WO2023037914A1 - 粘着剤組成物、硬化物、及び熱剥離型粘着シート - Google Patents

粘着剤組成物、硬化物、及び熱剥離型粘着シート Download PDF

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Publication number
WO2023037914A1
WO2023037914A1 PCT/JP2022/032336 JP2022032336W WO2023037914A1 WO 2023037914 A1 WO2023037914 A1 WO 2023037914A1 JP 2022032336 W JP2022032336 W JP 2022032336W WO 2023037914 A1 WO2023037914 A1 WO 2023037914A1
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Prior art keywords
group
ethylenically unsaturated
meth
adhesive composition
sensitive adhesive
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PCT/JP2022/032336
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English (en)
French (fr)
Japanese (ja)
Inventor
達宏 池谷
一博 佐々木
健一 中西
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株式会社レゾナック
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Priority to JP2023546889A priority Critical patent/JPWO2023037914A1/ja
Priority to KR1020247007146A priority patent/KR20240039184A/ko
Priority to CN202280060620.7A priority patent/CN117957295A/zh
Publication of WO2023037914A1 publication Critical patent/WO2023037914A1/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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—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 a pressure-sensitive adhesive composition, a cured product obtained by photocuring the pressure-sensitive adhesive composition, and a heat-peelable pressure-sensitive adhesive sheet having the cured product as an adhesive layer. More particularly, it relates to a heat-peelable pressure-sensitive adhesive sheet that can be easily peeled off from an adherend by heating to lower its adhesive force after being attached to the adherend.
  • removable adhesive sheets which can be attached to an adherend with appropriate adhesive strength and can be easily peeled off after use, have been used for labels, substrate protection, surface protection of products in the manufacturing process, and temporary adhesives. Widely used for fixed applications.
  • process of manufacturing electronic parts it is widely used in processes such as the process of manufacturing flexible printed circuit boards, the process of cutting semiconductor wafers, and the process of cutting laminated ceramic capacitors into small pieces.
  • an adhesive sheet having an ultraviolet curable adhesive layer provided on a base material, an adhesive sheet having an adhesive layer containing thermally expandable particles provided on a base material, etc. have been proposed and used.
  • Patent Document 1 the adhesive sheet provided with an adhesive layer containing thermally expandable particles expands the thermally expandable particles by heating to generate unevenness at the interface between the adherend and the adhesive layer, thereby increasing the adhesion between the adherend and the adhesive layer.
  • the contact area of the layers is reduced, and as a result, the adhesive force of the adhesive sheet is lowered. Therefore, compared with other pressure-sensitive adhesive sheets, it can be easily peeled from an adherend.
  • Patent Documents 2 and 3 propose adhesive compositions containing two or more types of thermally expandable microspheres and an adhesive.
  • JP 2019-116609 A Japanese Patent Application Laid-Open No. 2007-131661 JP 2015-28108 A
  • the disclosed method has been desired to be further improved from the viewpoint of ease of peeling and contamination resistance of the surface of the adherend.
  • the present invention has been made to solve the above problems, and the peeling force from the adherend is sufficiently high, and by heating after the completion of the process, it can be easily peeled from the adherend. It is an object of the present invention to provide a heat-peelable pressure-sensitive adhesive sheet that can be applied to the surface of an adherend without causing contamination. Another object of the present invention is to provide a pressure-sensitive adhesive composition suitable for the heat-peelable pressure-sensitive adhesive sheet.
  • the present invention includes the following aspects.
  • an unsaturated polyurethane (A); an ethylenically unsaturated group-containing monomer (B); Thermally expandable particles (C); and a photopolymerization initiator (D) does not contain an ethylenically unsaturated group-containing monomer (B')
  • the unsaturated polyurethane (A) has a weight average molecular weight of 10,000 to 200,000
  • the ethylenically unsaturated group-containing monomer (B) is a monomer having one ethylenically unsaturated group
  • the pressure-sensitive adhesive composition wherein the ethylenically unsaturated group-containing monomer (B') is a monomer having two or more ethylenically unsaturated groups.
  • the content of the thermally expandable particles (C) is 10 to 50 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyurethane (A) and the ethylenically unsaturated group-containing monomer (B).
  • the content of the photopolymerization initiator (D) is 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyurethane (A) and the ethylenically unsaturated group-containing monomer (B).
  • the adhesive composition according to any one of claims 1 to 3, which is a part.
  • the unsaturated polyurethane (A) is an unsaturated polyurethane obtained by adding a hydroxy group-containing ethylenically unsaturated compound or an isocyanato group-containing ethylenically unsaturated compound to a urethane prepolymer that is a reaction product of a polyol and a polyisocyanate.
  • the ethylenically unsaturated group-containing monomer (B) is one or two selected from alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, hydroxy group-containing (meth)acrylates, and (meth)acrylamides.
  • the ethylenically unsaturated group-containing monomer (B) contains 10 to 60% by mass of an alkyl (meth)acrylate having 4 to 12 carbon atoms and 3 to 20% by mass of a hydroxy group-containing (meth)acrylate.
  • the pressure-sensitive adhesive composition according to any one of [1] to [6].
  • the peeling force from the adherend is sufficiently high, and by heating after the completion of the process, it can be easily peeled from the adherend without causing contamination of the adherend surface.
  • a heat-peelable pressure-sensitive adhesive sheet can be provided.
  • the (meth)acryloyl group is one or more selected from a group represented by the chemical formula CH 2 ⁇ CH—CO— and a functional group represented by the chemical formula CH 2 ⁇ C(CH 3 )—CO—.
  • the pressure-sensitive adhesive composition of this embodiment contains an unsaturated polyurethane (A), an ethylenically unsaturated group-containing monomer (B), thermally expandable particles (C), and a photopolymerization initiator (D). .
  • the pressure-sensitive adhesive composition of this embodiment does not contain an ethylenically unsaturated group-containing monomer (B').
  • Unsaturated polyurethane (A) is a resin having an ethylenically unsaturated bond and a urethane bond.
  • the pressure-sensitive adhesive composition contains the unsaturated polyurethane (A)
  • the peel strength, flexibility, and cohesive strength of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape are improved.
  • a hydroxyl group-containing ethylenically unsaturated compound (when the urethane prepolymer has a terminal isocyanate group) is added to a urethane prepolymer which is a reaction product of a polyol and a polyisocyanate.
  • an unsaturated polyurethane to which an isocyanato group-containing ethylenically unsaturated compound (when the urethane prepolymer has a terminal hydroxy group) is added.
  • an isocyanato group-containing ethylenically unsaturated compound when the urethane prepolymer has a terminal hydroxy group
  • alkyl alcohol or alkyl isocyanate is used in combination during the addition reaction to the urethane prepolymer to adjust the amount of ethylenically unsaturated groups to be introduced into the unsaturated polyurethane (A).
  • Polyol which is one of the raw materials of the unsaturated polyurethane (A), is not particularly limited as long as it is a compound having two or more hydroxy groups. Examples include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and copolymers of these raw material monomers. Other polyols may also be used.
  • polyether polyols examples include alkylene oxides such as propylene oxide, tetrahydrofuran, ethylene oxide and butylene oxide; (poly)oxyalkylene polyols obtained by condensation of hexanediol, methylhexanediol, heptanediol, octanediol or mixtures thereof; Alternatively, glycols obtained by adding alkylene oxides such as ethylene oxide to bisphenols such as bisphenol A and bisphenol F can be used. Among them, (poly)oxyalkylene polyol is preferable from the viewpoint of flexibility of unsaturated polyurethane. Among them, polyethylene glycol, polypropylene glycol, and polybutylene glycol are more preferable.
  • polyester polyols examples include polyester polyols obtained by a condensation reaction between a polyfunctional alcohol and a dibasic acid.
  • polyfunctional alcohols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 3,3-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1, Compounds having two hydroxy groups such as 4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, bisphenol F; Compounds having 3 or more hydroxy groups such
  • dibasic acids examples include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid and trimellitic acid.
  • polyester polyols examples include polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones.
  • lactones include ⁇ -butyrolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -heptanolactone, ⁇ -methyl- ⁇ - and propiolactone.
  • polycarbonate polyol a known polycarbonate polyol having a structure represented by the following formula (1) in the molecule can be used.
  • -[-OR 1 -O-CO-] m - (1) (In formula (1), R 1 represents a divalent organic residue, and m represents an integer of 1 or more.)
  • Polycarbonate polyols can be obtained, for example, by reacting glycol or bisphenol with carbonate (reaction (1)), by reacting glycol or bisphenol with phosgene in the presence of alkali (reaction (2)), and the like.
  • reaction (1) examples include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate.
  • Examples of the glycol used in the reactions (1) and (2) include the compounds listed above as polyfunctional alcohols having two hydroxy groups.
  • Examples of the bisphenol used in the reactions (1) and (2) include bisphenols such as bisphenol A and bisphenol F; and bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols. be done.
  • polyolefin polyol for example, various commercially available polyols of saturated and unsaturated alkyl compounds can be used. Specific examples include polyethylene polyol, polypropylene polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.
  • Examples of the other polyols include diols such as ethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentyl glycol, and cyclohexanedimethanol.
  • Examples of other polyols include compounds having 3 or more hydroxyl groups, such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, and methylglucoside.
  • polyether polyol polyolefin polyol
  • polycarbonate polyol are preferable from the viewpoint of reactivity with polyisocyanate.
  • Polyisocyanate Polyisocyanate, which is one of raw materials for unsaturated polyurethane (A), is not particularly limited as long as it is a compound having two or more isocyanate groups. Examples include aromatic polyisocyanates, hydrogenated aromatic polyisocyanates, and aliphatic polyisocyanates.
  • aromatic polyisocyanate examples include 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like.
  • diisocyanate is preferred, and 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate are more preferred.
  • Examples of the hydrogenated aromatic polyisocyanate include those obtained by hydrogenating the compounds exemplified as the aromatic polyisocyanate.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2, 6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-m
  • polyisocyanates may be used alone or in combination of two or more.
  • hydrogenated aromatic polyisocyanates and aliphatic polyisocyanates are preferred, and hydrogenated 4,4'-diphenylmethane diisocyanates and isophorone diisocyanates are preferred. more preferred.
  • the hydroxyl group-containing ethylenically unsaturated compound is not particularly limited as long as it is a compound having a hydroxyl group and an ethylenically unsaturated group.
  • An ethylenically unsaturated group can be introduced into the unsaturated polyurethane (A) by adding a hydroxyl group-containing ethylenically unsaturated compound to the isocyanato group-terminated urethane prepolymer.
  • ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and allyl groups.
  • a compound having one hydroxy group and one ethylenically unsaturated group is preferable, and a compound having a hydroxy group and a (meth)acryloyl group is more preferable. Containing (meth)acrylates are more preferred.
  • Examples of compounds having a hydroxy group and a vinyl group include ethylene glycol monovinyl ether, propylene glycol monovinyl ether, diethylene glycol monovinyl ether, butanediol monovinyl ether, hexanediol monovinyl ether, cyclohexanedimethanol monovinyl ether, and the like.
  • Compounds having a hydroxyl group and an allyl group include allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether, butanediol monoallyl ether, hexanediol monoallyl ether, cyclohexanedimethanol monoallyl ether, and the like. is mentioned.
  • hydroxy group-containing (meth)acrylates examples include hydroxyalkyl (meth)acrylates and compounds obtained by (meth)acrylated by leaving one hydroxy group of various polyols.
  • Hydroxyalkyl (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,3-butanediol (meth)acrylate, 1 ,4-butanediol (meth)acrylate, 1,6-hexanediol (meth)acrylate, 3-methylpentanediol (meth)acrylate and the like. These hydroxyalkyl (meth)acrylates may be used alone or in combination of two or more.
  • hydroxyalkyl (meth)acrylates 2-hydroxyethyl acrylate and 4-hydroxybutyl (meth)acrylate are particularly preferable in terms of reactivity with isocyanato groups and photocurability of the pressure-sensitive adhesive composition.
  • alkyl alcohol When adding the hydroxyl group-containing ethylenically unsaturated compound to the isocyanate group-terminated urethane prepolymer, an alkyl alcohol may be added, if necessary.
  • Alkyl alcohols that can be used are not particularly limited as long as they are compounds having an alkyl group and one hydroxy group, and examples thereof include linear, branched, and alicyclic alkyl alcohols. Specific examples include ethanol, butanol, hexanol, and the like. These alkyl alcohols may be used alone or in combination of two or more. By adjusting the amounts of the hydroxyl group-containing ethylenically unsaturated compound and the alkyl alcohol used, the amount of ethylenically unsaturated groups introduced into the unsaturated polyurethane (A) can be adjusted.
  • the isocyanato group-containing ethylenically unsaturated compound is not particularly limited as long as it is a compound having an isocyanato group and an ethylenically unsaturated group.
  • An ethylenically unsaturated group can be introduced into the unsaturated polyurethane (A) by adding an isocyanato group-containing ethylenically unsaturated compound to the hydroxyl group-terminated urethane prepolymer.
  • ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and allyl groups.
  • compounds having one isocyanato group and one ethylenically unsaturated group are preferable, and compounds having an isocyanato group and a (meth)acryloyl group are more preferable, and isocyanato group-containing (meth) ) acrylates are more preferred.
  • Examples of compounds having an isocyanato group and a vinyl group include 2-isocyanatoethyl vinyl ether and 3-isocyanatopropyl vinyl ether.
  • Compounds having an isocyanato group and an allyl group include 2-isocyanatoethyl allyl ether, 3-isocyanatopropyl allyl ether and the like.
  • isocyanato group-containing (meth)acrylates examples include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate and the like.
  • examples of commercially available (meth)acrylates having an isocyanato group include Karenz MOI (registered trademark) and Karenz AOI (registered trademark) manufactured by Showa Denko K.K. These compounds may be used alone or in combination of two or more.
  • 2-isocyanatoethyl (meth)acrylate is particularly preferred in terms of reactivity with hydroxyl groups and photocurability of the pressure-sensitive adhesive composition.
  • alkyl isocyanate When adding the isocyanato group-containing ethylenically unsaturated compound to the hydroxyl group-terminated urethane prepolymer, alkyl isocyanate may be added, if necessary.
  • the alkyl isocyanate that can be used is not particularly limited as long as it is a compound having an alkyl group and one isocyanato group, and examples thereof include linear, branched, and alicyclic alkyl isocyanates. Specific examples include butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate and the like. These alkyl isocyanates may be used alone or in combination of two or more.
  • the amount of ethylenically unsaturated groups introduced into the unsaturated polyurethane (A) can be adjusted.
  • the weight average molecular weight of the unsaturated polyurethane (A) is 10,000 to 200,000, preferably 20,000 to 150,000, more preferably 30,000 to 100,000. If the weight average molecular weight of the unsaturated polyurethane (A) is less than 10,000, the heat releasability of the adhesive layer made of the cured adhesive composition will be insufficient. If the weight-average molecular weight of the unsaturated polyurethane (A) exceeds 200,000, handling of the pressure-sensitive adhesive composition may become difficult and workability may deteriorate.
  • the value of the weight average molecular weight of the unsaturated polyurethane (A) is measured using gel permeation chromatography (Shodex (registered trademark) GPC-101 manufactured by Showa Denko Co., Ltd.) under the following conditions and converted to polystyrene. is calculated by Column: LF-804 manufactured by Showa Denko K.K. Column temperature: 40°C Sample: 0.2% by mass tetrahydrofuran solution of unsaturated polyurethane (A) Flow rate: 1 ml/minute Eluent: Tetrahydrofuran Detector: RI detector (differential refractive index detector)
  • the content of the unsaturated polyurethane (A) is preferably 5 to 70% by mass, preferably 10 to 55% by mass, based on the total of the unsaturated polyurethane (A) and the ethylenically unsaturated group-containing monomer (B) described later. More preferably 15 to 45% by mass. If the content of the unsaturated polyurethane (A) is 5% by mass or more, an adhesive layer having sufficient cohesive force can be obtained, and when the heat-peelable adhesive sheet is peeled off from the adherend by heating, There is no adhesive residue left behind. If the content of the unsaturated polyurethane (A) is 70% by mass or less, a heat-peelable pressure-sensitive adhesive sheet with sufficient peeling force can be obtained.
  • the ethylenically unsaturated group-containing monomer (B) is a monomer having one ethylenically unsaturated group.
  • ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and allyl groups.
  • a (meth)acryloyl group is preferable from the viewpoint of photocurability as an adhesive composition.
  • the ethylenically unsaturated group-containing monomer (B) may have a functional group other than the ethylenically unsaturated group, such as a hydroxy group, an epoxy group, and an amino group.
  • Ethylenically unsaturated group-containing monomers (B) include (meth)acrylic acid, carboxy group-containing (meth)acrylates, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxyalkyl ( meth)acrylates, alkoxy(poly)alkylene glycol (meth)acrylates, fluorinated alkyl(meth)acrylates, dialkylaminoalkyl(meth)acrylates, acrylamide derivatives, epoxy group-containing (meth)acrylates, and the like.
  • Carboxy group-containing (meth)acrylates include ⁇ -carboxyethyl (meth)acrylate and the like.
  • Alkyl (meth)acrylates include methyl (meth)acrylate, n-propyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, Lauryl (meth)acrylate, tridecyl (meth)acrylate and the like.
  • Cyclic alkyl (meth)acrylates include cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, norbornanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate , dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, and the like.
  • Hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6 -hexanediol (meth)acrylate, 3-methylpentanediol (meth)acrylate and the like.
  • Alkoxyalkyl (meth)acrylates include ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-ethoxyethoxyethyl (meth)acrylate and the like.
  • Alkoxy(poly)alkylene glycol (meth)acrylates include methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate and the like.
  • fluorinated alkyl (meth)acrylates include octafluoropentyl (meth)acrylate and the like.
  • Dialkylaminoalkyl (meth)acrylates include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate and the like.
  • Acrylamide derivatives include acrylamide, dimethylacrylamide, diethylacrylamide, (meth)acryloylmorpholine and the like.
  • Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate and the like.
  • Examples of ethylenically unsaturated group-containing monomers (B) include (meth)acrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, N-vinylpyridine, N-vinylpyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, triethylene glycol monovinyl ether or diethylene glycol monovinyl ether, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, and the like. These compounds may be used alone or in combination of two or more.
  • alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, and hydroxy group-containing (meth) ) acrylates and (meth)acrylamides are preferred.
  • the content of the alkyl (meth)acrylate having 4 to 12 carbon atoms in the ethylenically unsaturated group-containing monomer (B) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
  • the content of the hydroxy group-containing (meth)acrylate in the ethylenically unsaturated group-containing monomer (B) is preferably 3 to 20% by mass, more preferably 4 to 10% by mass.
  • the content of the ethylenically unsaturated group-containing monomer (B) is preferably 30 to 95% by mass, preferably 45 to 90% by mass is more preferable, and 55 to 85% by mass is more preferable.
  • the content of the ethylenically unsaturated group-containing monomer (B) is 30% by mass or more, a heat-peelable pressure-sensitive adhesive sheet with sufficient peeling force can be obtained. If the content of the ethylenically unsaturated group-containing monomer (B) is 95% by mass or less, an adhesive layer having sufficient cohesive force can be obtained, and when the thermally peelable adhesive sheet is thermally peeled from the adherend, No adhesive remains on the adherend.
  • the pressure-sensitive adhesive composition of the present embodiment does not contain an ethylenically unsaturated group-containing monomer (B') having two or more ethylenically unsaturated groups.
  • the meaning of "not containing” is that the ethylenically unsaturated polyurethane (A) and the ethylenically unsaturated group-containing monomer (B) in the pressure-sensitive adhesive composition according to the present embodiment are added to a total of 100 parts by mass.
  • the content of the group-containing monomer (B') is 0 to 0.5% by mass, preferably 0 to 0.3% by mass, more preferably 0 to 0.1% by mass.
  • the ethylenically unsaturated group-containing monomer (B') is not particularly limited as long as it is a monomer having two or more ethylenically unsaturated groups.
  • ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and allyl groups.
  • ethylenically unsaturated group-containing monomer (B′) include trimethylolpropane triacrylate, dipropylene diacrylate, 1,6-hexanediol diacrylate, bisphenol A diacrylate, tricyclodecanedimethanol diacrylate, divinyl Benzene, pentaerythritol tetraacrylate, diallyl phthalate, and the like.
  • Thermally expandable particles (C) are particles whose volume increases when heated. For example, microencapsulated particles encapsulating a substance that is easily vaporized by heating are preferably used.
  • the substance contained in the thermally expandable particles (C) is preferably a substance that vaporizes at a temperature of 110 to 180° C. Examples include isobutane, propane, pentane, hexane, heptane and octane. These substances may be used alone or in combination of two or more. Moreover, these substances can be appropriately selected according to the desired temperature at which the thermally expandable particles (C) are to be expanded.
  • the material of the shell portion corresponding to the outside of the thermally expandable particles (C) is preferably made of a thermoplastic substance, a heat-melting substance, a substance that bursts due to thermal expansion, or the like.
  • a thermoplastic substance e.g., polyethylene glycol, polypropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol glycol
  • thermally expandable particles C
  • the trade name "Matsumoto Microsphere” manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. grades: F-30, F-30D, F-36D, F-36LV, F-50, F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D, HF-48D
  • the volume-based average particle diameter (D50) of the thermally expandable particles (C) is not particularly limited, but is preferably 1 to 50 ⁇ m, more preferably 5 to 30 ⁇ m, in terms of dispersibility and thickness of the adhesive layer. .
  • the thermally expandable particles (C) may be used alone or in combination of two or more.
  • the content of the thermally expandable particles (C) varies depending on the type and is not particularly limited. For example, it is preferably 10 to 50 parts by mass, preferably 15 to 45 parts by mass, with respect to a total of 100 parts by mass of the unsaturated polyurethane (A) and the ethylenically unsaturated group-containing monomer (B). More preferably, it is 20 to 40 parts by mass.
  • the thermally expandable particles (C) are expanded by heat treatment after the thermally peelable pressure-sensitive adhesive sheet is attached to the adherend, thereby forming an adhesive layer. Appropriate unevenness occurs on the surface. Therefore, the contact area between the adhesive layer and the adherend is sufficiently reduced, and good peelability can be achieved.
  • the photopolymerization initiator (D) is preferably a photopolymerization initiator that generates radicals upon irradiation with light such as ultraviolet rays and visible light.
  • Examples include carbonyl-based photopolymerization initiators, sulfide-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, quinone-based photopolymerization initiators, sulfochloride-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like. .
  • Carbonyl photopolymerization initiators include benzophenone, benzyl, benzoin, ⁇ -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoylform mate
  • Sulfide photopolymerization initiators include diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, tetramethylammonium monosulfide and the like.
  • Acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.
  • quinone photopolymerization initiators examples include benzoquinone and anthraquinone.
  • Thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.
  • sulfochloride-based photopolymerization initiators examples include 2-naphthalenesulfonyl chloride.
  • Thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.
  • carbonyl-based photopolymerization initiators and/or acylphosphine oxide-based photopolymerization initiators are preferable from the viewpoint of solubility in the adhesive composition, and 1-hydroxycyclohexylphenyl ketone and/or 2,4,6-trimethyl Benzoyldiphenylphosphine oxide is more preferred.
  • the content of the photopolymerization initiator (D) is 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyurethane (A) and the ethylenically unsaturated group-containing monomer (B). is preferred, and 0.3 to 3 parts by mass is more preferred.
  • the content of the photopolymerization initiator (D) is 0.1 parts by mass or more, sufficient photocurability as an adhesive composition can be obtained.
  • the content of the photopolymerization initiator (D) is 5 parts by mass or less, the heat-peelable pressure-sensitive adhesive sheet has good peel strength.
  • additives may be added to the pressure-sensitive adhesive composition as necessary.
  • Additives include, for example, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphorus
  • additives include acid ester-based and other flame retardants, antistatic agents such as surfactants, and dyes.
  • the pressure-sensitive adhesive composition contains an ethylenically unsaturated group-containing monomer (B) as a low molecular weight component. Therefore, the viscosity of the pressure-sensitive adhesive composition can be adjusted so that it can be applied without adding a solvent. That is, the pressure-sensitive adhesive composition contains a solvent in addition to the essential components of the unsaturated polyurethane (A), the ethylenically unsaturated group-containing monomer (B), the thermally expandable particles (C), and the photopolymerization initiator (D). It does not have to be substantially included.
  • the step of drying the solvent by heating can be omitted in the production of the heat-peelable pressure-sensitive adhesive sheet, resulting in high productivity.
  • the pressure-sensitive adhesive composition does not substantially contain a solvent.
  • the meaning of "substantially free” is that the content of the solvent in the adhesive composition according to the present embodiment is 0 to 1% by mass, preferably 0 to 0.5% by mass, more preferably It is 0 to 0.1% by mass.
  • a solvent may be added to the adhesive composition for the purpose of adjusting the viscosity during coating.
  • the solvent can be appropriately selected depending on other components contained in the pressure-sensitive adhesive composition, but organic solvents are preferred.
  • the organic solvent used is not particularly limited, but includes methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, isopropanol and the like. These organic solvents may be used alone or in combination of two or more. It is preferable that the solvent is removed by drying after applying the pressure-sensitive adhesive composition to a substrate or the like, and then photocuring.
  • unsaturated polyurethane (A) can be produced by the following method. First, a polyol and a polyisocyanate are reacted in such a proportion that the total amount of isocyanato groups in the polyisocyanate is greater than the total amount of hydroxy groups in the polyol to produce an isocyanato group-terminated urethane prepolymer. At this time, the molecular weight of the urethane prepolymer can be adjusted by adjusting the ratio of the total amount of hydroxy groups and the total amount of isocyanato groups.
  • the greater the amount of hydroxy groups relative to the isocyanate groups the greater the molecular weight of the resulting polyurethane compound. Conversely, the smaller the amount of hydroxy groups relative to the amount of isocyanate groups, the smaller the molecular weight of the resulting polyurethane compound.
  • an unsaturated polyurethane (A) is produced by adding a hydroxyl group-containing ethylenically unsaturated compound to the isocyanate groups of the obtained isocyanato group-terminated urethane prepolymer.
  • the unsaturated polyurethane (A) can be produced by the following method. First, a polyol and a polyisocyanate are reacted in such a proportion that the total amount of isocyanato groups in the polyisocyanate is less than the total amount of hydroxy groups in the polyol to form a hydroxy group-terminated urethane prepolymer. At this time, the molecular weight of the urethane prepolymer can be adjusted by adjusting the ratio of the total amount of hydroxy groups and the total amount of isocyanato groups. For example, the higher the ratio of isocyanato groups to hydroxy groups, the higher the molecular weight of the resulting polyurethane compound. Conversely, the smaller the isocyanato group weight relative to the hydroxyl group weight, the smaller the molecular weight of the resulting polyurethane compound.
  • an unsaturated polyurethane (A) is produced by adding an isocyanato group-containing ethylenically unsaturated compound to the hydroxy groups of the obtained hydroxy group-terminated urethane prepolymer.
  • All the reactions in the first embodiment and the second embodiment described above are reactions between hydroxyl groups and isocyanato groups. Both reactions are carried out in the presence of an organic solvent inert to isocyanato groups, using a urethanization catalyst, at a temperature of generally 30 to 100° C. and continuously for about 1 to 5 hours.
  • a urethanization catalyst such as dibutyltin dilaurate and dibutyltin diethylhexoate can be used as the urethanization catalyst.
  • the amount of the urethanization catalyst used is usually 50 to 500 ppm based on the total mass of raw materials used in the reaction.
  • the amount of ethylenically unsaturated groups introduced is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, relative to the number of moles of isocyanato groups or hydroxy groups, which are terminal groups of the urethane prepolymer. preferable.
  • the adhesive layer obtained by curing the adhesive composition has sufficiently high cohesive strength.
  • the adhesive composition comprises an unsaturated polyurethane (A), an ethylenically unsaturated group-containing monomer (B), thermally expandable particles (C), a photopolymerization initiator (D), and optionally added. , other additives, and an organic solvent.
  • the mixing method is not particularly limited, but for example, it can be carried out using a stirring device equipped with stirring blades such as Homodisper and paddle blades.
  • the order of mixing is not particularly limited, and all components may be added and mixed at once, or each component may be divided into multiple portions and added and mixed repeatedly. If there is a component that is solid at room temperature, it can be dissolved in a solvent, dispersed in a dispersion medium, or added after being melted by heating to make the component sticky. It becomes easy to mix with high uniformity in the agent composition.
  • the cured product of the pressure-sensitive adhesive composition can be obtained by irradiating the above-described pressure-sensitive adhesive composition with ultraviolet rays to photocure it.
  • the gel fraction of the photocured product of the adhesive composition excluding the thermally expandable particles (C) is preferably 85 to 100% by mass, more preferably 88 to 100% by mass, and 90 to 100% by mass. is more preferable.
  • the gel fraction is the mass fraction of the extractable insoluble matter with respect to the solvent, and the solvent selected here is one that can dissolve the non-crosslinked components in the cured product of the pressure-sensitive adhesive composition.
  • the gel fraction is measured by the method described in Examples below.
  • the gel fraction of the cured product of the adhesive composition is 85 to 100% by mass, so-called adhesive residue, which is a part of the adhesive layer etc. remaining on the adherend when the heat-peelable adhesive sheet is peeled off, is suppressed. can do.
  • the heat-peelable pressure-sensitive adhesive sheet of this embodiment has a pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition on one side or both sides of a substrate.
  • the thickness of the adhesive layer is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, even more preferably 15 to 100 ⁇ m. When the thickness of the adhesive layer is 5 ⁇ m or more, the strength of the adhesive layer is sufficient, and when the thickness is 200 ⁇ m or less, the thickness of the adhesive layer can be easily controlled.
  • the material of the substrate constituting the heat-peelable pressure-sensitive adhesive sheet of the present embodiment is not particularly limited, and can be appropriately selected according to the field of application of the heat-peelable pressure-sensitive adhesive sheet and the operating temperature.
  • the base material is composed of a synthetic resin such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polycarbonate, triacetylcellulose, cellophane, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polyethersulfone, aromatic polyamide, polysulfone, and the like. can do.
  • the substrate may be transparent or may be colored by blending various pigments or dyes. Also, a base material whose surface has been processed into a matt state can be used.
  • the thickness of the base material can be appropriately selected according to the application of the heat-peelable pressure-sensitive adhesive sheet, and is not particularly limited.
  • the thickness of the base material is preferably It is 5 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 20 ⁇ m or more.
  • the thickness of the substrate is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the base material may be subjected to antistatic treatment.
  • the antistatic treatment applied to the base material is not particularly limited, but a method of providing an antistatic layer on at least one side of the base material, a method of kneading an antistatic agent into the base material, or the like can be used.
  • the surface of the base material forming the adhesive layer may be subjected, if necessary, to an easy-adhesion treatment such as acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, ozone treatment, or the like.
  • the heat-peelable pressure-sensitive adhesive sheet can be laminated with a separator on the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive layer.
  • a separator for example, paper, plastic film, or the like can be used, but a plastic film is preferable because of its excellent surface smoothness.
  • the plastic film used as the separator is not particularly limited as long as it can protect the adhesive layer, and examples thereof include polyethylene, polypropylene, polyethylene terephthalate, polybutene and the like.
  • At least one of the substrate and the separator is preferably selected from a material that transmits light for curing the adhesive layer.
  • the method for producing a heat-peelable pressure-sensitive adhesive sheet according to the present embodiment includes, for example, applying a pressure-sensitive adhesive composition to a base material, laminating a separator, and then irradiating the applied pressure-sensitive adhesive composition with ultraviolet rays for photocuring. can be obtained by
  • the method of applying the adhesive composition to the substrate is not particularly limited and can be selected as appropriate.
  • various coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, and direct coaters can be used as a method of applying the adhesive composition to a substrate.
  • the method used, the screen printing method, etc. are mentioned.
  • Light sources for photocuring the pressure-sensitive adhesive composition include black lights, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, ultraviolet UV lights, and the like.
  • the irradiation intensity of light is preferably 50 to 3000 mW/cm 2 . If the irradiation intensity of light is low, it takes a long time for curing, resulting in a decrease in productivity.
  • the heat treatment for peeling it off from the adherend is not particularly limited, and can be performed using a heating means according to the application.
  • a heating means include heat treatment using a hot plate, hot air dryer, infrared lamp, near infrared lamp, air dryer, heated water, and the like.
  • the temperature of the heat treatment is not particularly limited as long as it is equal to or higher than the expansion start temperature of the thermally expandable particles. , heating means) can be appropriately set. Examples of the heat treatment include heating at 100 to 250° C. for 5 to 90 seconds using a hot plate and heating at 100 to 250° C. for 5 to 15 minutes using a hot air dryer.
  • the heat-peelable pressure-sensitive adhesive sheet according to the present embodiment is suitably used as a protective sheet in the production of electronic components, a backing sheet in the flexible printed circuit (FPC) production process, and a mask material in the plating process.
  • electronic components include semiconductor device components such as silicon wafers, multilayer capacitors, and LEDs.
  • Desmodur W Hydrogenated product of diphenylmethane diisocyanate, manufactured by Sumika Covestrourethane
  • Desmodur I Isophorone diisocyanate, manufactured by Sumika Covestrourethane Actcol D-2000: Polypropylene glycol, manufactured by Mitsui Chemicals, Inc., hydroxyl value: 56 mgKOH/ g
  • Actcol D-1000 polypropylene glycol, manufactured by Mitsui Chemicals, Inc., hydroxyl value: 111 mgKOH/g GI-3000: Hydrogenated polybutadiene having a terminal hydroxyl group, NISSO-PB GI-3000, manufactured by Nippon Soda Co., Ltd., hydroxyl value: 25 mgKOH/g PH-2000: polycarbonate diol, ETERNACOLL PH-2000, manufactured by Ube Industries, Ltd., hydroxyl value: 56 mgKOH/g
  • Example 1 ⁇ Preparation of adhesive composition> As the unsaturated polyurethane (A), 30 parts by mass of the unsaturated polyurethane (a-1) obtained in Synthesis Example 1; -5 parts by mass of hydroxyethyl acrylate and 35 parts by mass of cyclohexyl acrylate; temperature: 150 to 160°C) to 30 parts by mass; 1-hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins B.V.) as a photopolymerization initiator (D) was blended and dispersed at 25°C. to prepare the adhesive composition of Example 1.
  • 1-hydroxycyclohexylphenyl ketone Omnirad 184, manufactured by IGM Resins B.V.
  • the prepared pressure-sensitive adhesive composition was applied onto a 50 ⁇ m-thick corona-treated PET film (E5100 manufactured by Toyobo Co., Ltd.) using an applicator, and a 75 ⁇ m-thick release PET film ( It was covered with E7006 manufactured by Toyobo Co., Ltd.
  • an ultraviolet irradiation device manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp
  • the sheet covered with the release PET film is irradiated with ultraviolet rays from the surface on the release PET film side, and the adhesive is removed.
  • the composition was photocured.
  • the ultraviolet irradiation distance is 25 cm
  • the lamp moving speed is 1.0 m/min
  • the irradiation amount is 1000 mJ/cm 2 .
  • the thickness of the adhesive layer after curing was 75 ⁇ m.
  • the thickness of the adhesive layer was calculated by measuring the thickness of the heat-peelable adhesive sheet using a dial gauge and then subtracting the 50 ⁇ m thickness of the base film from the measured value.
  • the measuring surface of the dial gauge was a circular plane with a diameter of 5 mm, and the measuring force was 0.8N.
  • the initial peel force was measured and the heat-peelability was evaluated.
  • the evaluation method is shown below.
  • the heat-peelable pressure-sensitive adhesive sheet was cut into a size of 25 mm wide and 150 mm long, and the peelable PET film was peeled off to expose the pressure-sensitive adhesive layer. After that, the entire surface of the exposed adhesive layer was laminated on a SUS304 plate, and a rubber roller (diameter: 85 mm, width: 50 mm) with a mass of 2 kg (load: 19.6 N) was reciprocated once to obtain a sample for measurement. . The obtained measurement sample was left for 30 minutes in an environment with a temperature of 23° C. and a relative humidity of 50% RH. After that, according to JIS K6854-2, peel speed 0.3 m / min. A tensile test in the direction of 180° was performed at , and the peel strength (N/25 mm) against the SUS304 plate was measured. Table 2 shows the results.
  • the heat-peelable pressure-sensitive adhesive sheet is peeled off from the adherend.
  • ⁇ When the heat-peelable pressure-sensitive adhesive sheet is lightly touched with a finger, it is peeled off from the adherend.
  • x The heat-peelable pressure-sensitive adhesive sheet does not separate from the adherend even when force is applied because the expansion is insufficient or the adhesive strength is too high.
  • a pressure-sensitive adhesive composition excluding the component (C) was prepared in the same manner as the above-described pressure-sensitive adhesive composition, except that the heat-expandable particles (C) were not blended.
  • a 75 ⁇ m-thick release PET film (HY-S10-2 manufactured by Higashiyama Film Co., Ltd.) was used instead of the corona-treated PET film, and the adhesive was removed from component (C) so that the film thickness after curing was 100 ⁇ m.
  • a heat-peelable pressure-sensitive adhesive sheet was prepared by curing in the same manner as in the preparation of the heat-peelable pressure-sensitive adhesive sheet described above, except that the agent composition was applied.
  • Examples 2 to 9, Comparative Examples 1 to 3 The adhesive compositions of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the compounds and blending amounts shown in Tables 2 and 3 were used to prepare heat-peelable adhesive sheets. was evaluated. At the same time, the gel fraction measurement of the cured product of the pressure-sensitive adhesive composition excluding the component (C) was performed. The results are shown in Tables 2 and 3.
  • the peeling force from the adherend is sufficiently high, and by heating after the completion of the process, it can be easily peeled from the adherend without causing contamination of the adherend surface.
  • a heat-peelable pressure-sensitive adhesive sheet can be provided.

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JP2012052038A (ja) * 2010-09-01 2012-03-15 Nitto Denko Corp 電子部品製造工程用仮固定シート
JP2012056985A (ja) * 2010-09-06 2012-03-22 Nitto Denko Corp 発泡粘着体
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
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
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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JP2019116609A (ja) 2017-12-26 2019-07-18 日東電工株式会社 光学部材用表面保護シート

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012052038A (ja) * 2010-09-01 2012-03-15 Nitto Denko Corp 電子部品製造工程用仮固定シート
JP2012056985A (ja) * 2010-09-06 2012-03-22 Nitto Denko Corp 発泡粘着体
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
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
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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