aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate. Further, trimethylolpropane adducts of these diisocyanates, burettes reacted with water, trimers having an isocyanurate ring, etc. (trifunctional) are also preferably used. If the number of functional groups is too large, the adhesive strength may be too low.
  • aromatic diisocyanate examples include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and the like.
  • alicyclic diisocyanate examples include isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).
  • aliphatic diisocyanate examples include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
  • curing agent (C) shall be 1 to 5 mass parts with respect to 100 mass parts of (meth) acrylic acid ester polymer (A). If the amount is too large, bubbles are likely to be generated under high temperature conditions.
  • photopolymerization initiator (D) those that do not volatilize even at a high temperature of about 260 ° C. are preferably used.
  • 2-hydroxy-methyl-1-phenyl-propan-1-one manufactured by Ciba Japan, product name Darocur 1173
  • 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by Ciba Japan
  • Product names Irgacure 184 1- [4- (hydroxyethoxy) -phenyl] -2-hydroxy-2methyl-1-propan-1-one (manufactured by Ciba Japan, product name Irgacure 2959)
  • 2-hydroxy-1- Examples include ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one (product name Irgacure 127, manufactured by Ciba Japan).
  • the blending amount of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). If the blending amount is less than 0.1 parts by mass, the peelability from the adherend after light irradiation tends to be reduced. On the other hand, if the blending amount exceeds 100 parts by mass, it causes contamination due to bleeding out to the surface of the pressure-sensitive adhesive layer.
  • a silicone polymer may be blended in the adhesive as a material imparting peelability.
  • the silicone polymer is a polymer of a silicone-based macromonomer having a vinyl group at the end of a (meth) acrylic monomer and a polydimethylsiloxane bond, and is derived from a monomer having a vinyl group at the end of a polydimethylsiloxane bond. It has a monomer unit.
  • (Meth) acrylic monomer includes alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, modified hydroxy (meth) acrylate and (meth) acrylic acid.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate.
  • hydroxyalkyl (meth) acrylate examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
  • modified hydroxy (meth) acrylate examples include ethylene oxide-modified hydroxy (meth) acrylate and lactone-modified hydroxy (meth) acrylate.
  • the silicone-based macromonomer is preferably a compound in which the terminal of the polydimethylsiloxane bond is a vinyl group such as a (meth) acryloyl group or a styryl group.
  • the silicone polymer a reactive hydroxyalkyl (meth) acrylate, a modified hydroxy (meth) acrylate, and a silicone polymer having at least one vinyl group are used.
  • a reactive hydroxyalkyl (meth) acrylate, a modified hydroxy (meth) acrylate, and a silicone polymer having at least one vinyl group are used.
  • generation of minute adhesive residue called particles can be prevented, and even when the adhesive sheet and the adhesive semi-cured layer are laminated, the silicone polymer can be applied to the adhesive semi-cured layer. Migration can be prevented.
  • the proportion of the silicone-based macromonomer unit in the silicone polymer is preferably 15 to 50 parts by mass or less in 100 parts by mass of the silicone polymer.
  • this ratio decreases, the peelability from the adherend after light irradiation tends to decrease.
  • this ratio increases, it causes contamination due to bleeding out to the surface of the pressure-sensitive adhesive.
  • the blending amount of the silicone polymer is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). If the blending amount is less than 0.1 parts by mass, the peelability from the adherend after light irradiation tends to be reduced. On the other hand, when the amount exceeds 20 parts by mass, the initial adhesive strength is insufficient.
  • the thickness of the pressure-sensitive adhesive layer is 1 to 100 ⁇ m, preferably 2 to 40 ⁇ m. If the pressure-sensitive adhesive layer is too thick, the adhesive strength becomes too high and the peelability is lowered. Moreover, if the pressure-sensitive adhesive layer is too thin, the adhesive strength may be too low.
  • Example 1 An adhesive was prepared according to the formulation shown in “Table 1”. The pressure-sensitive adhesive was coated on a PET separator film using a comma coater so that the thickness of the pressure-sensitive adhesive layer after drying was 10 ⁇ m, dried at 100 ° C. for 3 minutes, and then laminated on a 25 ⁇ m substrate to form a pressure-sensitive adhesive sheet. Obtained. As the substrate, an ultraviolet transparent transparent polyimide film (Mitsubishi Gas Film Co., Neoprim L-3430, total light transmittance 90%) was used.
  • an ultraviolet transparent transparent polyimide film Mitsubishi Gas Film Co., Neoprim L-3430, total light transmittance 90%
  • the molecular weight GPC gel permeation chromatography measurement was performed under the following conditions.
  • Device name HLC-8120GPC (manufactured by Tosoh Corporation) Column: 1 TSK Guard HZ-L and 3 HZM-N in series Temperature: 40 ° C
  • Detection differential refractive index solvent: tetrahydrofuran concentration: 0.2 mass / volume%
  • Calibration curve prepared using standard polystyrene (PS) (manufactured by Varian), and molecular weight was expressed in terms of PS.
  • the (meth) acrylic acid ester polymer (A), photopolymerizable compound (B), polyfunctional isocyanate curing agent (C), photopolymerization initiator (D), and base material described in the table include the following: Was used.
  • (A) -2 a copolymer having a weight average molecular weight of 1,000,000 and a commercial product obtained by emulsion polymerization (acrylic rubber AR53L manufactured by ZEON CORPORATION; ethyl acrylate 54%, butyl acrylate 19%, methoxyethyl acrylate 24% Polymer).
  • (A) -3 In-house polymerized product made of a copolymer having a weight average molecular weight of 1,500,000 and obtained by emulsion polymerization.
  • (A) -4 In-house polymerized product made of a copolymer having a weight average molecular weight of 2.5 million and obtained by emulsion polymerization.
  • (B) -1 Bis A type epoxy acrylate. A commercial product of tetrafunctional acrylate and having a molecular weight of 1000 (manufactured by Showa Denko KK, product name Lipoxy PX-390HT).
  • the polyfunctional (meth) acrylate is mainly composed of dipentaerythritol hexaacrylate, with 75% of urethane acrylate oligomer and 25% of polyfunctional (meth) acrylate.
  • the urethane acrylate oligomer has a weight average molecular weight of 100,000, a dispersity of 10.7 and 15 vinyl groups (product name UN-905, manufactured by Negami Kogyo Co., Ltd.).
  • (C) Multifunctional isocyanate curing agent (C)]
  • C) -1 Trifunctional isocyanate which is a trimethylolpropane adduct of tolylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., product name Coronate L-45E).
  • C) -2 Tolylene diisocyanate (bifunctional isocyanate).
  • C) -3 In-house synthesized product of pentafunctional isocyanate.
  • UV transparent PI Polyimide film manufactured by Mitsubishi Gas Film Co., Neoprim L-3430.
  • UV-impermeable PI Toray DuPont polyimide film, Kapton 100H.
  • PO A film made of an ionomer resin (Mitsui / DuPont Chemicals, High Milan 1855) mainly composed of a Zn salt of ethylene-methacrylic acid-methacrylic acid alkyl ester copolymer. Melting point 96 ° C., MFR value measured at 210 ° C. according to JIS K7210, 1.5 g / 10 min.
  • Adhesiveness After adhering the adhesive sheet to glass and press-bonding it with one reciprocation of a 2 kg roller, the adhesive strength was measured under the condition of a pulling speed of 300 mm / min and evaluated according to the following criteria.
  • Examples 2 to 7 A pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive was changed as shown in “Table 1”. The results are shown in “Table 1”.
  • the pressure-sensitive adhesive sheet according to the present invention does not generate bubbles from the pressure-sensitive adhesive or melt the base material even under high temperature conditions, and can easily reduce the pressure-sensitive adhesive layer adhesive strength by light irradiation to easily adhere to the adherend. Can peel. Therefore, the pressure-sensitive adhesive sheet according to the present invention can be suitably used for manufacturing electronic components such as a semiconductor wafer including a heating step.

Abstract

[Problem] To provide a pressure-sensitive adhesive sheet whereby the occurrence of foaming from a pressure-sensitive adhesive and melting of the base material will not occur even under high-temperature conditions. [Solution] Provided is a pressure-sensitive adhesive sheet comprising a base material comprising an optically transparent polyimide film and a light-curable pressure-sensitive adhesive layer laminated onto one side of the base material, wherein the pressure-sensitive adhesive constituting the light-curable pressure-sensitive adhesive layer contains a (meth)acrylic acid ester copolymer (A), a photopolymerizable compound (B), a multi-functional isocyanate curing agent (C), and a photopolymerization initiator (D), the (meth)acrylic acid ester copolymer (A) having a weight-average molecular weight of 1,000,000-2,000,000 and being either a copolymer of a (meth)acrylic acid ester monomer or a copolymer of a (meth)acrylic acid ester monomer and vinyl compound monomer.

Description

粘着シートAdhesive sheet
　本発明は、電子部品の製造に用いられる粘着シートに関する。 This invention relates to the adhesive sheet used for manufacture of an electronic component.
　半導体ウエハは、通常、回路を形成した後に粘着シートを貼合してから、素子小片への切断（ダイシング）、洗浄、乾燥、粘着シートの延伸（エキスパンディング）、粘着シートからの素子小片の剥離（ピックアップ）、マウンティングなどの各工程へ配される。 For semiconductor wafers, the adhesive sheet is usually bonded after the circuit is formed, and then cut into element pieces (dicing), washed, dried, stretched (expanded) the adhesive sheet, and peeled off the element pieces from the adhesive sheet. (Pickup), mounting and other processes.
　粘着シートとして、紫外線及び／又は電子線などの活性光線に対し透過性を有する基材上に、紫外線等により重合硬化反応をする粘着剤層を塗布したものがある。この粘着シートでは、紫外線等を粘着剤層に照射し、粘着剤層を重合硬化させて粘着力を低下させた後、粘着シートから被着体を容易に剥離することができる。 As the pressure-sensitive adhesive sheet, there is one in which a pressure-sensitive adhesive layer that undergoes a polymerization and curing reaction with ultraviolet light or the like is coated on a base material that is transparent to active rays such as ultraviolet light and / or electron beams. In this pressure-sensitive adhesive sheet, the adherend can be easily peeled off from the pressure-sensitive adhesive sheet after the pressure-sensitive adhesive layer is irradiated with ultraviolet rays or the like to polymerize and cure the pressure-sensitive adhesive layer to reduce the pressure-sensitive adhesive force.
　このような粘着シートとして、特許文献１および特許文献２には、例えば活性光線によって三次元網状化しうる、分子内に光重合性不飽和二重結合を有する化合物（多官能性オリゴマー）を含有してなる粘着剤を基材面に塗布した粘着シートが開示されている。
　またこのような粘着シートにおいては、引用文献３又は４に記載されるように、粘着シートの保持力、ピックアップ時の剥離性や耐リフロー性などのバランスは非常に重要な要素である。 As such an adhesive sheet, Patent Document 1 and Patent Document 2 contain a compound (polyfunctional oligomer) having a photopolymerizable unsaturated double bond in the molecule, which can be three-dimensionally reticulated by, for example, actinic rays. A pressure-sensitive adhesive sheet having a base material surface coated with a pressure-sensitive adhesive is disclosed.
In such a pressure-sensitive adhesive sheet, as described in the cited document 3 or 4, the balance of the holding power of the pressure-sensitive adhesive sheet, the releasability at the time of pick-up, and the reflow resistance is a very important factor.
特開昭６０－１９６９５６号公報JP-A-60-196956 特開昭６０－２２３１３９号公報JP-A-60-223139 特開２０１１－４０７６３号公報JP 2011-40763 A 再公表ＷＯ２００８／０１５７５９Republished WO2008 / 015759
　半導体ウエハの製造工程では、例えば２６０℃といった高温の条件下に粘着シートがおかれる場合がある（例えば、リフロー工程）。高温条件下では、揮発した成分が粘着剤層に気泡を形成したり、基材が溶融したりする場合がある。粘着剤層に気泡が発生したり、基材が溶融したりすると、光照射によって粘着剤層の粘着力を十分に低下させられず、被着体を粘着シートから剥離することが困難になる。 In the manufacturing process of a semiconductor wafer, the adhesive sheet may be placed under a high temperature condition such as 260 ° C. (for example, a reflow process). Under high temperature conditions, the volatilized component may form bubbles in the pressure-sensitive adhesive layer or the substrate may melt. When bubbles are generated in the pressure-sensitive adhesive layer or the base material is melted, the adhesive force of the pressure-sensitive adhesive layer cannot be sufficiently reduced by light irradiation, and it becomes difficult to peel the adherend from the pressure-sensitive adhesive sheet.
　そこで、本発明は、高温条件下においても粘着剤からの気泡の発生や基材の溶融が生じない粘着シートを提供することを主な目的とする。 Therefore, the main object of the present invention is to provide a pressure-sensitive adhesive sheet that does not generate bubbles from the pressure-sensitive adhesive or melt the substrate even under high temperature conditions.
　上記課題解決のため、本発明は、基材と、該基材の片面に積層された光硬化型粘着剤層と、からなる粘着シートであって、光硬化型粘着剤層を構成する粘着剤が、（メタ）アクリル酸エステル共重合体（Ａ）と光重合性化合物（Ｂ）と多官能イソシアネート硬化剤（Ｃ）と光重合開始剤（Ｄ）を含有し、（メタ）アクリル酸エステル共重合体（Ａ）が、重量平均分子量１００万～２００万の、（メタ）アクリル酸エステル単量体の共重合体、又は、（メタ）アクリル酸エステル単量体とビニル化合物単量体との共重合体のいずれか一方である粘着シートを提供する。
　この粘着シートは、（メタ）アクリル酸エステル共重合体（Ａ）の成分として揮発し易い低分子量成分（重合平均分子量が１００万未満の成分）を含まないため、高温条件下においても粘着剤から気泡が発生し難い。 In order to solve the above-mentioned problems, the present invention is a pressure-sensitive adhesive sheet comprising a base material and a photocurable pressure-sensitive adhesive layer laminated on one side of the base material, the pressure-sensitive adhesive constituting the photocurable pressure-sensitive adhesive layer Contains a (meth) acrylic acid ester copolymer (A), a photopolymerizable compound (B), a polyfunctional isocyanate curing agent (C) and a photopolymerization initiator (D), and a (meth) acrylic acid ester copolymer. The polymer (A) is a copolymer of a (meth) acrylic acid ester monomer having a weight average molecular weight of 1,000,000 to 2,000,000, or a (meth) acrylic acid ester monomer and a vinyl compound monomer A pressure-sensitive adhesive sheet that is any one of copolymers is provided.
Since this pressure-sensitive adhesive sheet does not contain a low molecular weight component (a component having a polymerization average molecular weight of less than 1 million) that easily volatilizes as a component of the (meth) acrylic acid ester copolymer (A), Air bubbles are unlikely to occur.
　この粘着シートにおいて、多官能イソシアネート硬化剤（Ｃ）は３官能以上のイソシアネート基を有し、その配合量が（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、１～５質量部であることが好ましい。
　また、光重合性化合物（Ｂ）はビスフェノールＡ型エポキシアクリレートであることが好ましく、前記基材は光透過性のポリイミドフィルムであることが好適である。 In this pressure-sensitive adhesive sheet, the polyfunctional isocyanate curing agent (C) has a trifunctional or higher functional isocyanate group, and its blending amount is 1 to 5 masses per 100 mass parts of the (meth) acrylic acid ester copolymer (A). Part.
The photopolymerizable compound (B) is preferably a bisphenol A type epoxy acrylate, and the substrate is preferably a light transmissive polyimide film.
　本発明により、高温条件下においても粘着剤からの気泡の発生や基材の溶融が生じない粘着シートが提供される。 The present invention provides a pressure-sensitive adhesive sheet that does not generate bubbles from the pressure-sensitive adhesive or melt the substrate even under high temperature conditions.
　以下、本発明を実施するための好適な形態について説明する。なお、以下に説明する実施形態は、本発明の代表的な実施形態の一例を示したものであり、これにより本発明の範囲が狭く解釈されることはない。 Hereinafter, preferred embodiments for carrying out the present invention will be described. In addition, embodiment described below shows an example of typical embodiment of this invention, and, thereby, the range of this invention is not interpreted narrowly.
　本発明に係る粘着シートは、基材と、該基材の片面に積層された光硬化型粘着剤層と、からなる。 The pressure-sensitive adhesive sheet according to the present invention comprises a base material and a photocurable pressure-sensitive adhesive layer laminated on one side of the base material.
　基材は、紫外線及び／又は電子線などの活性光線（以下、単に「光」ともいう）に対して透過性を有し、２６０℃程度の高温条件下でも溶融しない耐熱性を備える材料からなる。材料としては、例えばポリイミドが挙げられ、全光線透過率が８０％以上である透明ポリイミドフィルムが好適に用いられる。 The base material is made of a material that is transparent to actinic rays such as ultraviolet rays and / or electron beams (hereinafter also simply referred to as “light”) and has heat resistance that does not melt even at a high temperature of about 260 ° C. . Examples of the material include polyimide, and a transparent polyimide film having a total light transmittance of 80% or more is preferably used.
　基材の厚さは１０～１５０μｍ、好ましくは２０～１００μｍである。基材の厚さをこの範囲にすることにより良好なハンドリング性を得ることができる。 The thickness of the substrate is 10 to 150 μm, preferably 20 to 100 μm. By making the thickness of the substrate within this range, good handling properties can be obtained.
粘着剤層
　光硬化型粘着剤層は、（メタ）アクリル酸エステル共重合体（Ａ）と光重合性化合物（Ｂ）と多官能イソシアネート硬化剤（Ｃ）と光重合開始剤（Ｄ）を含有してなる粘着剤によって形成できる。 Adhesive layer The photocurable pressure-sensitive adhesive layer contains a (meth) acrylic acid ester copolymer (A), a photopolymerizable compound (B), a polyfunctional isocyanate curing agent (C), and a photopolymerization initiator (D). It can form with the adhesive formed.
　（メタ）アクリル酸エステル共重合体（Ａ）は、（メタ）アクリル酸エステルの単量体のみの共重合体、又は、（メタ）アクリル酸エステルの単量体とビニル化合物単量体との共重合体であることが好ましい。（メタ）アクリル酸エステル共重合体（Ａ）は、重合平均分子量（Ｍｗ）が１００万以上２００万以下であることが好ましい。（メタ）アクリル酸エステル共重合体（Ａ）の成分として揮発し易い低分子量成分（重合平均分子量が１００万未満の成分）を含まないことにより、高温条件下における粘着剤からの気泡発生を防止できる。
　また、（メタ）アクリル酸エステル共重合体（Ａ）の重合平均分子量（Ｍｗ）を２００万以下とすることにより十分な粘着性を得ることができる。 The (meth) acrylic acid ester copolymer (A) is a copolymer of only a monomer of (meth) acrylic acid ester, or a monomer of (meth) acrylic acid ester and a vinyl compound monomer. A copolymer is preferred. The (meth) acrylic acid ester copolymer (A) preferably has a polymerization average molecular weight (Mw) of 1,000,000 to 2,000,000. Prevents the generation of bubbles from pressure-sensitive adhesives under high-temperature conditions by not containing low-molecular components that easily volatilize (components with a polymerization average molecular weight of less than 1 million) as components of (meth) acrylic acid ester copolymer (A) it can.
Moreover, sufficient adhesiveness can be obtained by setting the polymerization average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (A) to 2 million or less.
　（メタ）アクリル酸エステルの単量体としては、例えばブチル（メタ）アクリレート、２－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ラウリル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、トリデシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボロニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ベンジル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシメチル（メタ）アクリレート、エトキシ－ｎ－プロピル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレートなどが挙げられる。 Examples of the (meth) acrylic acid ester monomer include butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, tridecyl (meth) acrylate, myristyl ( (Meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) ) Acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate, ethoxy-n-propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Examples thereof include acrylate and 2-hydroxybutyl (meth) acrylate.
　（メタ）アクリル酸エステル単量体に共重合可能なビニル化合物単量体としては、酢酸ビニル、ビニルアルコール、（メタ）アクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、アクリルアミドＮ－グリコール酸、ケイ皮酸などが挙げられる。 Examples of vinyl compound monomers copolymerizable with (meth) acrylic acid ester monomers include vinyl acetate, vinyl alcohol, (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, Examples include acrylamide N-glycolic acid and cinnamic acid.
　光重合性化合物（Ｂ）は、下記一般式で示されるビスフェノールＡ型エポキシアクリレートが用いることが好ましい。 The photopolymerizable compound (B) is preferably a bisphenol A type epoxy acrylate represented by the following general formula.
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒは、水素原子あるいは（メタ）アクリレート基を表す。ｎは１以上の整数を表す。）
Figure JPOXMLDOC01-appb-C000001
(In the formula, R represents a hydrogen atom or a (meth) acrylate group. N represents an integer of 1 or more.)
　光重合性化合物（Ｂ）には、高温条件下での気泡発生を抑制するため、エポキシアクリレートを用いることが好ましい。例えば、ウレタンアクリレートの場合、加熱時に気泡が発生するおそれがある。 For the photopolymerizable compound (B), it is preferable to use epoxy acrylate in order to suppress the generation of bubbles under high temperature conditions. For example, in the case of urethane acrylate, there is a possibility that bubbles are generated during heating.
　光重合性化合物（Ｂ）は、３～４官能アクリレートであることが好ましい。３官能未満であると、光照射後の被着体との剥離性が低下する傾向がある。一方、５官能以上であると光照射後、被着体の剥離時に粘着剤層の割れが発生する傾向がある。 The photopolymerizable compound (B) is preferably a tri- to tetra-functional acrylate. If it is less than trifunctional, the peelability from the adherend after light irradiation tends to decrease. On the other hand, if it is pentafunctional or higher, the pressure-sensitive adhesive layer tends to crack when the adherend is peeled off after light irradiation.
　また、光重合性化合物（Ｂ）は、分子量が１０００～２０００であることが好ましい。分子量が１０００未満では、被着体の剥離時に粘着剤層の割れが発生する傾向ある。一方、分子量が２０００よりも大きいと、被着体との剥離性が低下する傾向がある。 Further, the photopolymerizable compound (B) preferably has a molecular weight of 1000 to 2000. When the molecular weight is less than 1000, the pressure-sensitive adhesive layer tends to crack when the adherend is peeled off. On the other hand, if the molecular weight is larger than 2000, the peelability from the adherend tends to decrease.
　光重合性化合物（Ｂ）の配合量は、（メタ）アクリル酸エステル重合体（Ａ）１００質量部に対して２０～２００質量部とすることが好ましい。配合量が２０質量部未満であるとピックアップ性が低下する傾向がある。一方、配合量が２００質量部を超えるとダイシング工程で粘着剤層の掻き上げが生じ、掻き上げられた粘着剤層がピックアップ工程での精度低下を引き起こすおそれがある。 The blending amount of the photopolymerizable compound (B) is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). If the blending amount is less than 20 parts by mass, the pickup property tends to be lowered. On the other hand, when the blending amount exceeds 200 parts by mass, the pressure-sensitive adhesive layer is scraped up in the dicing process, and the scraped pressure-sensitive adhesive layer may cause a decrease in accuracy in the pickup process.
　多官能イソシアネート硬化剤（Ｃ）には、芳香族ジイソシアネート、脂環族ジイソシアネート及び脂肪族ジイソシアネート等の三量体（３官能）が用いることが好ましい。また、これらのジイソシアネートのトリメチロールプロパンアダクト体、水と反応したビュウレット体及びイソシアヌレート環を有する三量体等（３官能）も好適に用いられる。官能基数が多過ぎると粘着力が低くなりすぎるおそれがある。 The polyfunctional isocyanate curing agent (C) is preferably a trimer (trifunctional) such as aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate. Further, trimethylolpropane adducts of these diisocyanates, burettes reacted with water, trimers having an isocyanurate ring, etc. (trifunctional) are also preferably used. If the number of functional groups is too large, the adhesive strength may be too low.
　芳香族ジイソシアネートとしては、例えばトリレンジイソシアネート、４，４－ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどが挙げられる。 Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and the like.
　脂環族ジイソシアネートとしては、例えばイソホロンジイソシアネート、メチレンビス（４－シクロヘキシルイソシアネート）などが挙げられる。 Examples of the alicyclic diisocyanate include isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).
　脂肪族ジイソシアネートとしては、例えばヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネートなどが挙げられる。 Examples of the aliphatic diisocyanate include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
　多官能イソシアネート硬化剤（Ｃ）の配合量は、（メタ）アクリル酸エステル重合体（Ａ）１００質量部に対して１質量部以上５質量部以下とすることが好ましい。配合量が多すぎると高温条件下で気泡が発生し易くなる。 It is preferable that the compounding quantity of a polyfunctional isocyanate hardening | curing agent (C) shall be 1 to 5 mass parts with respect to 100 mass parts of (meth) acrylic acid ester polymer (A). If the amount is too large, bubbles are likely to be generated under high temperature conditions.
　光重合開始剤（Ｄ）としては、２６０℃程度の高温条件下でも揮発しないものが好適に用いられる。
　具体的には、例えば、２－ヒドロキシ－メチル－１－フェニル－プロパン－１－オン（チバ・ジャパン社製、製品名Ｄａｒｏｃｕｒ１１７３）、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（チバ・ジャパン社製、製品名Ｉｒｇａｃｕｒｅ１８４）、１－［４－（ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２メチル－１－プロパン－１－オン（チバ・ジャパン社製、製品名Ｉｒｇａｃｕｒｅ２９５９）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］－フェニル｝－２－メチル－プロパン－１－オン（チバ・ジャパン社製、製品名Ｉｒｇａｃｕｒｅ１２７）などが挙げられる。 As the photopolymerization initiator (D), those that do not volatilize even at a high temperature of about 260 ° C. are preferably used.
Specifically, for example, 2-hydroxy-methyl-1-phenyl-propan-1-one (manufactured by Ciba Japan, product name Darocur 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Japan) Product names Irgacure 184), 1- [4- (hydroxyethoxy) -phenyl] -2-hydroxy-2methyl-1-propan-1-one (manufactured by Ciba Japan, product name Irgacure 2959), 2-hydroxy-1- Examples include {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (product name Irgacure 127, manufactured by Ciba Japan).
　光重合開始剤（Ｄ）の配合量は、（メタ）アクリル酸エステル重合体（Ａ）１００質量部に対して０．１～２０質量部とすることが好ましい。配合量が０．１質量部未満であると、光照射後の被着体との剥離性が低下する傾向がある。一方、配合量が１００質量部よりを超えると、粘着剤層表面へのブリードアウトにより汚染の要因となる。 The blending amount of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). If the blending amount is less than 0.1 parts by mass, the peelability from the adherend after light irradiation tends to be reduced. On the other hand, if the blending amount exceeds 100 parts by mass, it causes contamination due to bleeding out to the surface of the pressure-sensitive adhesive layer.
　粘着剤には剥離性を付与する材料として、例えばシリコーン重合体を配合してもよい。シリコーン重合体は、（メタ）アクリル単量体とポリジメチルシロキサン結合の末端にビニル基を有するシリコーン系マクロモノマの重合物であり、ポリジメチルシロキサン結合の末端にビニル基を有する単量体に由来する単量体単位を有するものである。 For example, a silicone polymer may be blended in the adhesive as a material imparting peelability. The silicone polymer is a polymer of a silicone-based macromonomer having a vinyl group at the end of a (meth) acrylic monomer and a polydimethylsiloxane bond, and is derived from a monomer having a vinyl group at the end of a polydimethylsiloxane bond. It has a monomer unit.
　（メタ）アクリル単量体としては、アルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、変性ヒドロキシ（メタ）アクリレート及び（メタ）アクリル酸がある。 (Meth) acrylic monomer includes alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, modified hydroxy (meth) acrylate and (meth) acrylic acid.
　アルキル（メタ）アクリレートとしては、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート及びヒドロキシアルキル（メタ）アクリレートがある。 Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate and hydroxyalkyl (meth) acrylate.
　ヒドロキシアルキル（メタ）アクリレートとしては、例えばヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、及びヒドロキシブチル（メタ）アクリレートがある。 Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
　変性ヒドロキシ（メタ）アクリレートとしては、例えばエチレンオキシド変性ヒドロキシ（メタ）アクリレート及びラクトン変性ヒドロキシ（メタ）アクリレートがある。 Examples of the modified hydroxy (meth) acrylate include ethylene oxide-modified hydroxy (meth) acrylate and lactone-modified hydroxy (meth) acrylate.
　シリコーン系マクロモノマは、ポリジメチルシロキサン結合の末端が（メタ）アクリロイル基又はスチリル基等のビニル基となっている化合物が好ましい。 The silicone-based macromonomer is preferably a compound in which the terminal of the polydimethylsiloxane bond is a vinyl group such as a (meth) acryloyl group or a styryl group.
　シリコーン重合体は、より具体的には、反応性を有するヒドロキシアルキル（メタ）アクリレート、変性ヒドロキシ（メタ）アクリレート及びビニル基を少なくとも一つ有するシリコーン重合体が用いられる。これらを用いると、ピックアップ工程において、パーティクルと呼ばれる微小な糊残りの発生を防止でき、粘着シートと接着剤半硬化層を積層した際であっても、シリコーン重合体の接着剤半硬化層へのマイグレーションを防止できる。 More specifically, as the silicone polymer, a reactive hydroxyalkyl (meth) acrylate, a modified hydroxy (meth) acrylate, and a silicone polymer having at least one vinyl group are used. When these are used, in the pick-up process, generation of minute adhesive residue called particles can be prevented, and even when the adhesive sheet and the adhesive semi-cured layer are laminated, the silicone polymer can be applied to the adhesive semi-cured layer. Migration can be prevented.
　シリコーン重合体のシリコーン系マクロモノマ単位の割合は、シリコーン重合体１００質量部中、１５～５０質量部以下が好ましい。この割合が少なくなると、光照射後の被着体との剥離性が低下する傾向がある。一方、この割合が多くなると、粘着剤表面へのブリードアウトにより汚染の要因となる。 The proportion of the silicone-based macromonomer unit in the silicone polymer is preferably 15 to 50 parts by mass or less in 100 parts by mass of the silicone polymer. When this ratio decreases, the peelability from the adherend after light irradiation tends to decrease. On the other hand, when this ratio increases, it causes contamination due to bleeding out to the surface of the pressure-sensitive adhesive.
　シリコーン重合体の配合量は、（メタ）アクリル酸エステル重合体（Ａ）１００質量部に対して０．１～２０質量部とすることが好ましい。配合量が０．１質量部未満であると、光照射後の被着体との剥離性が低下する傾向がある。一方、配合量が２０質量部よりを超えると、初期の粘着力が不足する。 The blending amount of the silicone polymer is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). If the blending amount is less than 0.1 parts by mass, the peelability from the adherend after light irradiation tends to be reduced. On the other hand, when the amount exceeds 20 parts by mass, the initial adhesive strength is insufficient.
　粘着剤層の厚さは１～１００μｍ、好ましくは２～４０μｍである。粘着剤層が厚過ぎると粘着力が高くなり過ぎ、剥離性が低下する。また、粘着剤層が薄過ぎると粘着力が低くなり過ぎる場合がある。 The thickness of the pressure-sensitive adhesive layer is 1 to 100 μm, preferably 2 to 40 μm. If the pressure-sensitive adhesive layer is too thick, the adhesive strength becomes too high and the peelability is lowered. Moreover, if the pressure-sensitive adhesive layer is too thin, the adhesive strength may be too low.
＜実施例１＞
　粘着剤を「表１」に示す配合に従って調製した。粘着剤をＰＥＴセパレーターフィルム上に乾燥後の粘着剤層の厚みが１０μｍとなるようにコンマコーターを用いて塗工し、１００℃で３分間乾燥後、２５μｍの基材に積層して粘着シートを得た。
　基材には、紫外線透過性透明ポリイミドフィルム（三菱ガスフィルム社、ネオプリムＬ－３４３０、全光線透過率９０％）を用いた。 <Example 1>
An adhesive was prepared according to the formulation shown in “Table 1”. The pressure-sensitive adhesive was coated on a PET separator film using a comma coater so that the thickness of the pressure-sensitive adhesive layer after drying was 10 μm, dried at 100 ° C. for 3 minutes, and then laminated on a 25 μm substrate to form a pressure-sensitive adhesive sheet. Obtained.
As the substrate, an ultraviolet transparent transparent polyimide film (Mitsubishi Gas Film Co., Neoprim L-3430, total light transmittance 90%) was used.
　分子量のＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）測定は以下の条件で行った。
装置名：ＨＬＣ－８１２０ＧＰＣ（東ソー社製）
カラム：ＴＳＫ Ｇｕａｒｄ ＨＺ－Ｌ１本とＨＺＭ－Ｎ３本を直列
温度：４０℃
検出：示差屈折率
溶媒：テトラヒドロフラン
濃度：０．２質量／体積％
検量線：標準ポリスチレン（ＰＳ）（Ｖａｒｉａｎ社製）を用いて作成し、分子量はＰＳ換算値で表した。 The molecular weight GPC (gel permeation chromatography) measurement was performed under the following conditions.
Device name: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: 1 TSK Guard HZ-L and 3 HZM-N in series Temperature: 40 ° C
Detection: differential refractive index solvent: tetrahydrofuran concentration: 0.2 mass / volume%
Calibration curve: prepared using standard polystyrene (PS) (manufactured by Varian), and molecular weight was expressed in terms of PS.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表中に記載した（メタ）アクリル酸エステル重合体（Ａ）、光重合性化合物（Ｂ）、多官能イソシアネート硬化剤（Ｃ）、光重合開始剤（Ｄ）、基材には、以下のものを用いた。
［（メタ）アクリル酸エステル重合体（Ａ）］
　（Ａ）－１：重量平均分子量５０万の共重合体からなり、乳化重合により得られる自社重合品。
　（Ａ）－２：重量平均分子量１００万の共重合体であり乳化重合より得られる市販品（日本ゼオン社製アクリルゴムＡＲ５３Ｌ；エチルアクリレート５４％、ブチルアクリレート１９％、メトキシエチルアクリレート２４％の共重合体）。
　（Ａ）－３：重量平均分子量１５０万の共重合体からなり、乳化重合により得られる自社重合品。
 （Ａ）－４：重量平均分子量２５０万の共重合体からなり、乳化重合により得られる自社重合品。 The (meth) acrylic acid ester polymer (A), photopolymerizable compound (B), polyfunctional isocyanate curing agent (C), photopolymerization initiator (D), and base material described in the table include the following: Was used.
[(Meth) acrylic acid ester polymer (A)]
(A) -1: In-house polymerized product made of a copolymer having a weight average molecular weight of 500,000 and obtained by emulsion polymerization.
(A) -2: a copolymer having a weight average molecular weight of 1,000,000 and a commercial product obtained by emulsion polymerization (acrylic rubber AR53L manufactured by ZEON CORPORATION; ethyl acrylate 54%, butyl acrylate 19%, methoxyethyl acrylate 24% Polymer).
(A) -3: In-house polymerized product made of a copolymer having a weight average molecular weight of 1,500,000 and obtained by emulsion polymerization.
(A) -4: In-house polymerized product made of a copolymer having a weight average molecular weight of 2.5 million and obtained by emulsion polymerization.
［光重合性化合物（Ｂ）］
　（Ｂ）－１：ビスＡ型エポキシアクリレート。４官能アクリレートであり、分子量１０００の市販品（昭和電工社製、製品名リポキシＰＸ－３９０ＨＴ）。
　（Ｂ）－２：ウレタンアクリレート：。ウレタンアクリレートオリゴマと多官能（メタ）アクリレートからなる。ウレタンアクリレートオリゴマは、イソホロンジイソシアネートの三量体のイソシアネートに、ジペタエリスリトールペンタアクリレートを主成分とする水酸基含有アクリレートを反応させたものである。多官能（メタ）アクリレートは、ジペンタエリスリトールヘキサアクリレートを主成分とし、ウレタンアクリレートオリゴマが７５％、多官能（メタ）アクリレートが２５％である。ウレタンアクリレートオリゴマは、重量平均分子量１０００００、分散度１０．７でビニル基の数が１５個である（根上工業社製、製品名ＵＮ－９０５）。 [Photopolymerizable compound (B)]
(B) -1: Bis A type epoxy acrylate. A commercial product of tetrafunctional acrylate and having a molecular weight of 1000 (manufactured by Showa Denko KK, product name Lipoxy PX-390HT).
(B) -2: Urethane acrylate: It consists of urethane acrylate oligomer and polyfunctional (meth) acrylate. The urethane acrylate oligomer is obtained by reacting a hydroxyl group-containing acrylate containing dipetaerythritol pentaacrylate as a main component with an isophorone diisocyanate trimer isocyanate. The polyfunctional (meth) acrylate is mainly composed of dipentaerythritol hexaacrylate, with 75% of urethane acrylate oligomer and 25% of polyfunctional (meth) acrylate. The urethane acrylate oligomer has a weight average molecular weight of 100,000, a dispersity of 10.7 and 15 vinyl groups (product name UN-905, manufactured by Negami Kogyo Co., Ltd.).
［多官能イソシアネート硬化剤（Ｃ）］
　（Ｃ）－１：トリレンジイソシアネートのトリメチロールプロパンアダクト体である３官能イソシアネート（日本ポリウレタン社製、製品名コロネートＬ－４５Ｅ）。
　（Ｃ）－２：トリレンジイソシアネート（２官能イソシアネート）。
　（Ｃ）－３：５官能イソシアネート自社合成品。 [Multifunctional isocyanate curing agent (C)]
(C) -1: Trifunctional isocyanate which is a trimethylolpropane adduct of tolylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., product name Coronate L-45E).
(C) -2: Tolylene diisocyanate (bifunctional isocyanate).
(C) -3: In-house synthesized product of pentafunctional isocyanate.
［光重合開始剤（Ｄ）］
　チバ・ジャパン社製、製品名Ｉｒｇａｃｕｒｅ１２７；２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］－フェニル｝－２－メチル－プロパン－１－オン。 [Photoinitiator (D)]
Product name Irgacure 127; 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one manufactured by Ciba Japan.
［基材］
　紫外線透過性ＰＩ：三菱ガスフィルム社製ポリイミドフィルム、ネオプリムＬ－３４３０。
　紫外線非透過性ＰＩ：東レデュポン社製ポリイミドフィルム、カプトン１００Ｈ。
　ＰＯ：エチレン-メタアクリル酸－メタアクリル酸アルキルエステル共重合体のＺｎ塩を主成分とするアイオノマ樹脂（三井・デュポンケミカル社製、ハイミラン１８５５）からなるフィルム。融点９６℃、ＪＩＳ　Ｋ７２１０に従って温度２１０℃で測定したＭＦＲ値１．５ｇ／１０分。 [Base material]
UV transparent PI: Polyimide film manufactured by Mitsubishi Gas Film Co., Neoprim L-3430.
UV-impermeable PI: Toray DuPont polyimide film, Kapton 100H.
PO: A film made of an ionomer resin (Mitsui / DuPont Chemicals, High Milan 1855) mainly composed of a Zn salt of ethylene-methacrylic acid-methacrylic acid alkyl ester copolymer. Melting point 96 ° C., MFR value measured at 210 ° C. according to JIS K7210, 1.5 g / 10 min.
　作成した粘着シートについて以下の評価を行った。 The following evaluation was performed on the prepared adhesive sheet.
（１）耐熱性
　２６０℃のホットプレート上で２分間粘着シートを加熱し、基材フィルムの寸法安定性を以下の基準で評価した。
　◎（優）　：基材フィルムの収縮率が３％以下であり、溶融しない。
　○（良）　：基材フィルムの収縮率が３％以上５％以下。
　×（不可）：基材フィルムの収縮率が５％以上。 (1) Heat resistance The adhesive sheet was heated on a hot plate at 260 ° C for 2 minutes, and the dimensional stability of the base film was evaluated according to the following criteria.
A (excellent): The shrinkage of the base film is 3% or less and does not melt.
○ (good): The shrinkage of the base film is 3% or more and 5% or less.
X (impossible): Shrinkage of the base film is 5% or more.
（２）揮発性
　粘着シートをガラスに貼り合わせ、２ｋｇロ－ラの１往復で圧着した後、粘着シートがホットプレートに直に接するように設置し、２６０℃のホットプレート上で２分間粘着シートを加熱し、気泡の発生程度を観察した。
　◎（優）　：気泡が１つ以下。
　○（良）　：気泡が２つ以上３つ以下。
　×（不可）：気泡が４つ以上。 (2) Volatile Adhesive sheet is attached to glass, and after pressure-bonding in one reciprocation of a 2 kg roller, the adhesive sheet is placed in direct contact with the hot plate, and the adhesive sheet is placed on the hot plate at 260 ° C for 2 minutes. Was heated and the generation of bubbles was observed.
◎ (excellent): One or less bubbles.
○ (good): 2 or more and 3 or less bubbles.
X (impossible): 4 or more bubbles.
（３）剥離性
　粘着シートをガラスに貼り合わせ、２ｋｇロ－ラの１往復で圧着した後、粘着シートがホットプレートに直に接するように設置し、２６０℃のホットプレート上で２分間粘着シートを加熱した。基材フィルム側から１５０ｍＪ／ｃｍ２の紫外線を照射した後、引張り速度３００ｍｍ／分の条件で粘着力を測定し、以下の基準により評価した。
　◎（優）　：粘着力が１．０Ｎ／２０ｍｍ以下。
　○（良）　：粘着力が１．０Ｎ／２０ｍｍ以上２．０Ｎ／２０ｍｍ以下。
　×（不可）：粘着力が２．０Ｎ／２０ｍｍ以上。 (3) Peelability After sticking the adhesive sheet on glass and press-bonding it with a 2-kg roller in one reciprocation, place it so that the adhesive sheet is in direct contact with the hot plate. Was heated. After irradiating 150 mJ / cm 2 of ultraviolet rays from the base film side, the adhesive strength was measured under the condition of a pulling speed of 300 mm / min, and evaluated according to the following criteria.
A (excellent): Adhesive strength is 1.0 N / 20 mm or less.
○ (good): Adhesive strength is 1.0 N / 20 mm or more and 2.0 N / 20 mm or less.
X (impossible): Adhesive strength is 2.0 N / 20 mm or more.
（４）粘着性
　粘着シートをガラスに貼り合わせ、２ｋｇロ－ラの１往復で圧着した後、引張り速度３００ｍｍ／分の条件で粘着力を測定し、以下の基準により評価した。
　◎（優）　：粘着力が０．５Ｎ／２０ｍｍ以上。
　○（良）　：粘着力が０．１Ｎ／２０ｍｍ以上０．５Ｎ／２０ｍｍ以下。
　×（不可）：粘着力が０．１Ｎ／２０ｍｍ以下。 (4) Adhesiveness After adhering the adhesive sheet to glass and press-bonding it with one reciprocation of a 2 kg roller, the adhesive strength was measured under the condition of a pulling speed of 300 mm / min and evaluated according to the following criteria.
A (excellent): Adhesive strength is 0.5 N / 20 mm or more.
○ (Good): Adhesive strength is 0.1 N / 20 mm or more and 0.5 N / 20 mm or less.
X (impossible): Adhesive strength is 0.1 N / 20 mm or less.
　評価結果を「表１」に示す。耐熱性、揮発性及び剥離性のいずれの評価項目においても、優の評価が得られた。 The evaluation results are shown in “Table 1”. Excellent evaluation was obtained in any of the evaluation items of heat resistance, volatility, and peelability.
＜実施例２～７＞
　「表１」に示すように粘着剤の配合を変更した以外は、実施例１と同様にして粘着シートを作成し、評価を行った。結果を「表１」に示す。 <Examples 2 to 7>
A pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive was changed as shown in “Table 1”. The results are shown in “Table 1”.
＜比較例１、４、５＞
　「表１」に示すように粘着剤層の配合を変更した以外は、実施例１と同様にして粘着シートを作成し、評価を行った。結果を「表１」に示す。 <Comparative Examples 1, 4, 5>
A pressure-sensitive adhesive sheet was prepared and evaluated in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive layer was changed as shown in “Table 1”. The results are shown in “Table 1”.
＜比較例２、３＞
　比較例２及び３では、基材フィルムにそれぞれ「紫外線非透過性透明ＰＩ」と「ＰＯ」を用い、かつ、イソシアネート硬化剤（Ｃ）の配合量を「表１」に示すように変更した以外は、実施例１と同様にして粘着シートを作成し、評価を行った。結果を「表１」に示す。 <Comparative Examples 2 and 3>
In Comparative Examples 2 and 3, “UV-opaque transparent PI” and “PO” were used for the base film, respectively, and the amount of the isocyanate curing agent (C) was changed as shown in “Table 1” Were prepared in the same manner as in Example 1 and evaluated. The results are shown in “Table 1”.
　本発明に係る粘着シートは、高温条件下においても粘着剤からの気泡の発生や基材の溶融が生じず、光照射によって粘着剤層の粘着力を十分に低下させて被着体を容易に剥離できる。従って、本発明に係る粘着シートは、加熱工程を含む半導体ウエハなどの電子部品の製造に好適に用いることができる。 The pressure-sensitive adhesive sheet according to the present invention does not generate bubbles from the pressure-sensitive adhesive or melt the base material even under high temperature conditions, and can easily reduce the pressure-sensitive adhesive layer adhesive strength by light irradiation to easily adhere to the adherend. Can peel. Therefore, the pressure-sensitive adhesive sheet according to the present invention can be suitably used for manufacturing electronic components such as a semiconductor wafer including a heating step.

Claims (3)

  1. 　光透過性のポリイミドフィルムからなる基材と、該基材の片面に積層された光硬化型粘着剤層と、からなる粘着シートであって、
    　光硬化型粘着剤層を構成する粘着剤が、（メタ）アクリル酸エステル共重合体（Ａ）と光重合性化合物（Ｂ）と多官能イソシアネート硬化剤（Ｃ）と光重合開始剤（Ｄ）を含有し、
    　（メタ）アクリル酸エステル共重合体（Ａ）は、重量平均分子量が１００万～２００万であり、（メタ）アクリル酸エステル単量体の共重合体、又は、（メタ）アクリル酸エステル単量体とビニル化合物単量体との共重合体のいずれか一方である粘着シート。     A pressure-sensitive adhesive sheet comprising a base material made of a light-transmitting polyimide film, and a photocurable pressure-sensitive adhesive layer laminated on one side of the base material,
    The pressure-sensitive adhesive constituting the photocurable pressure-sensitive adhesive layer is composed of (meth) acrylic acid ester copolymer (A), photopolymerizable compound (B), polyfunctional isocyanate curing agent (C), and photopolymerization initiator (D). Containing
    The (meth) acrylic acid ester copolymer (A) has a weight average molecular weight of 1,000,000 to 2,000,000, a copolymer of (meth) acrylic acid ester monomers, or a single amount of (meth) acrylic acid ester A pressure-sensitive adhesive sheet which is one of a copolymer of a polymer and a vinyl compound monomer.
  2. 　多官能イソシアネート硬化剤（Ｃ）が３官能以上のイソシアネート基を有し、その配合量が（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、１～５質量部である請求項１記載の粘着シート。 The polyfunctional isocyanate curing agent (C) has a trifunctional or higher functional isocyanate group, and the blending amount thereof is 1 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). The pressure-sensitive adhesive sheet according to 1.
  3. 　光重合性化合物（Ｂ）がビスフェノールＡ型エポキシアクリレートである請求項１又は２記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the photopolymerizable compound (B) is a bisphenol A type epoxy acrylate.
PCT/JP2012/063607 2011-05-27 2012-05-28 Pressure-sensitive adhesive sheet WO2012165368A1 (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014234422A (en) * 2013-05-31 2014-12-15 昭和電工株式会社 Active ray-curable tackifier composition for re-peelable protective tape targeting glass etching and re-peelable protective tape targeting glass etching
WO2014199993A1 (en) * 2013-06-14 2014-12-18 電気化学工業株式会社 Heat-resistant adhesive sheet for semiconductor inspection
CN106459688A (en) * 2014-05-12 2017-02-22 电化株式会社 Heat-resistant adhesive sheet for semiconductor inspection and semiconductor inspection method
JP2020017758A (en) * 2015-06-05 2020-01-30 リンテック株式会社 Composite sheet for forming protective film
JP2020032548A (en) * 2018-08-27 2020-03-05 日東電工株式会社 Laminate
JP2020105437A (en) * 2018-12-28 2020-07-09 フジコピアン株式会社 Thin film support adhesive film
JP2020105438A (en) * 2018-12-28 2020-07-09 フジコピアン株式会社 Thin film support adhesive film
CN112055734A (en) * 2018-05-28 2020-12-08 电化株式会社 Adhesive tape and method for manufacturing semiconductor device using the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1054906A (en) * 1996-08-09 1998-02-24 Sekisui Chem Co Ltd Phase difference plate and elliptic polarizing plate
JP2005298579A (en) * 2004-04-07 2005-10-27 Toyobo Co Ltd Adhesive tape
JP2008069185A (en) * 2006-09-12 2008-03-27 Denki Kagaku Kogyo Kk Adhesive sheet for fixing electronic part and method for producing electronic part by using the same
JP2008145366A (en) * 2006-12-13 2008-06-26 Toyobo Co Ltd Method for inspecting internal contamination of optically transparent material
JP2010053192A (en) * 2008-08-27 2010-03-11 Nitto Denko Corp Pressure-sensitive adhesive tape or sheet
WO2011077835A1 (en) * 2009-12-21 2011-06-30 電気化学工業株式会社 Adhesive sheet and production method for electronic component

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1054906A (en) * 1996-08-09 1998-02-24 Sekisui Chem Co Ltd Phase difference plate and elliptic polarizing plate
JP2005298579A (en) * 2004-04-07 2005-10-27 Toyobo Co Ltd Adhesive tape
JP2008069185A (en) * 2006-09-12 2008-03-27 Denki Kagaku Kogyo Kk Adhesive sheet for fixing electronic part and method for producing electronic part by using the same
JP2008145366A (en) * 2006-12-13 2008-06-26 Toyobo Co Ltd Method for inspecting internal contamination of optically transparent material
JP2010053192A (en) * 2008-08-27 2010-03-11 Nitto Denko Corp Pressure-sensitive adhesive tape or sheet
WO2011077835A1 (en) * 2009-12-21 2011-06-30 電気化学工業株式会社 Adhesive sheet and production method for electronic component

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014234422A (en) * 2013-05-31 2014-12-15 昭和電工株式会社 Active ray-curable tackifier composition for re-peelable protective tape targeting glass etching and re-peelable protective tape targeting glass etching
KR102216458B1 (en) * 2013-06-14 2021-02-17 덴카 주식회사 Heat-resistant adhesive sheet for semiconductor inspection
WO2014199993A1 (en) * 2013-06-14 2014-12-18 電気化学工業株式会社 Heat-resistant adhesive sheet for semiconductor inspection
CN105264034A (en) * 2013-06-14 2016-01-20 电化株式会社 Heat-resistant adhesive sheet for semiconductor inspection
KR20160019421A (en) * 2013-06-14 2016-02-19 덴카 주식회사 Heat-resistant adhesive sheet for semiconductor inspection
US20160130481A1 (en) * 2013-06-14 2016-05-12 Denka Company Limited Heat-resistant adhesive sheet for semiconductor testing
JPWO2014199993A1 (en) * 2013-06-14 2017-02-23 デンカ株式会社 Heat resistant adhesive sheet for semiconductor inspection
TWI618176B (en) * 2013-06-14 2018-03-11 電化股份有限公司 Heat-resistant adhesive sheet for use in checking semiconductor
US9963622B2 (en) 2013-06-14 2018-05-08 Denka Company Limited Heat-resistant adhesive sheet for semiconductor testing
CN106459688A (en) * 2014-05-12 2017-02-22 电化株式会社 Heat-resistant adhesive sheet for semiconductor inspection and semiconductor inspection method
JPWO2015174381A1 (en) * 2014-05-12 2017-04-20 デンカ株式会社 Heat-resistant adhesive sheet for semiconductor inspection, and semiconductor inspection method
CN106459688B (en) * 2014-05-12 2021-09-17 电化株式会社 Heat-resistant adhesive sheet for semiconductor inspection and semiconductor inspection method
JP2020017758A (en) * 2015-06-05 2020-01-30 リンテック株式会社 Composite sheet for forming protective film
CN112055734A (en) * 2018-05-28 2020-12-08 电化株式会社 Adhesive tape and method for manufacturing semiconductor device using the same
CN112055734B (en) * 2018-05-28 2022-07-01 电化株式会社 Adhesive tape and method for manufacturing semiconductor device using the same
KR20200024088A (en) * 2018-08-27 2020-03-06 닛토덴코 가부시키가이샤 Laminate
JP2020032548A (en) * 2018-08-27 2020-03-05 日東電工株式会社 Laminate
JP7111558B2 (en) 2018-08-27 2022-08-02 日東電工株式会社 laminate
KR102499644B1 (en) 2018-08-27 2023-02-15 닛토덴코 가부시키가이샤 Laminate
JP2020105437A (en) * 2018-12-28 2020-07-09 フジコピアン株式会社 Thin film support adhesive film
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JP7214303B2 (en) 2018-12-28 2023-01-30 フジコピアン株式会社 thin support adhesive film
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