WO2023021773A1 - Feuille autocollante - Google Patents

Feuille autocollante Download PDF

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Publication number
WO2023021773A1
WO2023021773A1 PCT/JP2022/013629 JP2022013629W WO2023021773A1 WO 2023021773 A1 WO2023021773 A1 WO 2023021773A1 JP 2022013629 W JP2022013629 W JP 2022013629W WO 2023021773 A1 WO2023021773 A1 WO 2023021773A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
meth
adhesive layer
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Ceased
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PCT/JP2022/013629
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English (en)
Japanese (ja)
Inventor
高正 平山
昭徳 西尾
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to CN202280056450.5A priority Critical patent/CN117858930A/zh
Priority to JP2023542212A priority patent/JP7744994B2/ja
Priority to KR1020237044237A priority patent/KR102930766B1/ko
Publication of WO2023021773A1 publication Critical patent/WO2023021773A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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

Definitions

  • the present invention relates to an adhesive sheet. More particularly, it relates to a pressure-sensitive adhesive sheet that can exhibit easy peelability in response to thermal stimulation.
  • an adhesive sheet is used as a temporary fixing material for cutting semiconductor wafers or ceramic sheets, or as a temporary fixing material in the process of sealing a semiconductor chip with resin (chip size package: CSP or wafer level package: WLP).
  • An adhesive sheet may be used.
  • a pressure-sensitive adhesive sheet that has an adhesive layer containing heat-expandable microspheres and whose adhesive strength is reduced by expansion of the heat-expandable microspheres by heating has been studied.
  • the above adhesive sheet usually comprises an adhesive layer formed by coating (applying and drying) an adhesive containing a base polymer and a solvent.
  • aromatic hydrocarbon solvents such as toluene and dichlorobenzene are often used as the solvent.
  • An aromatic hydrocarbon solvent has excellent solubility and a high boiling point, and is therefore advantageous in that a pressure-sensitive adhesive having excellent storage stability can be obtained by using it.
  • non-aromatic hydrocarbon solvents having a boiling point of less than 100° C., such as acetone, methyl ethyl ketone, and ethyl acetate.
  • an adhesive containing a non-aromatic hydrocarbon solvent with a boiling point of less than 100°C is used to form an adhesive layer, an adhesive layer that does not exhibit sufficient adhesive strength may be formed. Even if it contains a base polymer that can achieve sufficient adhesive strength when combined with an aromatic hydrocarbon solvent, it contains the above non-aromatic hydrocarbon solvent instead of the aromatic hydrocarbon solvent. , a PSA sheet that does not have sufficient adhesive strength may be obtained.
  • the present invention has been made to solve the above-mentioned conventional problems, and the object thereof is to provide a pressure-sensitive adhesive layer that consumes less heat energy when forming the pressure-sensitive adhesive layer and that can exhibit excellent adhesive strength.
  • a pressure-sensitive adhesive sheet comprising
  • the pressure-sensitive adhesive sheet of the present invention comprises a base material and a pressure-sensitive adhesive layer disposed on at least one side of the base material, the pressure-sensitive adhesive layer comprising a (meth)acrylic polymer as a base polymer and a cross-linking agent.
  • a (meth)acrylic polymer as a base polymer and a cross-linking agent.
  • an isocyanate-based cross-linking agent and/or an epoxy-based cross-linking agent and an amino compound having a tertiary amino group capable of multidentate coordination as a low-molecular-weight compound and/or an organic tin (IV) compound capable of multidentate coordination , and heat-expandable microspheres
  • the (meth)acrylic polymer contains a structural unit having an active hydrogen group.
  • the content of the amino compound having a tertiary amino group capable of multidentate coordination and the organotin (IV) compound capable of multidentate coordination is relative to 100 parts by weight of the base polymer. , 0.001 to 10 parts by weight.
  • the amino compound having a tertiary amino group capable of multidentate coordination is an amino compound containing at least two tertiary amino groups in the molecule.
  • the amino compound having a tertiary amino group capable of multidentate coordination is 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0 ]undec-7-ene and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.
  • the organotin(IV) compounds capable of multidentate coordination are dialkyltin(IV) fatty acid esters.
  • the organotin(IV) compound capable of multidentate coordination consists of dibutyltin(IV) dilaurate, dibutyltin(IV) dioctate, dioctyltin(IV) dilaurate and dibutyltin(IV) diacetate. At least one selected from the group.
  • the active hydrogen group is a hydroxyl group and/or a carboxyl group.
  • the thermally expandable microspheres have an expansion temperature of 80°C to 250°C.
  • another pressure-sensitive adhesive layer is further provided on the opposite side of the base material to the pressure-sensitive adhesive layer. According to another aspect of the present invention, there is provided a method for producing the pressure-sensitive adhesive sheet.
  • This adhesive sheet manufacturing method includes forming an adhesive coating layer by applying an adhesive to a substrate, and forming an adhesive layer by drying the adhesive coating layer.
  • the product of drying temperature and drying time when drying the pressure-sensitive adhesive coating layer is 100° C. ⁇ min to 500° C. ⁇ min.
  • the pressure-sensitive adhesive contains a solvent, and the boiling point of the solvent is less than 100°C.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer that consumes less heat energy when forming the pressure-sensitive adhesive layer and that can exhibit excellent adhesive strength.
  • FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention.
  • the adhesive sheet 100 includes a substrate 10 and an adhesive layer 20 arranged on at least one side of the substrate 10 .
  • the pressure-sensitive adhesive layer comprises a (meth)acrylic polymer as a base polymer, an isocyanate-based cross-linking agent and/or an epoxy-based cross-linking agent as a cross-linking agent, and a tertiary amino group capable of multidentate coordination as a low-molecular-weight compound. and/or an organotin (IV) compound capable of multidentate coordination (hereinafter also referred to as a multidentate tin (IV) compound), and heat-expandable microspheres including.
  • (meth)acryl means acryl and/or methacryl.
  • the thermally expandable microspheres can expand at a predetermined temperature.
  • the heat-expandable microspheres are foamed by heating, resulting in irregularities on the pressure-sensitive adhesive surface (that is, the surface of the pressure-sensitive adhesive layer), and the adhesive strength is reduced or lost.
  • the pressure-sensitive adhesive sheet of the present invention is used as a sheet for temporarily fixing a workpiece during processing of an electronic component (e.g., printed circuit board), the workpiece is subjected to a predetermined process (e.g., dicing, sealing, etc.). ), the adhesiveness necessary for temporary fixing is exhibited, and when the work piece is peeled off from the adhesive sheet after processing, the adhesive strength is reduced or lost by heating, and good peelability is exhibited. be.
  • a pressure-sensitive adhesive layer having excellent adhesive strength can be formed by including the low-molecular-weight compound.
  • the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the present invention can be formed using a solvent having a low boiling point (e.g., less than 100°C, preferably 80°C or less, more preferably 60°C or less). It has excellent adhesive strength even if it is formed using According to the present invention, by using the above-described low-molecular-weight compound, even if the thermal energy applied during the formation of the pressure-sensitive adhesive layer (typically, the thermal energy when volatilizing the solvent from the pressure-sensitive adhesive) is small, the base polymer can be crosslinked. proceeds favorably, and as a result, a pressure-sensitive adhesive layer having high cohesion and excellent adhesiveness is obtained.
  • an adhesive layer with less thermal energy consumption by using a low boiling point solvent as described above.
  • a sheet can be provided. It is also possible to use thermally expandable microspheres with a low foaming initiation temperature. Furthermore, it is also possible to provide a pressure-sensitive adhesive sheet in which deterioration of the heat-expandable microspheres is suppressed by heat, and the adhesive sheet is excellent in peelability.
  • the adhesive strength at 23° C. when the adhesive layer of the adhesive sheet is attached to polyethylene terephthalate is preferably 0.5 N/20 mm or more, more preferably 1 N/20 mm to 20 N/20 mm, and still more preferably It is 2 N/20 mm to 20 N/20 mm, more preferably 4 N/20 mm to 20 N/mm. Within such a range, for example, it is possible to obtain a pressure-sensitive adhesive sheet that is useful as a temporary fixing sheet used in the manufacture of electronic components.
  • the adhesive strength is the adhesive strength in a state where the adhesive strength is not reduced due to the expansion of the heat-expandable microspheres, and means the adhesive strength in the state where the heat history of 40° C. or more has not been passed.
  • adhesive strength refers to adhesive strength measured by a method according to JIS Z 0237:2009 (bonding conditions: one reciprocation of a 2 kg roller, peeling speed (tensile speed): 300 mm/min, peeling angle of 180°).
  • the adhesive strength when the adhesive layer of the adhesive sheet is attached to polyethylene terephthalate is reduced to 0.3 N/20 mm or less (preferably 0.2 N/20 mm or less, more preferably 0.1 N/20 mm) by heating. preferably lower.
  • the heating temperature is preferably 70°C to 300°C, more preferably 100°C to 280°C.
  • the adhesive sheet may further include any other appropriate layer.
  • the pressure-sensitive adhesive sheet further comprises an undercoat layer arranged between the pressure-sensitive adhesive layer and the substrate. If the undercoat layer is provided, it is possible to obtain a pressure-sensitive adhesive sheet having excellent conformability to adherends. When the pressure-sensitive adhesive layer containing heat-expandable microspheres is heated, the heat-expandable microspheres expand and deform due to the expansion of the heat-expandable microspheres. Therefore, peelability is improved.
  • another adhesive layer may be provided on the opposite side of the substrate from the adhesive layer. of pressure-sensitive adhesive layers in this order.
  • the thickness of the adhesive sheet is preferably 3 ⁇ m to 300 ⁇ m, more preferably 5 ⁇ m to 150 ⁇ m, and even more preferably 10 ⁇ m to 100 ⁇ m.
  • the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed from an acrylic pressure-sensitive adhesive, that is, contains a (meth)acrylic polymer as a base polymer as described above.
  • the (meth)acrylic polymer may be a polymer (homopolymer or copolymer) using one or more of (meth)acrylic acid alkyl esters as monomer components.
  • the content of the (meth)acrylic polymer is preferably 70 parts by weight or more, more preferably 90 parts by weight or more, and still more preferably 95 parts by weight or more with respect to 100 parts by weight of the polymer in the pressure-sensitive adhesive layer. and particularly preferably 100 parts by weight.
  • (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, ( isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid Octyl, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic undecyl acid, dodecyl (meth)acrylate,
  • (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 4 to 20 carbon atoms (more preferably 6 to 20, particularly preferably 8 to 18 carbon atoms) are more preferable.
  • the (meth)acrylic polymer contains a structural unit having an active hydrogen group.
  • a (meth)acrylic polymer containing a structural unit having an active hydrogen group can be preferably crosslinked during formation, and by using such a polymer, a pressure-sensitive adhesive layer with excellent adhesiveness can be formed at a relatively low temperature. can be done.
  • active hydrogen groups include hydroxyl groups (alcoholic hydroxyl groups, phenolic hydroxyl groups), carboxyl groups, amino groups, and the like. A hydroxyl group and/or a carboxyl group are particularly preferred.
  • the number of active hydrogen groups contained in the (meth)acrylic polymer may be one, or two or more.
  • Structural units having an active hydrogen group include, for example, structural units derived from carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; ) hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, (meth)acrylic structural units derived from hydroxyl group-containing monomers such as hydroxyl lauryl acid and (4-hydroxymethylcyclohexyl)methyl methacrylate;
  • carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid,
  • the content of the structural unit derived from the monomer having an active hydrogen group is preferably 0.1% by weight to 40% by weight, more preferably 0.5% by weight, based on the total structural units constituting the acrylic polymer. % to 30% by weight, particularly preferably 1% to 20% by weight.
  • the acrylic polymer may optionally be a unit corresponding to another monomer component copolymerizable with the (meth)acrylic acid alkyl ester.
  • monomer components include acid anhydride monomers such as maleic anhydride and itaconic anhydride; styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, Sulfonic acid group-containing monomers such as acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-butyl (meth)acrylamide , N-methylol (meth) acrylamide, N-methylolpropane (meth) (N-substituted)
  • Epoxy group-containing acrylic monomers polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methyl (meth) acrylate
  • Glycol-based acrylic ester monomers such as methoxyethylene glycol and methoxypolypropylene glycol (meth)acrylate
  • heterocycles such as tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, and silicone (meth)acrylate, halogen atoms, and silicon atoms
  • Polyfunctional monomers such as di(meth)acrylate, trimethylolpropane tri(meth)acrylate
  • the acrylic pressure-sensitive adhesive may contain any suitable additive as necessary.
  • the additives include, for example, tackifiers, plasticizers (e.g., trimellitic ester plasticizers, pyromellitic ester plasticizers, etc.), pigments, dyes, fillers, anti-aging agents, conductive materials, and electrification agents. Examples include inhibitors, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, and the like.
  • tackifier is used as the tackifier contained in the acrylic pressure-sensitive adhesive.
  • a tackifier resin is used.
  • the tackifying resin include rosin-based tackifying resins (e.g., unmodified rosin, modified rosin, rosin phenol-based resin, rosin ester-based resin, etc.), terpene-based tackifying resins (e.g., terpene-based resin, terpene phenolic resin, styrene-modified terpene-based resin, aromatic-modified terpene-based resin, hydrogenated terpene-based resin), hydrocarbon-based tackifying resin (e.g., aliphatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, aromatic Hydrocarbon resins (e.g., styrene resins, xylene resins, etc.), aliphatic/aromatic petroleum resins, aliphatic hydrocarbon resins, alipha
  • rosin-based tackifying resins terpene-based tackifying resins, and hydrocarbon-based tackifying resins (styrene-based resins, etc.) are preferred.
  • a tackifier may be used alone or in combination of two or more.
  • the amount of the tackifier added is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, relative to 100 parts by weight of the base polymer.
  • the pressure-sensitive adhesive layer contains a cross-linking agent.
  • a cross-linking agent an isocyanate-based cross-linking agent and/or an epoxy-based cross-linking agent is used. By using such a cross-linking agent, a pressure-sensitive adhesive layer with excellent adhesiveness can be formed at a relatively low temperature.
  • the isocyanate-based cross-linking agent is a compound having an isocyanate group, and specific examples thereof include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; Cyclic isocyanates; aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate and xylylene diisocyanate; trade name "Coronate L”), trimethylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL”), isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate adducts such as the product name "Coronate HX";
  • the epoxy-based cross-linking agent is a compound having an epoxy group.
  • N-glycidylaminomethyl)cyclohexane manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C”
  • 1,6-hexanediol diglycidyl ether manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 1600”
  • neopentyl glycol diglycidyl Ether manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 1500NP
  • ethylene glycol diglycidyl ether manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 40E
  • propylene glycol diglycidyl ether manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 70P”
  • polyethylene glycol diglycidyl ether manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 70P”
  • the content of the epoxy-based cross-linking agent can be set to any appropriate amount depending on the desired adhesive strength. Typically, it is 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight.
  • the pressure-sensitive adhesive layer is an amino compound having a tertiary amino group capable of multidentate coordination as a low-molecular compound (also referred to as a multidentate amino compound) and/or capable of multidentate coordination.
  • organotin(IV) compounds also referred to as multidentate tin(IV) compounds.
  • a low-molecular-weight compound is a compound that can function as a catalyst in the cross-linking reaction of the base polymer during the formation of the pressure-sensitive adhesive layer.
  • the active hydrogen group in the base polymer and the functional group (isocyanate group or epoxy group) of the cross-linking agent can be coordinated to a single molecule at the same time.
  • a pressure-sensitive adhesive layer having excellent adhesiveness can be formed at a relatively low temperature.
  • an amino compound containing at least two tertiary amino groups in the molecule is used as the polydentate amino compound.
  • polydentate amino compounds include 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7- and triazabicyclo[4.4.0]dec-5-ene. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Among them, 1,4-diazabicyclo[2.2.2]octane is preferably used as the polydentate amino compound.
  • 1,4-Diazabicyclo[2.2.2]octane is liquid at room temperature and has a high boiling point, so it is easy to disperse in the adhesive, and it is difficult to volatilize during the heating process (for example, the drying process of the adhesive coating layer).
  • a (meth)acrylic polymer having an alcoholic hydroxyl group that is, a (meth)acrylic polymer containing a structural unit derived from a monomer having an alcoholic hydroxyl group
  • a polydentate amino compound used. This is because the alcoholic hydroxyl group has a low ability to dissociate active hydrogen.
  • polydentate tin (IV) compounds include dialkyltin (IV) fatty acid esters such as dibutyltin (IV) dilaurate, dibutyltin (IV) dioctate, dioctyltin (IV) dilaurate, and dibutyltin (IV) diacetate; Distannoxane such as -n-butyl-1,3-diacetoxy-distannoxane and tetra-n-butyl-1,3-dichloro-distannoxane. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • dioctyltin (IV) diacetate is preferably used as the polydentate tin (IV) compound.
  • Dioctyltin (IV) diacetate is liquid at room temperature and has a high boiling point, so it is easy to disperse in the adhesive, and is advantageous in that it is difficult to volatilize during the heating process (for example, the process of drying the adhesive coating layer). It is also advantageous in that it has very poor reactivity to heat-expandable microspheres.
  • a (meth)acrylic polymer having a carboxyl group and/or a phenolic hydroxyl group that is, a monomer-derived structural unit having a carboxyl group and/or a monomer having a phenolic hydroxyl group.
  • a (meth)acrylic polymer) and a polydentate tin (IV) compound are used in combination. This is because a carboxyl group or a phenolic hydroxyl group has high hydrogen dissociation ability, and may strongly bond with a polydentate amino compound to terminate the cross-linking reaction.
  • the content of the amino compound having a tertiary amino group capable of multidentate coordination and the organotin (IV) compound capable of multidentate coordination is preferably 0.001 wt. parts to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and even more preferably 0.05 to 3 parts by weight. Within such a range, a pressure-sensitive adhesive layer having excellent adhesiveness can be formed at a relatively low temperature. If the content of the polydentate amino compound and the polydentate tin (IV) compound is too high, complex formation (pseudo-crosslinking) may occur between these low-molecular-weight compounds and the cross-linking agent, and the desired adhesive strength may not be obtained. .
  • the content of the amino compound having a tertiary amino group capable of multidentate coordination and the organotin (IV) compound capable of multidentate coordination refers to the polydentate amino compound and the polydentate It is the total amount of stannous (IV) compounds. Therefore, when the pressure-sensitive adhesive layer does not contain a multidentate tin (IV) compound, "containing an amino compound having a tertiary amino group capable of multidentate coordination and an organic tin (IV) compound capable of multidentate coordination “Amount” is the content of the polydentate amino compound.
  • the pressure-sensitive adhesive layer does not contain a polydentate amino compound
  • content of an amino compound having a tertiary amino group capable of polydentate coordination and an organotin (IV) compound capable of polydentate coordination is the content of polydentate tin(IV) compounds.
  • the boiling point of the low molecular compound is preferably 100°C or higher, more preferably 120°C or higher, and even more preferably 150°C or higher.
  • a low-molecular-weight compound with a boiling point in this range is liquid at room temperature and has a high boiling point, so it is easy to disperse in the adhesive, and it is advantageous in that it is difficult to volatilize during the heating process (for example, the process of drying the adhesive coating layer). .
  • thermally expandable microspheres any appropriate thermally expandable microspheres can be used as long as they are microspheres that can be expanded or foamed by heating.
  • heat-expandable microspheres for example, microspheres in which a substance that easily expands by heating is encapsulated in an elastic shell can be used.
  • heat-expandable microspheres can be produced by any appropriate method such as coacervation, interfacial polymerization, and the like.
  • Substances that easily expand when heated include, for example, propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, normal hexane, isohexane, heptane, octane, petroleum ether, methane halides, and tetraalkylsilanes.
  • low boiling point liquid such as; azodicarbonamide gasified by thermal decomposition; and the like.
  • substances constituting the shell include nitrile monomers such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethoxyacrylonitrile, and fumaronitrile; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, Carboxylic acid monomers such as citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (Meth)acrylic acid esters such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, ⁇ -carboxyethyl acrylate; styrene monomers such as styrene, ⁇ -methyl
  • copolymer examples include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, acrylonitrile-methacrylonitrile-itaconic acid copolymer, A polymer etc. are mentioned.
  • An inorganic foaming agent or an organic foaming agent may be used as the thermally expandable microspheres.
  • inorganic foaming agents include ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, and various azides.
  • organic foaming agents include chlorofluoroalkane compounds such as trichloromonofluoromethane and dichloromonofluoromethane; and azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate.
  • hydrazine compounds such as paratoluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonyl hydrazide, 4,4′-oxybis(benzenesulfonyl hydrazide), allylbis(sulfonyl hydrazide); p-toluylenesulfonyl semicarbazide, 4, Semicarbazide compounds such as 4'-oxybis(benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; N,N'-dinitrosopentamethylenetetramine, N,N' -dimethyl-N,N'-dinitrosoterephthalamide; and other N-nitroso compounds.
  • the particle size of the heat-expandable microspheres before heating is preferably 0.5 ⁇ m to 80 ⁇ m, more preferably 5 ⁇ m to 45 ⁇ m, even more preferably 10 ⁇ m to 20 ⁇ m, and particularly preferably 10 ⁇ m to 15 ⁇ m. . Therefore, the average particle size of the heat-expandable microspheres before heating is preferably 6 ⁇ m to 45 ⁇ m, more preferably 15 ⁇ m to 35 ⁇ m.
  • the above particle size and average particle size are values determined by a particle size distribution measurement method in a laser scattering method.
  • the thermally expandable microspheres have an appropriate strength such that they do not burst until the volume expansion coefficient is preferably 5 times or more, more preferably 7 times or more, and still more preferably 10 times or more.
  • the adhesive strength can be efficiently reduced by heat treatment.
  • the expansion start temperature of the heat-expandable microspheres is preferably 80°C to 250°C, more preferably 80°C to 230°C, still more preferably 80°C to 200°C, still more preferably 80°C to 150°C, particularly preferably 80°C to 120°C, most preferably 80°C to 100°C.
  • the expansion start temperature of the thermally expandable microspheres means that the adhesive layer thickness (when an undercoat layer is arranged, the sum of the undercoat layer thickness and the adhesive layer thickness) is 5% or more thicker than at room temperature. means the lowest temperature
  • the foaming initiation temperature can correspond to the temperature at which the adhesive force of the adhesive tape becomes 1.0 N/20 mm or less and 50% or less of the initial adhesive force.
  • the content of the heat-expandable microspheres in the pressure-sensitive adhesive layer can be appropriately set according to the desired decrease in adhesive force.
  • the content of the thermally expandable microspheres is, for example, 1 part by weight to 150 parts by weight, preferably 10 parts by weight to 130 parts by weight, more preferably 100 parts by weight of the base polymer forming the pressure-sensitive adhesive layer. is 25 to 100 parts by weight.
  • the arithmetic surface roughness Ra of the adhesive layer before the thermally expandable microspheres are expanded is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.
  • the thickness of the adhesive layer is preferably 5 ⁇ m to 70 ⁇ m, more preferably 10 ⁇ m to 60 ⁇ m, still more preferably 15 ⁇ m to 55 ⁇ m, most preferably 20 ⁇ m to 50 ⁇ m.
  • the substrate may be composed of any suitable material.
  • Various sheet materials such as plastic film, plastic sheet, paper, cloth, nonwoven fabric, metal foil, a plastic laminate thereof, and a laminate of plastics can be used as the base material.
  • plastic films and plastic sheets are most preferable from the viewpoint of handling and cost.
  • the material for the plastic film can be selected according to need from the viewpoint of strength, heat resistance, and the like.
  • polyethylene polyethylene
  • PP polypropylene
  • EVA ethylene-vinyl acetate copolymer
  • PBT polyethylene terephthalate
  • PET polyethylene
  • Polyesters such as naphthalate (PEN) and polybutylene terephthalate (PBT)
  • PVC polyvinyl chloride
  • PPS polyphenylene sulfide
  • amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); Ketone (PEEK), polyimide, polyetherimide, polystyrene, acrylic resin and the like.
  • any of an unstretched film, a uniaxially oriented film, and a biaxially oriented film may be used.
  • these films may be laminated films composed of two or more film layers, or films to which a lubricant such as inert particles is appropriately added may be used from the viewpoint of handleability.
  • the thickness of the substrate is preferably 200 ⁇ m or less, more preferably 1 ⁇ m to 200 ⁇ m, still more preferably 5 ⁇ m to 200 ⁇ m, particularly preferably 10 ⁇ m to 200 ⁇ m, particularly preferably 20 ⁇ m to 200 ⁇ m, Most preferred is 30 ⁇ m to 200 ⁇ m.
  • the base material may be surface-treated.
  • surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, and coating treatment with a primer.
  • the undercoat layer contains any suitable adhesive.
  • the adhesive that constitutes the undercoat layer include acrylic adhesives, rubber adhesives, silicone adhesives, and the like. Among them, an acrylic pressure-sensitive adhesive can be preferably used.
  • an active energy ray-curable acrylic adhesive (hereinafter referred to as an active energy ray-curable adhesive) may be used.
  • the same pressure-sensitive adhesive as that constituting the above-described pressure-sensitive adhesive layer is used as the pressure-sensitive adhesive that constitutes the undercoat layer.
  • the undercoat layer may be an organic substance exhibiting rubber-like elasticity other than those shown above. Therefore, it is sometimes called a rubber-like organic elastic body.
  • the thickness of the undercoat layer is preferably 1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 80 ⁇ m, still more preferably 1 ⁇ m to 60 ⁇ m, still more preferably 1 ⁇ m to 40 ⁇ m, particularly preferably 5 ⁇ m to 35 ⁇ m. , most preferably between 10 ⁇ m and 30 ⁇ m. Within such a range, it is possible to obtain a pressure-sensitive adhesive sheet which is excellent in liner peeling operability and in which the effect of heating the thermally expandable microspheres on the substrate side is suppressed.
  • the elastic modulus of the undercoat layer is preferably 0.001 MPa to 10 MPa, more preferably 0.01 MPa to 8 MPa, and more preferably 0.5 MPa to 5 MPa.
  • the elastic modulus means the elastic modulus measured by the nanoindentation method in a 23° C. environment.
  • the elastic modulus by the nanoindentation method is the load applied to the indenter and the depth of indentation when the indenter (triangular pyramid type) is pushed into the sample (indentation speed: 1000 nm / sec, indentation depth: 800 nm).
  • indentation speed 1000 nm / sec
  • indentation depth 800 nm
  • the separate adhesive layer may contain any suitable adhesive.
  • adhesives constituting another adhesive layer include acrylic adhesives, rubber adhesives, silicone adhesives, and the like.
  • an active energy ray-curable acrylic adhesive hereinafter referred to as an active energy ray-curable adhesive
  • Details of the adhesive are described, for example, in JP-A-2015-168711. The description of the publication is incorporated herein by reference.
  • the above-mentioned adhesive sheet can be produced by any appropriate method.
  • a method for producing an adhesive sheet for example, a method of coating (applying and drying) an adhesive directly on a substrate, or a method of coating (applying and drying) an adhesive onto any appropriate substrate.
  • the undercoat layer can be formed, for example, by applying a composition (adhesive) for forming the undercoat layer onto the base material or the pressure-sensitive adhesive layer. .
  • a method for producing a pressure-sensitive adhesive sheet includes forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive to a substrate, and drying the pressure-sensitive adhesive layer to form a pressure-sensitive adhesive layer. including doing
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer comprises the (meth)acrylic polymer as the base polymer, the cross-linking agent, and the multidentate amino compound and/or the multidentate tin (IV) compound as the low-molecular-weight compound. , and the heat-expandable microspheres described above.
  • the adhesive further contains any suitable solvent.
  • a solvent having a boiling point of less than 100°C is preferably used as the solvent.
  • the pressure-sensitive adhesive sheet of the present invention can exhibit sufficient pressure-sensitive adhesive strength even when a solvent having a relatively low boiling point is used and the pressure-sensitive adhesive coating layer is dried at a low temperature. In such a pressure-sensitive adhesive sheet, energy consumption during production can be suppressed. In addition, in the pressure-sensitive adhesive sheet, deterioration of the heat-expandable microspheres can be prevented, and the peelability is also excellent.
  • a non-aromatic hydrocarbon solvent can be preferably used as the solvent.
  • the non-aromatic hydrocarbon-based solvent may be a solvent comprising one non-aromatic hydrocarbon solvent, or may be a solvent comprising two or more non-aromatic hydrocarbon solvents. Moreover, the non-aromatic hydrocarbon solvent may contain a solvent other than the non-aromatic hydrocarbon solvent.
  • non-aromatic hydrocarbon solvents include aliphatic hydrocarbons such as cyclone and heptane; halogen-containing hydrocarbons such as methylene chloride and chloroform; ketones such as acetone, ethyl acetate and 2-butanone; Cyclic ether etc. are mentioned. Among them, ethyl acetate or 2-butanone is preferred.
  • Examples of the method of applying the adhesive include a method using a die coater, a comma coater, a gravure coater, and the like.
  • Heat drying is preferably employed as the drying method.
  • drying can be performed by placing the adhesive coating layer in a dryer equipped with a blower capable of forcibly convecting air at a predetermined temperature for an arbitrary period of time.
  • the drying temperature is preferably 55°C or higher and lower than 100°C, more preferably 60°C to 90°C, even more preferably 65°C to 90°C. Within such a range, the pressure-sensitive adhesive layer can be efficiently formed, and unnecessary foaming of the heat-expandable microspheres and deterioration of the heat-expandable microspheres can be prevented. Moreover, a pressure-sensitive adhesive layer having a preferable surface shape can be formed.
  • the drying temperature may be changed stepwise. For example, the drying temperature may be increased over time to form the pressure-sensitive adhesive layer.
  • the drying time can be any appropriate time depending on the pressure-sensitive adhesive layer composition, drying temperature, and the like.
  • the drying time is, for example, 1 minute to 10 minutes. Within such a range, the pressure-sensitive adhesive layer can be efficiently formed.
  • the drying process may be controlled by the product of the drying temperature and the drying time when drying the adhesive coating layer.
  • the product of drying temperature and drying time is preferably 100° C. ⁇ min to 500° C. ⁇ min, more preferably 100° C. ⁇ min to 350° C. ⁇ min. Within such a range, a pressure-sensitive adhesive layer having excellent adhesiveness can be efficiently formed.
  • the pressure-sensitive adhesive sheet can be preferably used as a temporary fixing sheet when processing any appropriate member (for example, electronic parts such as semiconductor chips).
  • the pressure-sensitive adhesive sheet can be used as a sheet for temporarily fixing a semiconductor chip when manufacturing a CSP (Chip Size/Scale Package) or a WLP (Wafer Level Package).
  • the adhesive sheet is roll-shaped.
  • the expansion start temperature of the thermally expandable microspheres is determined by the following method. On a hot plate (Shamal hot plate “HHP-411”) set to a predetermined temperature, the adhesive sheet is sandwiched between 10 mm thick heat-resistant glass plates (140 mm ⁇ 140 mm) set to the same temperature as the predetermined temperature described later.
  • the predetermined temperature is a temperature set in increments of 5°C starting from 50°C (that is, 50°C, 55°C, 60°C, and so on), and each time the predetermined temperature is changed, the adhesive sheet is renewed. to use.
  • the adhesive layer whose thickness is measured is the adhesive layer (containing thermally expandable microspheres), and when the undercoat layer (rubber-like organic elastic layer) is present, shall be measured including
  • the expansion initiation temperature of thermally expandable microspheres F-36D and F-50D measured by this method is 85°C and 105°C, respectively.
  • Example 1 Preparation of undercoat layer/substrate laminate
  • a toluene solution of polymer 6 polymer 6: 100 parts
  • 1.5 parts of an isocyanate-based cross-linking agent manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L”
  • dioctyltin dilaurate are mixed and mixed.
  • a solution A was prepared.
  • the mixed solution A was applied to one surface of a substrate (manufactured by Toray Industries, Inc., product name “Lumirror S10”, thickness: 25 ⁇ m) using an applicator so that the thickness after solvent evaporation (drying) was 13 ⁇ m. .
  • a liner coated with a silicone-based release agent (PET film, manufactured by Mitsubishi Plastics, Inc., product name “MRF-38”) was coated with the release agent so that the thickness after the solvent volatilization (drying) was 35 ⁇ m.
  • the adhesive mixed solution B
  • the solvent was volatilized (dried) at 65° C. for 5 minutes using a forced convection hot air drying oven to obtain an MRF38 (liner)/adhesive layer (containing thermally expandable microspheres) laminate.
  • MRF38 (liner)/adhesive layer (containing heat-expandable microspheres)/undercoat layer/substrate laminate) MRF38 (liner)/adhesive layer (containing thermally expandable microspheres) and undercoat layer/substrate laminate are laminated so that the adhesive layer (containing thermally expandable microspheres) and the undercoat layer face each other.
  • a laminate of MRF38 (liner)/adhesive layer (containing heat-expandable microspheres)/undercoat layer/substrate was obtained.
  • a liner coated with a silicone-based release agent (PET film, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) was coated with the release agent so that the thickness after solvent volatilization (drying) was 7 ⁇ m.
  • the mixed solution C was applied. Thereafter, the solvent was volatilized (dried) at 150° C. for 1 minute using a forced convection hot air drying oven to obtain MRF50 (liner)/another adhesive layer laminate.
  • MRF38 (liner)/adhesive layer (containing thermally expandable microspheres)/undercoat layer/substrate laminate and MRF50 (liner)/another adhesive layer laminate were combined with the substrate and another adhesive layer.
  • Example 2 to 5 Comparative Examples 1 to 4
  • the base polymer shown in Table 1 was used (in Example 5, a 2-butanone solution of polymer 4 was used, and in Comparative Examples 2 and 3, a toluene solution of polymer 5 was used),
  • the low-molecular compound shown in Table 1 was used in the amount shown in Table 1
  • the crosslinking agent shown in Table 1 was used in the amount shown in Table 1
  • the thermally expandable microspheres shown in Table 1 were used in the amount shown in Table 1
  • the amount shown in Table 1 was used.
  • a pressure-sensitive adhesive sheet with a liner was obtained in the same manner as in Example 1, except that the pressure-sensitive adhesive coating layer was dried at the temperature and time shown in 1.
  • the heat-expandable microspheres “F-50D” are trade name “F-50D” manufactured by Matsumoto Yushi Seiyaku Co., Ltd. (expansion initiation temperature: 105° C., average particle size: 14 ⁇ m).
  • the cross-linking agent “TC” is an epoxy-based cross-linking agent (Mitsubishi Gas Chemical Co., Ltd., trade name “Tetrad C”).
  • Example 6 A pressure-sensitive adhesive sheet with a liner was obtained in the same manner as in Example 1, except that the undercoat layer did not contain dioctyltin dilaurate.
  • Adhesive strength The adhesive sheets obtained in Examples and Comparative Examples were cut into a size of 20 mm in width and 140 mm in length.
  • a polyethylene terephthalate film (trade name “Lumirror S-10” manufactured by Toray Industries, Inc.; thickness: 25 ⁇ m, width: 30 mm) as an adherend was protruded in the width direction by 5 mm on each side.
  • JIS Z 0237:2009 a 2-kg roller was reciprocated once to bond them together.
  • a measurement sample was prepared by bonding a metal plate (SUS304 plate, thickness 3 mm) to another adhesive layer side via a double-sided tape (manufactured by Nitto Denko Co., Ltd., trade name “No. 500”). After that, the adherend was peeled off from the adhesive sheet in the longitudinal direction under the conditions of a peeling angle of 180° and a peeling speed (tensile speed) of 300 mm/min. The maximum value of the load excluding the peak top at the initial stage of measurement) was obtained, and this maximum load was divided by the tape width to obtain the adhesive strength (N/20 mm width). The above operation was performed in an atmosphere at a temperature of 23°C.
  • the sample was placed on a hot plate (Shamal hot plate "HHP-411") set to 120 ° C with the adhesive sheet facing upward, and the heat-resistant glass plate set at 120 ° C was placed on the adhesive sheet ( That is, a laminated structure of hot plate/metal plate/adhesive sheet/glass plate was used).
  • the time until the adhesive layer was peeled off (separated) from the SUS plate was measured.
  • the time required for separation is excellent if it is within 3 minutes ( ⁇ in the table), good if it is over 3 minutes and within 7 minutes ( ⁇ in the table), and over 7 minutes but within 10 minutes. was rated as acceptable ( ⁇ in the table), and as unacceptable (x in the table) when 10 minutes or more or no separation occurred.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une feuille autocollante comprenant une couche autocollante qui peut être formée avec une faible énergie thermique et peut présenter une excellente force adhésive.　Cette feuille autocollante comprend un substrat et une couche autocollante disposée sur au moins un côté du substrat, la couche autocollante comprenant : un polymère (méth)acrylique en tant que polymère de base ; un agent de réticulation à base d'isocyanate et/ou un agent de réticulation à base d'époxy, en tant qu'agent de réticulation ; un composé amino ayant un groupe amino tertiaire et capable de coordination multidentée et/ou un composé étain organique (IV) capable de coordination multidentée, en tant que composé de faible poids moléculaire ; et de fines sphères expansibles à la chaleur. Le polymère (méth)acrylique comprend une unité constitutive ayant un groupe hydrogène actif.
PCT/JP2022/013629 2021-08-19 2022-03-23 Feuille autocollante Ceased WO2023021773A1 (fr)

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WO2025215897A1 (fr) * 2024-04-08 2025-10-16 日東電工株式会社 Feuille adhésive

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WO2025215897A1 (fr) * 2024-04-08 2025-10-16 日東電工株式会社 Feuille adhésive

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