WO2013042698A1 - 電子部品切断用加熱剥離型粘着シート及び電子部品切断方法 - Google Patents

電子部品切断用加熱剥離型粘着シート及び電子部品切断方法 Download PDF

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Publication number
WO2013042698A1
WO2013042698A1 PCT/JP2012/073983 JP2012073983W WO2013042698A1 WO 2013042698 A1 WO2013042698 A1 WO 2013042698A1 JP 2012073983 W JP2012073983 W JP 2012073983W WO 2013042698 A1 WO2013042698 A1 WO 2013042698A1
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Prior art keywords
heat
sensitive adhesive
energy ray
layer
peelable pressure
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PCT/JP2012/073983
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English (en)
French (fr)
Japanese (ja)
Inventor
高正 平山
下川　大輔
一之 木内
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to JP2013534732A priority Critical patent/JP6000958B2/ja
Priority to KR1020147006874A priority patent/KR101950051B1/ko
Priority to CN201280045943.5A priority patent/CN103827241A/zh
Publication of WO2013042698A1 publication Critical patent/WO2013042698A1/ja

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    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • 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
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • 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
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
    • 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
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane 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
    • 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
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer

Definitions

  • the present invention relates to a heat-peelable pressure-sensitive adhesive sheet for cutting electronic components and an electronic component cutting method.
  • the pressure-sensitive adhesive layer is soft and thick, so that sufficient processing accuracy cannot be obtained due to the fluctuation of the pressure-sensitive adhesive due to stress during processing.
  • it is effective to make the pressure-sensitive adhesive layer thin, but if the pressure-sensitive adhesive layer is made too thin, the unevenness of the surface of the pressure-sensitive adhesive layer due to the thermally expandable microsphere particles causes poor appearance due to entrapment of bubbles and the like. And sufficient adhesiveness cannot be obtained, and the function as a fixing pressure-sensitive adhesive sheet cannot be exhibited.
  • an energy ray-curable heat formed by laminating a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres on a base material via an energy ray-curable elastic layer.
  • the peelable adhesive sheet secures electronic components and semiconductor wafers, and the energy ray curable elastic layer is cured during processing to improve the processing accuracy by reducing the blurring of the adhesive during processing.
  • the conventional energy ray curable heat-peelable pressure-sensitive adhesive sheet used in this method does not have sufficient adhesion between the cured energy ray curable elastic layer and the substrate, and the energy ray curable elastic layer There may be partial peeling (throwing failure) between the materials, adhesive residue may be generated on the adherend, and the cross section by the cutting process is not perpendicular to the surface and cannot be cut accurately. was there.
  • the inventors of the present invention have revealed that a method for chemically increasing the affinity between the pressure-sensitive adhesive layer and the substrate and the surface of the substrate.
  • a method used in a normal pressure-sensitive adhesive sheet such as a method of forming fine irregularities on the surface to increase the contact area between the two.
  • the trial and error about the structure of the heat-peelable adhesive sheet which can suppress the throwing destruction about this kind of adhesive sheet effectively was repeated, and it came to completion of this invention.
  • the heat-peelable pressure-sensitive adhesive sheet of the present invention is 1.
  • a heat-peelable pressure-sensitive adhesive sheet comprising a heat-peelable pressure-sensitive adhesive layer containing heat-expandable microspheres on at least one side of a base material via an energy-ray-curable elastic layer, wherein the base material and the energy beam are cured
  • the heat-peelable pressure-sensitive adhesive sheet according to claim 1 or 2 wherein the heat-peelable pressure-sensitive adhesive layer has a thickness of 50 ⁇ m or less. 4). 4. The heat-peelable pressure-sensitive adhesive sheet according to claim 1, wherein the energy ray-curable elastic layer has a thickness of 3 to 150 ⁇ m. 5. A method for cutting an electronic component, comprising temporarily fixing the electronic component with the heat-peelable pressure-sensitive adhesive sheet according to any one of 1 to 4 and cutting the electronic component.
  • the unevenness caused by the heat-expandable microspheres generated in the heat-peelable pressure-sensitive adhesive layer made thinner than the maximum particle diameter of the heat-expandable microspheres is softened before curing to improve the processing accuracy.
  • a pressure-sensitive adhesive sheet having a good appearance and surface smoothness is manufactured by adhering to an energy ray curable elastic layer and absorbed, and then the energy ray curable elastic layer is cured after being attached to a work piece or
  • a pressure-sensitive adhesive sheet in which the thickness of the soft pressure-sensitive adhesive layer (in this case, a heat-peelable pressure-sensitive adhesive) is reduced can be obtained. Furthermore, a small part can be processed with high accuracy by processing the workpiece using the adhesive sheet.
  • difference of an adhesive, winding up, and a chipping at the time of a press process or a cutting process can be suppressed, and it can cut
  • the cut piece cut with high accuracy can be easily peeled and collected. Therefore, the operability and workability in the process of peeling and collecting the cut pieces can be remarkably improved, and as a result, the productivity of cut pieces such as small or thin semiconductor chips and multilayer capacitor chips can be greatly improved.
  • a pressure-sensitive adhesive sheet having a good appearance and surface smoothness is produced by laminating and absorbing by bonding to a mold elastic layer, etc., and after that or after being attached to a work piece, the energy ray curable elastic layer is cured. And found that small parts can be processed with high precision by using a processing method for processing a workpiece using an adhesive sheet with a thin thickness of a soft adhesive layer (in this case, a heat-peelable adhesive layer), The present invention has been reached.
  • the heat-peelable sheet of the present invention is provided with a heat-peelable pressure-sensitive adhesive layer containing thermally expandable microspheres on at least one side of a base material via an energy-ray-curable elastic layer.
  • An organic coating layer is disposed between the mold elastic layer and the heat-peelable pressure-sensitive adhesive sheet.
  • the energy ray-curable elastic layer and the heat-peelable pressure-sensitive adhesive layer may be provided on one side of the substrate or on both sides.
  • an adhesive layer can also be formed on the other side of the substrate, and when processing an electronic component, the heating having the heat-peelable pressure-sensitive adhesive layer to which the electronic component is fixed.
  • a peelable pressure-sensitive adhesive sheet can be placed on the stage of a processing apparatus and fixed to the stage with an adhesive layer on the other surface of the substrate. Of course, it is not always necessary to form the adhesive layer on the other surface of the substrate.
  • the heat-peelable pressure-sensitive adhesive sheet having the heat-peelable pressure-sensitive adhesive layer to which the electronic component is fixed is used as the processing device. It can also be fixed by a fixing means provided on the stage, such as a vacuum chuck.
  • the base material 1 serves as a support base for the organic coating layer 2 and the energy ray curable elastic layer 3, and has heat resistance that does not impair mechanical properties by heat treatment of the heat-peelable pressure-sensitive adhesive layer 4. used.
  • a substrate 1 include, but are not limited to, plastic films and sheets such as polyester, olefin resin, and polyvinyl chloride.
  • the substrate 1 preferably has a cutting property with respect to a cutting means such as a cutter used for cutting the adherend.
  • a base material having heat resistance and stretchability such as a flexible polyolefin film or sheet
  • the base material is later Therefore, it is suitable for a cut piece collection method that requires a gap between the cut pieces.
  • the substrate 1 and the organic coating layer 2 can transmit a predetermined amount or more of energy rays. It needs to be composed of materials.
  • the substrate 1 may be a single layer or a multilayer body. Further, the substrate 1 is subjected to a surface treatment with an appropriate release agent described later, an energy ray curable elastic layer is formed on the treated surface, and the obtained energy ray curable thermally expandable adhesive sheet is irradiated with energy rays. Then, after the energy ray-curable elastic layer is cured, the energy ray-curable thermally expandable pressure-sensitive adhesive sheet itself can be thinned by peeling off the substrate 1.
  • the thickness of the substrate 1 can be appropriately selected within a range that does not impair the operability and workability in each step such as bonding of the adherend, cutting of the adherend, peeling of the cut piece, and recovery, but is usually 500 ⁇ m or less.
  • the thickness is preferably about 3 to 300 ⁇ m, more preferably about 5 to 250 ⁇ m.
  • the surface of the substrate 1 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion and retention with adjacent layers.
  • a physical treatment, a coating treatment with an undercoat for example, an adhesive substance described later, or the like may be performed.
  • Organic coating layer 2 needs to adhere well to the substrate 1 and the energy ray-curable elastic layer must not be thrown away after the heat peeling. Whether or not the throwing destruction occurs can be evaluated by, for example, the method described in the following examples. By not throwing and destroying, the substrate and the heat-peelable pressure-sensitive adhesive layer are more strongly bonded via the organic coating layer 2, so that the heat-peelability is good when the heat-peelable pressure-sensitive adhesive sheet of the present invention is used. It is possible to exert an effect that the adhesive peels off, that is, the adhesive residue does not occur.
  • any material may be used.
  • various coating materials as shown in the literature (Plastic Hard Coat Material II, CMC Publishing, (2004)) can be used.
  • urethane polymers are preferred. This is because it exhibits excellent adhesion to the substrate and excellent anchoring properties for the energy ray curable elastic layer (particularly after curing).
  • polyacryl urethane, polyester polyurethane, and precursors thereof are more preferable. These materials are practical, such as simple application and application to the substrate 1, and various industrial materials can be selected and can be obtained at low cost.
  • polyacryl urethane and polyester polyurethane any of those described in the literature (Plastic Hard Coat Material II, P17-21, CMC Publishing, (2004)) and literature (Latest Polyurethane Material and Applied Technology, CMC Publishing, (2005)) Can also be used. These are polymers composed of a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound). As further components, chain extenders such as polyamines, anti-aging agents, oxidation stabilizers and the like may be included.
  • polyacryl urethane and polyester polyurethane those prepared by reacting the above-described monomers may be used, or those commercially available or used as a binder resin for coating materials or inks and paints may be used ( Literature: Latest polyurethane materials and applied technology, see P190, CMC Publishing (2005)).
  • a polyurethane “NB300” manufactured by Dainichi Seika, “Adekabon titer (registered trademark)” manufactured by ADEKA, “Takelac® A / Takenate® A” manufactured by Mitsui Chemicals, DIC Commercial products such as “UC Sealer” manufactured by Graphics are listed.
  • a dye may be added to such a polymer, and the ink may be printed on a film layer as an ink.
  • a polyurethane-modified resin such as polyurethane-based vinyl acetate-vinyl chloride copolymer (Daiichi Seika Co., Ltd. NB300) can be used, and the design of the pressure-sensitive adhesive sheet can be enhanced by such printing.
  • polyacryl urethane and polyester urethane exhibit good adhesion to the substrate is that the isocyanate component contained as a monomer reacts with polar functional groups such as hydroxyl groups and carboxyl groups present on the substrate surface. This is considered to form a strong bond.
  • the reason why the anchoring property with the energy ray curable elastic layer is improved after energy ray curing is that the radical species generated in the vicinity of the urethane bond and the radical generated in the energy ray curable elastic layer upon irradiation with ultraviolet rays or the like This is presumed to be due to the reaction with the seed to form a strong bond (Reference: Structure / physical properties and high functionality of polyurethane and its application development, p191-194, Technical Information Association (1999)).
  • the thickness of the organic coating layer is not particularly limited, but is preferably about 0.1 to 10 ⁇ m, preferably about 0.1 to 5 ⁇ m, and more preferably about 0.5 to 5 ⁇ m.
  • the energy ray curable elastic layer 3 contains an energy ray curable compound (or energy ray curable resin) for imparting energy ray curable properties, and is heated when the heat-peelable pressure-sensitive adhesive layer 4 is pressure-bonded. It has viscoelasticity to the extent that the unevenness of the expandable microsphere can be relaxed (see the enlarged view of FIG. 1).
  • the energy ray curable elastic layer 3 is preferably an elastic body after irradiation with energy rays. From this point of view, the energy ray curable elastic layer 3 uses a base material (adhesive) chemically modified with an energy ray reactive functional group, or an energy ray curable compound (or energy ray curable resin). ) Is preferably composed of a composition blended in an elastic base material.
  • the base material examples include natural rubber and synthetic rubber or rubber-based pressure-sensitive adhesives using them, silicone rubber or pressure-sensitive adhesives thereof, (meth) acrylic acid alkyl esters [for example, (meth) acrylic acid methyl ester, ethyl Ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, hexyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, isodecyl ester, C1-20 alkyl ester such as dodecyl ester, etc.] alone or in combination Combined or alkyl (meth) acrylic acid ester and other monomer [for example, monomer containing carboxyl group or acid anhydride group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride; (meth) Acrylic acid 2-H Hydroxyl group-containing monomers such as
  • the energy ray curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 are adhered to each other by using the same or the same kind of component as the pressure-sensitive adhesive constituting the heat-peelable pressure-sensitive adhesive layer 4 described later as the base material.
  • a preferred base material includes an adhesive substance such as an acrylic adhesive.
  • the base material may be composed of one component, or may be composed of two or more components.
  • Examples of the energy ray-reactive functional group used for chemical modification include functional groups having a carbon-carbon multiple bond such as acryloyl group, methacryloyl group, vinyl group, allyl group, and acetylene group. You may use these individually or in combination of 2 or more types. These functional groups can form radicals by cleavage of carbon-carbon multiple bonds upon irradiation with energy rays, and these radicals can form a crosslinking point to form a three-dimensional network structure.
  • the (meth) acryloyl group is preferable from the viewpoints of reactivity and workability, such as being relatively highly reactive to energy rays and being able to be selected and used in combination from various acrylic pressure-sensitive adhesives.
  • a monomer containing a reactive functional group such as a hydroxyl group and / or a carboxyl group for example, (meth) acrylic acid 2 -Reactive functional group-containing acrylic polymer obtained by copolymerizing -hydroxyethyl, (meth) acrylic acid, etc.] with (meth) acrylic acid alkyl ester, a group (isocyanate group) that reacts with the reactive functional group in the molecule.
  • the ratio of the monomer containing a reactive functional group in the reactive functional group-containing acrylic polymer is, for example, 5 to 40% by weight, preferably 10 to 30% by weight, based on the total monomers.
  • the amount of the compound having a group that reacts with the reactive functional group and an energy ray reactive functional group in the molecule is such that when the reactive functional group-containing acrylic polymer is reacted with the reactive functional group-containing acrylic polymer.
  • the amount is, for example, 20 to 100 mol%, preferably 40 to 95 mol%, based on the reactive functional group (hydroxyl group, carboxyl group, etc.) in the coalescence.
  • the reaction including the addition reaction of the reactive functional group in the reactive functional group-containing acrylic polymer with the compound having the reactive functional group in the molecule and the compound having the energy ray reactive functional group and the reactive functional group-containing acrylic polymer is promoted. Therefore, you may mix
  • the energy ray-curable elastic layer 3 for curing the energy ray-curable elastic layer 3 is not particularly limited as long as it can be cured by energy rays such as visible light, ultraviolet rays, and electron beams. It is preferable that the energy beam curable elastic layer 3a is efficiently three-dimensionally reticulated.
  • the energy ray-curable compound can be used alone or in combination of two or more.
  • energy ray-curable compounds include, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, Examples include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, and polyethylene glycol diacrylate.
  • An energy ray curable resin may be used as the energy ray curable compound.
  • the energy ray curable resin include an ester (meth) acrylate having a (meth) acryloyl group at a molecular end, a urethane (meth) acrylate, an epoxy ( Meth) acrylate, melamine (meth) acrylate, acrylic resin (meth) acrylate, thiol-ene addition type resin having an allyl group at the molecular end, photocationic polymerization type resin, cinnamoyl group-containing polymer such as polyvinyl cinnamate, diazotized
  • Examples include amino novolak resins and acrylamide type polymers, photosensitive reactive group-containing polymers, and photosensitive reactive group-containing oligomers.
  • examples of the polymer that reacts with high energy rays include epoxidized polybutadiene, unsaturated polyester, polyglycidyl methacrylate, polyacrylamide, and polyvinylsiloxane.
  • the said base material is not necessarily required.
  • the amount of the energy beam curable compound is, for example, in the range of about 5 to 500 parts by weight, preferably 15 to 300 parts by weight, and more preferably about 20 to 150 parts by weight with respect to 100 parts by weight of the base material.
  • the dynamic elastic modulus of the energy ray curable elastic layer 3 after irradiation with the energy ray is 20 ⁇ 10 6 to 1 ⁇ 10 10 Pa (frequency: 1 Hz, sample: thickness 1. When the thickness is 5 mm, it is possible to achieve both excellent cutting workability and heat peelability.
  • This storage elastic modulus can be adjusted by appropriately selecting the type and blending amount of the energy ray curable compound, the energy ray irradiation conditions, and the like.
  • the energy ray curable elastic layer 3 includes, in addition to the above components, an energy ray polymerization initiator for curing the energy ray curable compound, and a thermal polymerization initiator for obtaining appropriate viscoelasticity before and after the energy ray curing.
  • an appropriate additive such as a crosslinking agent, a tackifier, a vulcanizing agent, a filler, an anti-aging agent, an antioxidant, and a coloring agent can be blended as necessary.
  • the energy beam polymerization initiator a known or commonly used polymerization initiator can be appropriately selected according to the type of energy beam used.
  • a photopolymerization initiator is included for curing.
  • the photopolymerization initiator is not particularly limited, and examples thereof include benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and 2,2-dimethoxy-1,2-diphenylethane-1-one; substituted benzoin ethers such as anisole methyl ether Substituted acetophenones such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexyl-phenylketone; substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone; 2 An aromatic sulfonyl chloride such as naphthalenesulfonyl chloride; a photoactive oxime such as 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime; 2,4,6-trimethylbenzoyl-diphe Le - phosphine oxide, bis (2,4,6-tri
  • the energy ray curable elastic layer 3 is based on, for example, an energy ray curable resin or a coating liquid containing a base material, an energy ray polymerizable compound, an energy ray polymerization initiator, and, if necessary, an additive, a solvent and the like.
  • a method of coating on the material 1 a method of forming the energy ray-curable elastic layer 3 by coating the coating liquid on an appropriate separator (release paper or the like), and transferring (transferring) it onto the substrate 1. It can be formed by a conventional method.
  • a release-treated sheet is placed on a mixture of a urethane polymer and a radical polymerizable monomer coated on a separator.
  • Oxygen may be blocked by placing it, or the substrate may be placed in a container filled with an inert gas to lower the oxygen concentration.
  • the type of energy beam and the type of lamp used by irradiation can be selected as appropriate. Low pressure lamps such as fluorescent chemical lamps, black lights and sterilization lamps, high pressure lamps such as metal halide lamps and high pressure mercury lamps, etc. Can be used.
  • the irradiation amount of ultraviolet rays or the like can be arbitrarily set according to the required characteristics of the energy ray curable elastic layer.
  • the thickness of the energy ray curable elastic layer 3 is selected from the viewpoint of relaxation of unevenness of the thermally expandable microspheres contained in the heat-peelable pressure-sensitive adhesive layer 4, prevention of vibration by a rotary blade when cutting the adherend, and the like. It is about 3 to 150 ⁇ m, preferably 5 to 150 ⁇ m, more preferably about 10 to 150 ⁇ m, more preferably about 15 to 100 ⁇ m.
  • the heat-peelable pressure-sensitive adhesive layer 4 includes an adhesive substance for imparting adhesiveness and thermally expandable microspheres for imparting thermal expandability.
  • the heat-peelable pressure-sensitive adhesive layer 4 is a layer that can be easily peeled off by reducing the bonding area due to foaming of thermally expandable microspheres caused by heat.
  • Thermally expandable microspheres can be used alone or in combination of two or more.
  • the average particle diameter of the thermally expandable microspheres is preferably about 1 ⁇ m to 25 ⁇ m. More preferably, it is 5 ⁇ m to 15 ⁇ m, particularly about 10 ⁇ m.
  • the maximum particle size of the thermally expandable microsphere is larger than this average particle size.
  • the heat-expandable microsphere can be appropriately selected from known heat-expandable microspheres.
  • thermally expandable microspheres heat-expandable microspheres that are not microencapsulated may not be able to stably exhibit good peelability. It can be used suitably.
  • the surface of the heat-peelable pressure-sensitive adhesive layer 4 should be smooth without having irregularities reflecting the shape of the thermally expandable microspheres contained therein. desirable.
  • the adhesive material a material having elasticity that allows foaming and / or expansion of the heat-expandable microspheres during heating and does not restrain them is used. For this reason, a conventionally well-known pressure sensitive adhesive (adhesive) etc. can be used.
  • pressure-sensitive adhesives include rubber-based pressure-sensitive adhesives such as natural rubber and various synthetic rubbers; silicone-based pressure-sensitive adhesives; (meth) acrylic acid alkyl ester and other copolymerizable with this ester Examples thereof include acrylic pressure-sensitive adhesives such as copolymers with unsaturated monomers (for example, acrylic pressure-sensitive adhesives described as the base material of the energy ray-curable elastic layer 3) and the like.
  • an energy ray curable pressure sensitive adhesive can be used for the heat-peelable pressure sensitive adhesive layer 4.
  • the shear elastic modulus of elasticity is 1 ⁇ 10 5 to 5 ⁇ 10 7 Pa (frequency: 1 Hz, sample: thickness) in the temperature range where the dynamic elastic modulus after irradiation with energy rays starts expansion of the thermally expandable microspheres. Good peelability can be obtained when the thickness is 1.5 mm.
  • the thermally expandable microsphere for example, a microsphere in which a substance that expands easily by gasification by heating, such as isobutane, propane, or pentane, is encapsulated in an elastic shell.
  • the shell is usually formed of a thermoplastic material, a hot-melt material, a material that bursts due to thermal expansion, or the like.
  • the substance forming the shell include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
  • Thermally expandable microspheres can be produced by a conventional method such as a coacervation method or an interfacial polymerization method.
  • a commercially available product such as Matsumoto Microsphere (trade name, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) can be used.
  • the average particle diameter of the heat-expandable microspheres is generally about 1 to 80 ⁇ m, preferably about 3 to 50 ⁇ m, from the viewpoint of dispersibility and thin layer formation.
  • the thermally expandable microspheres are not ruptured until the volume expansion coefficient is 5 times or more, particularly 10 times or more in order to efficiently reduce the adhesive strength of the heat-peelable adhesive layer containing the adhesive by heat treatment. What has moderate intensity
  • strength is preferable.
  • the amount of the heat-expandable microspheres varies depending on the type, but for example, 10 to 200 parts by weight, preferably 20 to 125 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive base polymer constituting the heat-peelable pressure-sensitive adhesive layer 4. About parts by weight. If it is less than 10 parts by weight, the effective decrease in the adhesive strength after heat treatment tends to be insufficient, and if it exceeds 200 parts by weight, cohesive failure of the heat-peelable pressure-sensitive adhesive layer 4 or energy ray curable type Interfacial breakage between the elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 tends to occur.
  • the heat-peelable pressure-sensitive adhesive layer 4 includes a crosslinking agent (for example, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent) and a tackifier (for example, a polyfunctional epoxy compound).
  • a crosslinking agent for example, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent
  • a tackifier for example, a polyfunctional epoxy compound.
  • plasticizers for example, pigments, fillers, anti-aging agents, surfactants, antistatic agents, etc. You may mix
  • the heat-peelable pressure-sensitive adhesive layer 4 is formed by directly applying a coating liquid containing pressure-sensitive adhesives, thermally expandable microspheres, and additives, solvents, and the like onto the energy ray-curable elastic layer 3, for example.
  • An appropriate method such as a transfer (transfer) method can be used.
  • This separator 5 is a sheet formed by forming a release agent layer on one side of the base film as necessary, in order to protect the surface layer of the heat-peelable pressure-sensitive adhesive sheet of the present invention and expose it before use. It is also a sheet to be peeled off and a sheet serving as a base when the heat-peelable pressure-sensitive adhesive layer 4 is formed.
  • separator base film known ones can be used, for example, polyetheretherketone, polyetherimide, polyarylate, polyethylene naphthalate, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polychlorinated film.
  • Vinyl film vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, ionomer resin film, ethylene- (meth) acrylic acid copolymer film, ethylene- ( Select from a plastic film such as a (meth) acrylic acid ester copolymer film, a polystyrene film, and a polycarbonate film. Bets are possible.
  • the release agent layer that can be used is a known release agent such as a fluorinated silicone resin release agent, a fluorine resin release agent, a silicone resin release agent, a polyvinyl alcohol resin, a polypropylene resin, a long chain alkyl compound, It is a layer selected and contained according to the resin of the pressure-sensitive adhesive layer.
  • the thickness of the heat-peelable pressure-sensitive adhesive layer 4 can be appropriately determined according to the purpose of use of the pressure-sensitive adhesive sheet or the reduction of the adhesive strength by heating, but is thin in order to improve the workability of the workpiece. Is preferred. For this reason, the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 50 ⁇ m or less, preferably 25 ⁇ m or less, and more preferably 10 ⁇ m or less. If the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 50 ⁇ m or less, the deformation amount of the pressure-sensitive adhesive layer is reduced, and the workability accuracy is improved.
  • the heat-peelable pressure-sensitive adhesive sheet of the present invention can reliably hold the electronic component against this applied force. If the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 50 ⁇ m or less, when processing a workpiece fixed by the heat-peelable pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive layer 4 is adhered by a pressing force by a processing member such as a cutting blade. The deformation amount of the agent layer does not increase, and the position and orientation of the workpiece can be prevented from changing slightly, and as a result, accurate processing can be performed.
  • the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more.
  • the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 1 ⁇ m or more, it has an adhesive force that can sufficiently fix the adherend, and thus can be processed without causing chip jumping at the time of cutting, for example.
  • the separator 5 for example, a base material made of a plastic film or paper whose surface is coated with a release agent typified by a silicone resin, a long-chain alkyl acrylate resin, a fluorine resin, or the like, or nonpolarity such as polyethylene or polypropylene A low-viscosity base material made of a polymer can be used.
  • the separator 5 is used as a temporary support when the heat-peelable pressure-sensitive adhesive layer 4 is pressure-transferred (transferred) onto the energy ray-curable elastic layer 3 as described above. Used as a protective material for protecting the agent layer 4.
  • the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 provided thereon can be formed not only on one side of the substrate 1 but also on both sides.
  • the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 can be sequentially provided on one surface of the substrate 1, and a normal adhesive layer can be provided on the other surface.
  • an adhesive layer is further provided on the heat-peelable pressure-sensitive adhesive layer 4. May be provided.
  • the pressure-sensitive adhesive material of the pressure-sensitive adhesive layer As the pressure-sensitive adhesive material of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive described in the aforementioned heat-peelable pressure-sensitive adhesive layer 4 can be used.
  • the thickness of the pressure-sensitive adhesive layer is preferably 0.1 to 8 ⁇ m, particularly 1 to 5 ⁇ m from the viewpoint of reducing or losing the adhesive force to the adherend, and is formed by a method according to the heat-expandable pressure-sensitive adhesive layer 4. be able to.
  • FIG. 2 is a schematic sectional view showing another example of the heat-peelable pressure-sensitive adhesive sheet of the present invention.
  • an organic coating layer 2 an energy ray curable elastic layer 3, a heat-peelable pressure-sensitive adhesive layer 4, and a separator 5 are laminated in this order on one surface of the base material 1, and the other side of the base material 1.
  • the adhesive layer 6 and the separator 7 are laminated on the surface.
  • This pressure-sensitive adhesive sheet is provided with an adhesive layer 6 and a separator 7 on the surface opposite to the surface on which the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 are formed. It is different from the adhesive sheet of FIG.
  • the adhesive layer 6 contains a sticky substance.
  • the same adhesive substance (adhesive) as in the heat-peelable adhesive layer 4 can be used, and if necessary, a crosslinking agent (for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent). Etc.), tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), plasticizers, fillers, anti-aging agents, surfactants, and other suitable additives Good.
  • a crosslinking agent for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent.
  • Etc. tackifiers
  • plasticizers for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.
  • plasticizers for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.
  • the thickness of the adhesive layer 6 can be appropriately set within a range that does not impair the operability in the pressure bonding of the heat-peelable pressure-sensitive adhesive layer 4 to the adherend, the cutting of the adherend, the peeling of the cut piece, and the recovery. In general, the thickness is about 1 to 50 ⁇ m, preferably about 3 to 30 ⁇ m. Formation of the adhesive layer 6 can be performed by a method according to the heat-peelable pressure-sensitive adhesive layer 4. As the separator 7, the same separator as the separator 5 on the heat-peelable pressure-sensitive adhesive layer 4 can be used. Such an adhesive sheet can be used by being fixed to the pedestal surface by using the adhesive layer 6.
  • the organic coating layer 2 is provided on one side or both sides of the substrate 1, and the composition before curing constituting the energy ray curable elastic layer 3 is uniformly applied thereon by any means. And when said energy ray hardening-type elastic layer 3 formed in the single side
  • the heat-peelable pressure-sensitive adhesive layer 4 formed on the separator is laminated on the surface of the energy ray-curable elastic layer 3 before curing so that the surface on which the convex portions are formed is aligned.
  • the energy beam curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 are pressed against each other from the base material and the separator side, so that the energy beam curable elastic layer 3 is not cured.
  • the convex portion is embedded.
  • a sheet obtained by laminating the base material 1, the organic coating layer 2, the uncured energy ray curable elastic layer 3, the heat-peelable pressure-sensitive adhesive layer 4 and the separator in this order can be obtained. .
  • the uncured energy ray curable elastic layer 3 is cured by irradiating the uncured energy ray curable elastic layer 3 with energy rays from the substrate 1 side and / or the separator side.
  • the heat-peelable pressure-sensitive adhesive sheet of the present invention can be obtained.
  • the method for producing the heat-peelable pressure-sensitive adhesive sheet is a method in which the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 are provided on one surface of the substrate 1.
  • this method may be sequentially performed on each side of the substrate, or may be performed on both sides of the substrate at the same time.
  • an adhesive layer is provided on the other surface of the substrate 1, the adhesive layer is formed at any stage before or after the step of providing the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4. May be.
  • FIG. 3 is a schematic process diagram showing an example of a method for producing a cut piece using the heat-peelable pressure-sensitive adhesive sheet of the present invention. More specifically, FIG. 3 shows an adherend (cut object) on the surface of the heat-peelable pressure-sensitive adhesive layer 4 of the energy ray-curable heat-peelable pressure-sensitive adhesive sheet (with the separator 5 peeled off) in FIG. 8 is bonded by pressure bonding, and in some cases, the energy ray curable elastic layer 3 is cured by irradiation with an energy ray 9, and then cut into a predetermined size along the cutting line 10, and then heated by heat treatment.
  • adherend cut object
  • 1 is a base material
  • 3a is a cured energy beam-curable elastic layer after irradiation with energy rays
  • 4a is a heat-peelable pressure-sensitive adhesive after expansion of heat-expandable microspheres by heating after irradiation with energy beams. Indicates the layer.
  • the pressure-bonding between the heat-peelable pressure-sensitive adhesive layer 4 of the energy ray-curable heat-peelable pressure-sensitive adhesive sheet 4 and the adherend 8 is performed by, for example, a method of pressure-bonding with an appropriate pressing means such as a rubber roller, a laminate roll, or a press device. be able to.
  • an appropriate pressing means such as a rubber roller, a laminate roll, or a press device.
  • Visible light, ultraviolet rays, electron beams, etc. can be used as the energy rays 9.
  • Irradiation of the energy beam 9 can be performed by an appropriate method.
  • the heat-expandable microspheres may start to expand due to the heat of irradiation of the energy beam 9, the heat-expandable microspheres are limited to irradiation for as short a time as possible, or the heat-peelable adhesive sheet is air-cooled. It is desirable to maintain a temperature at which the sphere does not begin to expand.
  • the adherend 8 can be cut by conventional cutting means such as dicing.
  • a cutting line 10 is formed as shown by a cutting line 10 in FIG.
  • the heating conditions can be appropriately set depending on the surface state of the adherend 8 (or the cut piece 8a), the heat resistance, the type of thermally expandable microsphere, the heat resistance of the adhesive sheet, the heat capacity of the adherend (cut object), and the like.
  • general conditions are a temperature of 350 ° C. or less and a treatment time of 30 minutes or less, and a temperature of 80 to 200 ° C. and a treatment time of about 1 second to 15 minutes are particularly preferable.
  • a heating system although a hot-air heating system, a hot plate contact system, an infrared heating system, etc. are mentioned, it is not specifically limited.
  • the stretching process is performed, for example, by using a conventional stretching means used when stretching the sheets two-dimensionally. Can do.
  • the heat-peelable pressure-sensitive adhesive sheet of the present invention has the heat-peelable pressure-sensitive adhesive layer 4 containing an adhesive substance (pressure-sensitive adhesive), the adherend 8 can be firmly adhered and held, for example, by vibration during transportation. Body 8 does not peel off. Further, the heat-peelable pressure-sensitive adhesive layer 4 can be formed thin, and the energy ray-curable elastic layer 3 is cured by irradiating energy rays before the cutting step. Chipping and the like accompanying the roll-up of the layer and the shaking of the adhesive layer can be cut to a predetermined size while being greatly reduced as compared with the conventional heat-expandable pressure-sensitive adhesive sheet.
  • an adhesive substance pressure-sensitive adhesive
  • the heat-peelable pressure-sensitive adhesive layer 4 includes thermally expandable microspheres and has thermal expandability, the heat expandable microspheres are rapidly foamed or expanded as a result of the heat treatment after the cutting step. As shown in the figure on the right, the heat-peelable pressure-sensitive adhesive layer 4 changes in volume to form an uneven three-dimensional structure on the surface, and the adhesion area with the cut piece 8a and thus the adhesive strength is greatly reduced. Or lost.
  • operability and work in the cutting process of the adherend 8, the separation of the cut piece 8 a, and the recovery process due to the curing of the energy beam curable elastic layer 3 by the irradiation of the energy beam and the significant decrease or loss of the adhesive strength by the heat treatment The productivity is greatly improved and the production efficiency can be greatly improved.
  • the energy ray curable heat-peelable pressure-sensitive adhesive sheet of the present invention can be used for applications in which the adherend is permanently bonded, but after adhering the adherend for a predetermined period and achieving the bonding purpose, the adhesion is performed. Suitable for applications where it is desired or desired to release the state.
  • carrier tapes for temporarily transporting parts in addition to fixing materials for semiconductor wafers and ceramic laminated sheets, carrier tapes for temporarily transporting parts, temporarily fixing carrier tapes for assembly of various electrical devices, electronic devices, display devices, etc. Examples thereof include a surface protective material or a masking material for the purpose of preventing contamination damage such as a material or a fixing material, a metal plate, a plastic plate, and a glass plate.
  • it can be suitably used for manufacturing processes such as small or thin semiconductor chips and multilayer capacitor chips.
  • PET film was prepared as a substrate.
  • Toray Industries, Inc. single-sided corona-treated, Lumirror S105 (thickness 50 ⁇ m) was used as this PET film.
  • an organic coating layer was applied with a gravure coater so as to have a dry film thickness of 1 to 2 ⁇ m and dried to obtain a substrate 1 with an organic coating layer.
  • a light blue printing ink NB300 (Daiichi Seika Co., Ltd.) was used for this organic coating layer.
  • NB300 contained a polyurethane-based vinyl acetate-vinyl chloride copolymer as a binder resin, and an intensity peak considered to be urethane was confirmed by IR.
  • Substrate 2 with Organic Coating Layer A PET film was prepared as a substrate. Toray Industries, Inc., single-sided corona-treated, Lumirror S105 (thickness 50 ⁇ m) was used as this PET film. On the corona surface treatment side of this substrate, an organic coating layer was applied with a gravure coater so as to have a dry film thickness of 1 to 2 ⁇ m and dried to obtain a substrate 2 with an organic coating layer. For this organic coating layer, printing ink NB300 (Daiichi Seika Co., Ltd.) containing no light blue pigment was used. NB300 contained a polyurethane-based vinyl acetate-vinyl chloride copolymer as a binder resin, and an intensity peak considered to be urethane was confirmed by IR.
  • Toray Industries, Inc. single-sided corona-treated, Lumirror S105 (thickness 50 ⁇ m) was used as this PET film.
  • an organic coating layer was applied with a gravure coater so as
  • PET film was prepared as a base material.
  • Toray Industries, Inc. single-sided corona-treated, Lumirror S105 (thickness 50 ⁇ m) was used as this PET film.
  • an organic coating layer was applied with a gravure coater so as to have a dry film thickness of 1 to 2 ⁇ m and dried to obtain a substrate 3 with an organic coating layer.
  • an ethyl acetate solution of 71 parts by weight of Adekabon titer U500 (manufactured by ADEKA) as a polyurethane primer and 28 parts by weight of coronate HL (manufactured by Nippon Polyurethane Industry) as an isocyanate resin was used.
  • urethane polymer-acrylic monomer mixture was obtained.
  • the obtained urethane polymer-acrylic monomer mixture was applied onto a 38 ⁇ m thick polyethylene terephthalate film (trade name: S-10, manufactured by Toray Industries, Inc.) so that the thickness after curing was 3 to 4 ⁇ m.
  • a PET film (thickness: 38 ⁇ m) that has been peeled is coated on top of this, and the coated PET film surface is irradiated with ultraviolet rays (illuminance: 163 mW / cm 2 , light amount: 2100 mJ / cm 2 ) using a high-pressure mercury lamp. And cured to obtain a polyethylene terephthalate / acrylic urethane laminate sheet.
  • PET film was prepared as a base material.
  • Toray Industries, Inc. single-sided corona-treated, Lumirror S105 (thickness 38 ⁇ m) was used as this PET film.
  • the organic coating layer was applied with a gravure coater so that the dry film thickness was 1 to 2 ⁇ m and dried to obtain a substrate 5 with an organic coating layer.
  • blue printing ink CVL-PR (manufactured by DIC Graphics) was used.
  • CVL-PR contains a hydroxyl group-containing vinyl acetate-vinyl chloride copolymer as a binder resin, and IR did not confirm an intensity peak considered to be urethane.
  • PET film was prepared as a substrate.
  • Toray Industries, Inc. single-sided corona-treated, Lumirror S105 (thickness 50 ⁇ m) was used as this PET film.
  • an organic coating layer was applied with a gravure coater so as to have a dry film thickness of 1 to 2 ⁇ m and dried to obtain a substrate 6 with an organic coating layer.
  • an amorphous saturated copolymerized polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) was used.
  • the resulting acrylic polymer is subjected to an addition reaction with respect to 50 parts by weight of 2-hydroxyethyl acrylate-derived hydroxyl group methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate) and 100 parts by weight of the acrylic polymer. 0.03 part by weight of catalyst dibutyltin dilaurate was blended and reacted in an air atmosphere at 50 ° C. for 24 hours to produce an acrylic polymer having a methacrylate group in the side chain.
  • trifunctional acrylic photopolymerizable monomer trimethylolpropane triacrylate (trade name: Aronics M320, manufactured by Toagosei Co., Ltd.)
  • radical light based on 100 parts by weight of the obtained acrylic polymer 1 part by weight of a polymerization initiator (Irgacure 651,2,2-dimethoxy-1,2-diphenylethane-1-one, manufactured by Ciba Geigy), isocyanate compound (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) 1 Part by weight was added to obtain a mixture.
  • a polymerization initiator Irgacure 651,2,2-dimethoxy-1,2-diphenylethane-1-one, manufactured by Ciba Geigy
  • isocyanate compound trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.
  • the obtained mixture was applied to a release-treated surface of a release-treated PET film MRF38 (manufactured by Mitsubishi Polyester) using a die coater so that the dry film thickness was 30 ⁇ m.
  • the peel-treated PET film MRF38 was used as a separator.
  • Example 1 The energy ray-curable pressure-sensitive adhesive layer was bonded to the organic coating layer side of the substrate 1 with an organic coating layer, and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet.
  • Example 2 The energy ray-curable pressure-sensitive adhesive layer was bonded to the organic coating layer side of the substrate 2 with an organic coating layer, and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet.
  • Example 3 The energy ray-curable pressure-sensitive adhesive layer was bonded to the organic coating layer side of the substrate 3 with an organic coating layer, and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet.
  • Example 4 The energy ray-curable pressure-sensitive adhesive layer was bonded to the organic coating layer side of the base material 4 with the organic coating layer, and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet.
  • Comparative Example 1 The energy ray-curable pressure-sensitive adhesive layer was bonded to Toray Co., Ltd. PET film, Lumirror S10 (thickness 50 ⁇ m), and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet. Comparative Example 2 The energy ray-curable pressure-sensitive adhesive layer was bonded to Toray Co., Ltd., single-sided corona-treated, Lumirror S105 (thickness 50 ⁇ m), and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet.
  • Reference example 1 The energy ray-curable pressure-sensitive adhesive layer was bonded to the organic coating layer side of the substrate 5 with an organic coating layer, and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet.
  • Reference example 2 The energy ray-curable pressure-sensitive adhesive layer was bonded to the organic coating layer side of the substrate 6 with an organic coating layer, and then the heat-peelable pressure-sensitive adhesive layer was bonded to prepare a heat-peelable pressure-sensitive adhesive sheet.
  • the obtained heat-peelable pressure-sensitive adhesive sheet was irradiated with ultraviolet rays of 300 mJ / cm 2 using a UV irradiation machine NEL UM810 (high pressure mercury lamp light source, 20 mW / cm 2 ) manufactured by Nitto Seiki Co., Ltd. Was cured.
  • NEL UM810 high pressure mercury lamp light source, 20 mW / cm 2
  • the ceramic sheet before firing of 120 mm ⁇ 100 mm ⁇ thickness 0.5 mm was pasted on the pressure-sensitive adhesive surface of the heat-peelable pressure-sensitive adhesive sheet, and full cut into 0.4 mm ⁇ 0.2 mm chips. Thereafter, heat treatment was performed on a hot plate at 120 ° C. for 3 minutes, and after cooling, the chip was recovered by inversion vibration.
  • Cutting accuracy The following method was adopted to obtain the cutting accuracy.
  • the cross section of the chip after cutting was observed with an optical microscope, the angle of the cross section with respect to the ceramic sheet surface was determined, and this was defined as the cutting accuracy. This means that the closer to 90 °, the better the cutting accuracy.
  • the improvement is greatly improved.
  • both the heat-peelability and the adhesive peel-off were poor.
  • the result of adhesive peeling is good, it can be seen that the cutting accuracy is low, and the workability when the fixed ceramic sheet is fully cut is deteriorated.
  • the heat-peelable pressure-sensitive adhesive sheets of Reference Examples 1 and 2 are examples in which a layer made of a material other than a urethane polymer is used as the organic coating layer, but both heat-peelability and adhesive peeling are poor as in Comparative Examples 1 and 2. Met.

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PCT/JP2012/073983 2011-09-20 2012-09-20 電子部品切断用加熱剥離型粘着シート及び電子部品切断方法 WO2013042698A1 (ja)

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JP2019199561A (ja) * 2018-05-17 2019-11-21 日東電工株式会社 粘着シート
WO2020196757A1 (ja) * 2019-03-28 2020-10-01 リンテック株式会社 粘着シート、粘着シートの製造方法及び半導体装置の製造方法
WO2020196758A1 (ja) * 2019-03-28 2020-10-01 リンテック株式会社 粘着シート、粘着シートの製造方法及び半導体装置の製造方法
WO2020196755A1 (ja) * 2019-03-28 2020-10-01 リンテック株式会社 粘着シート、粘着シートの製造方法及び半導体装置の製造方法
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