TWI651385B - Temperature sensitive adhesive, temperature sensitive adhesive sheet, temperature sensitive adhesive tape, manufacturing method of ceramic member, and manufacturing method of laminated ceramic capacitor - Google Patents
Temperature sensitive adhesive, temperature sensitive adhesive sheet, temperature sensitive adhesive tape, manufacturing method of ceramic member, and manufacturing method of laminated ceramic capacitor Download PDFInfo
- Publication number
- TWI651385B TWI651385B TW104107709A TW104107709A TWI651385B TW I651385 B TWI651385 B TW I651385B TW 104107709 A TW104107709 A TW 104107709A TW 104107709 A TW104107709 A TW 104107709A TW I651385 B TWI651385 B TW I651385B
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- Prior art keywords
- temperature
- sensitive adhesive
- meth
- alkyl group
- acrylate
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- 239000000853 adhesive Substances 0.000 title claims abstract description 61
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 60
- 239000002390 adhesive tape Substances 0.000 title claims description 34
- 239000000919 ceramic Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000003985 ceramic capacitor Substances 0.000 title claims description 11
- -1 polysiloxane Polymers 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 239000012790 adhesive layer Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 16
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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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
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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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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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
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- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
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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
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
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- 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
- C09J7/35—Heat-activated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
- H01G4/308—Stacked capacitors made by transfer techniques
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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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
- 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
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
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- Chemical & Material Sciences (AREA)
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- Ceramic Engineering (AREA)
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Abstract
本發明之感溫性黏著劑係含有藉由使至少具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯聚合所得之側鏈結晶性聚合物，以前述側鏈結晶性聚合物之未達融點之溫度降低黏著力。前述側鏈結晶性聚合物為進一步使反應性聚矽氧烷化合物聚合所得之共聚物，前述至少具有碳數16以上之直鏈狀烷基之(甲基)丙烯酸酯及前述反應性聚矽氧烷化合物之比率，以重量比計，至少具有碳數16以上之直鏈狀烷基之(甲基)丙烯酸酯：反應性聚矽氧烷化合物=91：9至99：1。 The temperature-sensitive adhesive of the present invention contains a side chain crystalline polymer obtained by polymerizing a (meth) acrylate having a linear alkyl group having at least 16 carbon atoms, and the side chain crystalline polymer is Temperatures below the melting point reduce adhesion. The side chain crystalline polymer is a copolymer obtained by further polymerizing a reactive polysiloxane compound, the (meth) acrylate having at least a linear alkyl group having 16 or more carbon atoms, and the reactive polysiloxane The ratio of the alkane compound is a (meth) acrylate having at least a linear alkyl group having 16 or more carbon atoms by weight ratio: a reactive polysiloxane compound = 91: 9 to 99: 1.
Description
本發明係可藉由熱而可逆性控制黏著力之感溫性黏著劑。 The present invention is a thermosensitive adhesive capable of reversibly controlling adhesion by heat.
感溫性黏著劑係可藉由熱而可逆性控制黏著力之感溫性黏著劑。更具體地，感溫性黏著劑係若冷卻至含有主成分之側鏈結晶性聚合物的未達融點之溫度時，可藉由側鏈結晶性聚合物的結晶化而降低黏著力者。 The temperature-sensitive adhesive is a temperature-sensitive adhesive that can control the adhesive force reversibly by heat. More specifically, if the temperature-sensitive adhesive is cooled to a temperature below the melting point of the side chain crystalline polymer containing the main component, the adhesive force can be reduced by crystallization of the side chain crystalline polymer.
作為感溫性黏著劑之一使用形態的感溫性黏著膠帶係適用於積層陶瓷電容器等之陶瓷構件的製造(例如參照特許文獻1)。在陶瓷構件之製造中，感溫性黏著膠帶係使用於構件之暫時固定用途。如此之用途所使用之感溫性黏著膠帶，係希望為將一度貼黏之黏著膠帶再剝離後，黏著性與剝離性之均衡性優異者。 The temperature-sensitive adhesive tape used as one of the temperature-sensitive adhesives is suitable for the manufacture of ceramic members such as laminated ceramic capacitors (for example, refer to Patent Document 1). In the manufacture of ceramic components, thermosensitive adhesive tapes are used for temporary fixing of components. The temperature-sensitive adhesive tape used for such applications is preferably one which is excellent in the balance between the adhesiveness and the peelability after the once-adhesive adhesive tape is peeled again.
另一方面，本案申請人係先開發出一種藉由將反應性聚矽氧烷化合物與側鏈結晶性聚合物共聚合而發揮優異之剝離性的特許文獻2所述之感溫性黏著膠帶。反應性聚矽氧烷化合物係因價格比較高，故希望使之共聚合的比率愈少愈好。又，若反應性聚矽氧烷化合物之比率 變多，有感溫性黏著膠帶之黏著性與剝離性之均衡性有變得不安定之虞。 On the other hand, the applicant of the present application first developed a thermosensitive adhesive tape described in Patent Document 2 that exhibits excellent peelability by copolymerizing a reactive polysiloxane compound and a side chain crystalline polymer. Since the reactive polysiloxane compound is relatively expensive, it is desirable to make the copolymerization ratio as small as possible. If the ratio of the reactive polysiloxane compound is As the number increases, the balance between the adhesiveness and the peelability of the temperature-sensitive adhesive tape may become unstable.
[特許文獻1]日本特開平9-251923號公報 [Patent Document 1] Japanese Patent Laid-Open No. 9-251923
[特許文獻2]日本特許第5231775號公報 [Patent Document 2] Japanese Patent No. 5231775
本發明之課題係提供一種可降低成本，且黏著性及剝離性之均衡性優異的感溫性黏著劑。 An object of the present invention is to provide a temperature-sensitive adhesive which can reduce cost and is excellent in the balance between adhesiveness and peelability.
本發明之感溫性黏著劑，係含有藉由使至少具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯聚合所得之側鏈結晶性聚合物，以前述側鏈結晶性聚合物之未達融點之溫度降低黏著力，前述側鏈結晶性聚合物係包含藉由使反應性聚矽氧烷化合物進一步聚合所得之共聚物，前述至少具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯及前述反應性聚矽氧烷化合物之比率，以重量比計，至少具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯：反應性聚矽氧烷化合物=91：9至99：1。 The temperature-sensitive adhesive of the present invention contains a side chain crystalline polymer obtained by polymerizing a (meth) acrylate having a linear alkyl group having at least 16 carbon atoms, and is polymerized by the side chain crystalline The temperature below the melting point of the material reduces the adhesive force. The aforementioned side chain crystalline polymer includes a copolymer obtained by further polymerizing a reactive polysiloxane compound, and the aforementioned linear alkane having at least 16 carbon atoms. The ratio of the (meth) acrylic acid ester based on the base and the reactive polysiloxane compound is based on the weight ratio, and the (meth) acrylic acid ester having at least a linear alkyl group having 16 or more carbons: Alkanes = 91: 9 to 99: 1.
若依據本發明，具有可降低成本，且黏著性及剝離性之均衡性優異的效果。 According to the present invention, it is possible to reduce the cost and to provide an excellent balance between adhesion and peelability.
以下，詳細說明有關本發明之一實施形態的感溫性黏著劑。本實施形態之感溫性黏著劑係含有側鏈結晶性聚合物。側鏈結晶性聚合物係具有融點之聚合物。所謂融點係藉由某種平衡程序，最初係被整合成有秩序排列的聚合體之特定部分變成無秩序狀態之溫度，藉示差熱掃描熱量計(DSC)而以10℃/分之測定條件測定所得之值。 Hereinafter, a temperature-sensitive adhesive according to an embodiment of the present invention will be described in detail. The temperature-sensitive adhesive of this embodiment contains a side chain crystalline polymer. The side chain crystalline polymer is a polymer having a melting point. The so-called melting point is the temperature at which a specific part of an aggregate that is integrated into an ordered array becomes disordered at first through some equilibrium procedure. It is measured by a differential scanning calorimeter (DSC) at 10 ° C / min. The value obtained.
側鏈結晶性聚合物係以上述的未達融點之溫度進行結晶化，且在融點以上之溫度進行相轉移而顯示流動性。亦即，側鏈結晶性聚合物係具有對應於溫度變化，可逆性地造成結晶狀態與流動狀態之感溫性。而且，本實施形態之感溫性黏著劑係以側鏈結晶性聚合物以未達融點之溫度進行結晶化時黏著力降低之比率含有側鏈結晶性聚合物。也就是說，本實施形態之感溫性黏著劑係含有側鏈結晶性聚合物作為主成分，且實質上藉由側鏈結晶性聚合物而構成，故從構件剝離感溫性黏著劑時，若使感溫性黏著劑冷卻至側鏈結晶性聚合物之未達融點之溫度，會由於側鏈結晶性聚合物的結晶化而降低黏著力。又，若使感溫性黏著劑加熱至側鏈結晶性聚合物之融點以上之溫度，側鏈結晶性聚合物顯示流動性而恢復黏著力，故可重複使用。 The side chain crystalline polymer is crystallized at a temperature below the melting point described above, and undergoes phase transfer at a temperature above the melting point to exhibit fluidity. That is, the side chain crystalline polymer has a temperature sensitivity that reversibly causes a crystalline state and a flowing state in response to a temperature change. In addition, the temperature-sensitive adhesive of the present embodiment contains the side chain crystalline polymer at a rate at which the adhesion decreases when the side chain crystalline polymer is crystallized at a temperature not reaching the melting point. That is, the temperature-sensitive adhesive of this embodiment contains a side-chain crystalline polymer as a main component and is substantially composed of a side-chain crystalline polymer. Therefore, when the temperature-sensitive adhesive is peeled from a member, If the temperature-sensitive adhesive is cooled to a temperature below the melting point of the side chain crystalline polymer, the adhesion force will be reduced due to the crystallization of the side chain crystalline polymer. In addition, if the temperature-sensitive adhesive is heated to a temperature above the melting point of the side-chain crystalline polymer, the side-chain crystalline polymer exhibits fluidity and restores adhesion, so it can be reused.
就融點而言，以30℃以上為較佳，以40至65℃為更佳，以50至60℃為最佳。融點係可藉由調整側鏈結晶性聚合物之組成等而控制成所希望之值。本實施形態之側鏈結晶性聚合物係包含：藉由使具有至少碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯、及反應性聚矽氧烷化合物聚合所得之共聚物。 In terms of melting point, 30 ° C or higher is preferable, 40 to 65 ° C is more preferable, and 50 to 60 ° C is most preferable. The melting point can be controlled to a desired value by adjusting the composition of the side chain crystalline polymer and the like. The side chain crystalline polymer of this embodiment includes a copolymer obtained by polymerizing a (meth) acrylate having a linear alkyl group having at least 16 carbon atoms and a reactive polysiloxane compound.
具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯係其碳數16以上之直鏈狀烷基發揮側鏈結晶性聚合物中之側鏈結晶性部位的作用。亦即，側鏈結晶性聚合物係於側鏈具有碳數16以上之直鏈狀烷基的梳形之聚合物，此側鏈藉由分子間力等而整合成有秩序之排列以進行結晶化。如此之具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯係可舉例如(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十烷基酯、(甲基)丙烯酸二十二烷基酯等之具有碳數16至22之線狀烷基的(甲基)丙烯酸酯，此等係1種或混合2種以上而使用。所例示之此等(甲基)丙烯酸酯之中，以(甲基)丙烯酸二十二烷基酯為較佳。又，(甲基)丙烯酸酯係意指丙烯酸酯或甲基丙烯酸酯。 The (meth) acrylic acid ester having a linear alkyl group having 16 or more carbon atoms has a linear alkyl group having 16 or more carbon atoms serving as a side chain crystalline site in the side chain crystalline polymer. That is, the side-chain crystalline polymer is a comb-shaped polymer having a linear alkyl group having 16 or more carbon atoms in the side chain, and this side chain is integrated into an orderly arrangement by intermolecular force to perform crystallization. Into. Examples of the (meth) acrylic acid ester having a linear alkyl group having 16 or more carbon atoms include cetyl (meth) acrylate, stearyl (meth) acrylate, and eicosane (meth) acrylate. (Meth) acrylates having a linear alkyl group having 16 to 22 carbons such as benzyl (meth) acrylate and behenyl (meth) acrylate, and these are used alone or in combination of two or more. Among these (meth) acrylates exemplified, behenyl (meth) acrylate is preferred. The (meth) acrylate means an acrylate or a methacrylate.
反應性聚矽氧烷化合物意指具有顯示反應性之官能基，且於主鏈具有矽氧烷鍵之聚矽氧烷化合物。反應性聚矽氧烷化合物係在室溫(23℃)可為蠟狀，但在效率佳使之聚合的方面，在室溫顯示流動性之油狀、亦即聚矽氧油為較佳。 The reactive polysiloxane compound means a polysiloxane compound having a functional group exhibiting reactivity and having a siloxane bond in the main chain. The reactive polysiloxane compound may be waxy at room temperature (23 ° C), but in terms of efficient polymerization, it is preferably an oily substance that exhibits fluidity at room temperature, that is, polysiloxane oil.
又、上述之官能基係可舉例如乙烯基、烯 丙基、(甲基)丙烯酸基、(甲基)丙烯醯基、(甲基)丙烯醯氧基等之乙烯性不飽和雙鍵；環氧基(包含縮水甘油基及環氧基環烷基)、氫硫基、甲醇基、羧基、矽烷醇基、酚基、胺基、羥基等。 In addition, the functional groups described above may be, for example, vinyl, olefin Ethylenically unsaturated double bonds such as propyl, (meth) acrylic, (meth) acrylfluorenyl, (meth) acrylfluorenyl, etc .; epoxy (including glycidyl and epoxycycloalkyl ), Hydrogen thio group, methanol group, carboxyl group, silanol group, phenol group, amine group, hydroxyl group and the like.
所例示之官能基係可導入於主鏈所具有之側鏈，亦可導入於主鏈之兩末端或單末端。亦即，反應性聚矽氧烷化合物係依所導入之官能基的鍵結位置，可舉例如所謂側鏈型、兩末端型、單末端型及側鏈兩末端型之4種類，尤其，可得到優異之黏著性與剝離性外，以單末端型，亦即單末端反應性聚矽氧烷化合物為較佳。推斷此理由係若使用單末端型而聚合，可於聚合體之主鏈使聚矽氧烷成分呈梳形接枝，藉此，無損黏著性，且側鏈結晶性聚合物經結晶化時以聚矽氧烷化合物所產生之離型性有效率地顯現。 The exemplified functional group may be introduced into a side chain of the main chain, or may be introduced into both ends or a single end of the main chain. That is, the reactive polysiloxane compound may be, for example, four types of a side chain type, a two terminal type, a single terminal type, and a side chain both terminal type depending on a bonding position of a functional group to be introduced. In addition to obtaining excellent adhesion and peelability, a single-end type, that is, a single-end reactive polysiloxane compound is preferred. It is presumed that if the polymerization is performed using a single-end type, the polysiloxane component can be graft-grafted on the main chain of the polymer, thereby preventing loss of adhesion and crystallization of the side chain crystalline polymer. The release property produced by the polysiloxane compound is effectively exhibited.
單末端反應性聚矽氧烷化合物之具體例係可舉例如以下述通式(I)所示之改質聚二甲基矽氧烷化合物。此化合物係與上述具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯之相溶性優異，故可效率佳地得到共聚物。 Specific examples of the single-terminal reactive polysiloxane compound include modified polydimethylsiloxane compounds represented by the following general formula (I). This compound is excellent in compatibility with the aforementioned (meth) acrylate having a linear alkyl group having a carbon number of 16 or more, so that a copolymer can be obtained efficiently.
通式I)中，R1表示之烷基係可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、戊基、異戊基、新戊基、己基等之碳數1至6之直鏈或分支的烷基。R3表示之伸烷基係可舉例如亞甲基、亞乙基、三亞甲基、甲基伸乙基、伸丙基、四亞甲基、五亞甲基、六亞甲基等之碳數1至6之直鏈或分枝的伸烷基等。 Examples of the alkyl group represented by R 1 in the general formula I) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, Pentyl, isopentyl, neopentyl, hexyl, etc. straight or branched alkyl groups having 1 to 6 carbon atoms. Examples of the alkylene group represented by R 3 include carbons such as methylene, ethylene, trimethylene, methylethylene, propylene, tetramethylene, pentamethylene, and hexamethylene. Straight-chain or branched alkylene groups of 1 to 6, etc.
以通式(I)所示之改質聚二甲基矽氧烷化合物之具體例係可舉例如下述以通式(I)所示之化合物等。 Specific examples of the modified polydimethylsiloxane compound represented by the general formula (I) include the following compounds represented by the general formula (I).
改質聚二甲基矽氧烷化合物係可使用市售者，具體例可舉例如任一者均為信越化學工業(股)製之單末端反應性聚矽氧油「X-22-2475」、「X-24-8201」、「X-22-2426」、「KF-2012」等。 Modified polydimethylsiloxane compounds are commercially available. Specific examples include a single-end reactive polysiloxane oil "X-22-2475" manufactured by Shin-Etsu Chemical Industry Co., Ltd. , "X-24-8201", "X-22-2426", "KF-2012", etc.
另一方面，上述之具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯、及反應性聚矽氧烷化合物之共聚物所構成之本實施形態的側鏈結晶性聚合物係可進一步使例如具有碳數1至8之烷基的(甲基)丙烯酸酯、極性單體等聚合。 On the other hand, the side chain crystalline polymer system according to this embodiment, which is a copolymer of a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms and a reactive polysiloxane compound, as described above. For example, a (meth) acrylate having a C1-C8 alkyl group, a polar monomer, or the like can be further polymerized.
具有碳數1至8之烷基的(甲基)丙烯酸酯係 可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯等，此等係可1種或混合2種以上而使用。所例示之此等的(甲基)丙烯酸酯之中，以(甲基)丙烯酸甲酯為較佳。 (Meth) acrylic esters having alkyl groups having 1 to 8 carbon atoms Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate. These may be used alone or in combination of two or more. Among these (meth) acrylates exemplified, methyl (meth) acrylate is preferred.
極性單體係可舉例如丙烯酸、甲基丙烯酸、巴豆酸、伊康酸、馬來酸、富馬酸等之含有羧基之乙烯不飽和單體；(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥己酯等之具有羥基之乙烯不飽和單體等，此等係可1種或混合2種以上而使用。所例示之此等極性單體之中以丙烯酸為較佳。 Examples of polar monosystems include ethylenically unsaturated monomers containing carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; 2-hydroxyethyl (meth) acrylate, ( The ethylenically unsaturated monomers having a hydroxyl group, such as 2-hydroxypropyl (meth) acrylate and 2-hydroxyhexyl (meth) acrylate, etc., may be used singly or in combination of two or more. Among the exemplified polar monomers, acrylic acid is preferred.
此處，本實施形態係至少具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯及反應性聚矽氧烷化合物之比率，以重量比計，至少具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯：反應性聚矽氧烷化合物=91：9至99：1，較佳係95：5至99：1，更佳係96：4至99：1。如此之比率係價格比較高之反應性聚矽氧烷化合物之比率少，因此，若依本實施形態，可降低成本。又，若採用上述之比率，可抑制因反應性聚矽氧烷化合物之比率變多而使感溫性黏著劑之黏著性與剝離性之均衡性造成的不安定，同時可得到由聚矽氧烷化合物所產生的離型性，故即使黏著力提高設計，剝離時亦可充分降低黏著力，結果，可發揮優異之黏著性及剝離性。 Here, the ratio of the (meth) acrylic acid ester having a linear alkyl group having at least 16 carbon atoms and the reactive polysiloxane compound in the present embodiment has at least 16 carbon atoms in terms of weight ratio. (Meth) acrylate of chain alkyl group: Reactive polysiloxane compound = 91: 9 to 99: 1, preferably 95: 5 to 99: 1, more preferably 96: 4 to 99: 1. Such a ratio is small because the ratio of a relatively expensive reactive polysiloxane compound is small. Therefore, according to this embodiment, costs can be reduced. In addition, if the above ratio is used, it is possible to suppress the instability caused by the increase in the ratio of the reactive polysiloxane compound and the balance between the adhesiveness and the releasability of the thermosensitive adhesive. Since the release property of the alkane compound is high, even if the design of the adhesion is improved, the adhesion can be sufficiently reduced during peeling. As a result, excellent adhesion and peelability can be exhibited.
上述之具有至少碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯，在僅有具有碳數16以上之直鏈狀烷基 的(甲基)丙烯酸酯與反應性聚矽氧烷化合物聚合時，係意指為具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯，進一步使上述之具有碳數1至8之烷基的(甲基)丙烯酸酯、極性單體等聚合時，係意指進一步含有具有碳數1至8之烷基的(甲基)丙烯酸酯、極性單體等。 The (meth) acrylic acid esters having a linear alkyl group having at least 16 carbon atoms are the only linear alkyl groups having a carbon number of 16 or more. When (meth) acrylate is polymerized with a reactive polysiloxane compound, it means a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, and further having the above-mentioned carbon number of 1 to When the (meth) acrylic acid ester, polar monomer, etc. of the alkyl group of 8 is polymerized, it means the (meth) acrylic acid ester, polar monomer, etc. which further have an alkyl group having 1 to 8 carbon atoms.
進一步使具有碳數1至8之烷基的(甲基)丙烯酸酯及極性單體聚合時之比率係以重量比計，較佳係具有碳數16以上之直鏈狀烷基的(甲基)丙烯酸酯：具有碳數1至8之烷基的(甲基)丙烯酸酯：極性單體：反應性聚矽氧烷化合物=44至46：39至51：4至6：1至9，更佳係44至46：43至51：4至6：1至5，最佳係44至46：44至51：4至6：1至4。 The ratio of the (meth) acrylic acid ester having an alkyl group having 1 to 8 carbons and the polar monomer when polymerization is further based on a weight ratio, and preferably the (methyl group having a linear alkyl group having 16 or more carbon atoms) ) Acrylate: (meth) acrylate having an alkyl group having 1 to 8 carbons: polar monomer: reactive polysiloxane compound = 44 to 46: 39 to 51: 4 to 6: 1 to 9 and more The best line is 44 to 46:43 to 51: 4 to 6: 1 to 5, and the best line is 44 to 46:44 to 51: 4 to 6: 1 to 4.
聚合方法係並無特別限定，可採用例如溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等。採用溶液聚合法時係只要將上述之單體混合於溶劑中，以40至90℃左右攪拌2至10小時左右即可。 The polymerization method is not particularly limited, and for example, a solution polymerization method, a block polymerization method, a suspension polymerization method, an emulsion polymerization method, and the like can be adopted. In the case of the solution polymerization method, the above-mentioned monomers can be mixed in a solvent and stirred at about 40 to 90 ° C for about 2 to 10 hours.
構成側鏈結晶性聚合物之共聚物之重量平均分子量，較佳為25萬至100萬，更佳為50萬至70萬。重量平均分子量係將共聚物藉由凝膠滲透層析(GPC)測定所得之測定值以聚苯乙烯換算之值。 The weight average molecular weight of the copolymer constituting the side chain crystalline polymer is preferably 250,000 to 1 million, and more preferably 500,000 to 700,000. The weight-average molecular weight is a value obtained by measuring the copolymer by gel permeation chromatography (GPC) in terms of polystyrene.
本實施形態較佳係在80℃之環境溫度中對於聚對苯二甲酸乙二酯薄膜之180°剝離強度為0.1N/25mm以上，以0.2N/25mm以上更佳。藉此，即使在高溫環境下以可固定構件。在80℃之環境溫度中對於聚對苯二甲酸乙 二酯薄膜的180°剝離強度係依據JIS Z0237而測定所得到之值。 In this embodiment, the 180 ° peel strength of the polyethylene terephthalate film at an ambient temperature of 80 ° C. is preferably 0.1N / 25mm or more, and more preferably 0.2N / 25mm or more. Thereby, the members can be fixed even in a high-temperature environment. For polyethylene terephthalate at an ambient temperature of 80 ° C The 180 ° peel strength of the diester film is a value measured in accordance with JIS Z0237.
又，本實施形態較佳係在23℃之環境溫度中對於聚對苯二甲酸乙二酯薄膜之180°剝離強度為0.1N/25mm，以0.05N/25mm以下為更佳。藉此，可從構件順利地剝離。在23℃之環境溫度中對於聚對苯二甲酸乙二酯薄膜之180°剝離強度係在80℃之環境溫度中貼黏於聚對苯二甲酸乙二酯薄膜後，使環境溫度從80℃冷卻至23℃，使180°剝離強度依據JIS Z0237而測定所得之值。 In this embodiment, the 180 ° peel strength of the polyethylene terephthalate film at an ambient temperature of 23 ° C. is preferably 0.1 N / 25 mm, and more preferably 0.05 N / 25 mm or less. Thereby, peeling from a member can be performed smoothly. The 180 ° peel strength of the polyethylene terephthalate film at an ambient temperature of 23 ° C is obtained by adhering the polyethylene terephthalate film at an ambient temperature of 80 ° C, and the ambient temperature is changed from 80 ° C. After cooling to 23 ° C, the 180 ° peel strength was measured in accordance with JIS Z0237.
上述之本實施形態之感溫性黏著劑係例如可以無基材之片狀之形態使用。使用感溫性黏著劑作為感溫性黏著片時，其厚度以5至100μm為較佳，以10至50μm更佳。 The above-mentioned thermosensitive adhesive of the present embodiment can be used in the form of a sheet without a substrate, for example. When a temperature-sensitive adhesive is used as the temperature-sensitive adhesive sheet, the thickness is preferably 5 to 100 μm, and more preferably 10 to 50 μm.
又，本實施形態之感溫性黏著劑係亦可以膠帶狀之形態使用。使用感溫性黏著劑作為感溫性黏著膠帶時，只要使由感溫性黏著劑所構成之黏著劑層積層於薄膜狀之基材之單面或兩面即可。所謂薄膜狀係並非僅限定於薄膜狀，只要無損及本實施形態之效果，亦包含薄膜狀乃至片狀之概念。 Moreover, the thermosensitive adhesive system of this embodiment can also be used in the form of a tape. When a thermosensitive adhesive is used as the thermosensitive adhesive tape, an adhesive composed of a thermosensitive adhesive may be laminated on one or both sides of a film-shaped substrate. The so-called film-like system is not limited to a film-like system, and includes the concept of a film-like or even a sheet-like film as long as the effect of this embodiment is not impaired.
基材之構成材料係可舉例如聚乙烯、聚對苯二甲酸乙二酯、聚丙烯、聚酯、聚醯胺、聚醯亞胺、聚碳酸酯、乙烯乙酸乙烯酯共聚物、乙烯乙基丙烯酸酯共聚物、乙烯聚丙烯共聚物、聚氯乙烯等之合成樹脂。 The material of the base material can be, for example, polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl Synthetic resins such as acrylate copolymer, ethylene polypropylene copolymer, and polyvinyl chloride.
基材係可為單層體或複層體之任一者，其 厚度一般為5至500μm左右。基材係就提高對於黏著劑層之密著性上，可施予例如電暈處理、電漿處理、噴砂處理、化學蝕刻處理、底漆處理等之表面處理。 The substrate system may be any of a single layer body and a multilayer body. The thickness is generally about 5 to 500 μm. The base material can improve the adhesion to the adhesive layer, and can be subjected to surface treatments such as corona treatment, plasma treatment, sandblasting treatment, chemical etching treatment, and primer treatment.
於基材之單面或兩面設有黏著劑層，係只要將於感溫性黏著劑中加入溶劑之塗布液藉由塗佈器等而塗佈於基材之單面或兩面而使之乾燥即可。塗佈器係可舉例如刮刀塗佈器、輥塗佈器、輾壓塗佈器、缺角輪塗佈器、凹版塗佈器、桿棒塗佈器等。 Adhesive layers are provided on one or both sides of the substrate, as long as the coating solution in which a solvent is added to the thermosensitive adhesive is applied to one or both sides of the substrate through a coater and the like, and dried. Just fine. Examples of the applicator include a blade applicator, a roll applicator, a roll applicator, a notch wheel applicator, a gravure applicator, and a rod applicator.
黏著劑層之厚度係以5至60μm為較佳，以10至60μm為更佳，以10至50μm為最佳。單面之黏著劑層之厚度、及另一面之黏著劑層之厚度係可為相同，亦可為相異。 The thickness of the adhesive layer is preferably 5 to 60 μm, more preferably 10 to 60 μm, and most preferably 10 to 50 μm. The thickness of the adhesive layer on one side and the thickness of the adhesive layer on the other side may be the same or different.
又，本實施形態係只要單面之黏著劑層由感溫性黏著劑所構成，另一面之黏著劑層係無特別限定。使另一面之黏著劑層以例如由感溫性黏著劑所構成之黏著劑層構成時，其組成係可與單面之黏著劑層之組成相同，亦可相異。 In this embodiment, as long as the adhesive layer on one side is made of a thermosensitive adhesive, the adhesive layer on the other side is not particularly limited. When the adhesive layer on the other side is composed of, for example, an adhesive layer composed of a thermosensitive adhesive, its composition may be the same as or different from that of the one-sided adhesive layer.
又，亦可使另一面之黏著劑層以例如感壓性接著劑所構成之黏著劑層構成。感壓性接著劑係具有黏著性之聚合物，可舉例如天然橡膠接著劑、合成橡膠接著劑、苯乙烯/丁二烯乳膠基質接著劑、丙烯酸系接著劑等。 Moreover, the adhesive layer on the other surface may be comprised with the adhesive layer which consists of a pressure sensitive adhesive, for example. The pressure-sensitive adhesive is an adhesive polymer, and examples thereof include natural rubber adhesives, synthetic rubber adhesives, styrene / butadiene latex matrix adhesives, and acrylic adhesives.
上述之感溫性黏著片及感溫性黏著膠帶之表面係以積層離型薄膜為較佳。離型薄膜係可舉例如於由聚對苯二甲酸乙二酯等所構成之薄膜之表面，塗佈聚矽氧 等之離型劑者等。又，上述之感溫性黏著劑、感溫性黏著片及感溫性黏著膠帶係可添加例如交聯劑、增黏劑、可塑劑、抗老化劑、紫外線吸收劑等之各種添加劑。 The surface of the above-mentioned thermosensitive adhesive sheet and thermosensitive adhesive tape is preferably a laminated release film. The release film can be, for example, coated with polysiloxane on the surface of a film made of polyethylene terephthalate. Wait for the release agent and so on. In addition, various additives such as a cross-linking agent, a tackifier, a plasticizer, an anti-aging agent, and an ultraviolet absorber can be added to the above-mentioned thermosensitive adhesive, thermosensitive adhesive sheet, and thermosensitive adhesive tape.
然後，說明有關本發明之一實施形態的陶瓷構件之製造方法及積層陶瓷電容器之製造方法。本實施形態之陶瓷構件之製造方法係使用上述之感溫性黏著膠帶，同時具備以下之(i)至(iv)之步驟。本實施形態之積層陶瓷電容器之製造方法係更具備以下之(v)之步驟。 Next, a method for manufacturing a ceramic member and a method for manufacturing a multilayer ceramic capacitor according to an embodiment of the present invention will be described. The manufacturing method of the ceramic member of this embodiment uses the above-mentioned temperature-sensitive adhesive tape and includes the following steps (i) to (iv). The method for manufacturing a multilayer ceramic capacitor according to this embodiment further includes the following step (v).
(i)將感溫性黏接膠帶貼黏於陶瓷生胚片積層體。 (i) Stick the thermosensitive adhesive tape to the ceramic green sheet laminate.
(ii)隔著感溫性黏著膠帶而將陶瓷生胚片積層體固定於基座上。 (ii) The ceramic green sheet laminate is fixed to the base via a thermosensitive adhesive tape.
(iii)切斷陶瓷生胚片積層體而形成複數之初粒體。 (iii) The ceramic green sheet laminate is cut to form a plurality of primary granules.
(iv)使感溫性黏著膠帶設為側鏈結晶性聚合物之未達融點的溫度，以降低黏著劑層之黏著力，並從感溫性黏著膠帶取出前述複數之初粒體。 (iv) The temperature-sensitive adhesive tape is set to a temperature below the melting point of the side chain crystalline polymer to reduce the adhesive force of the adhesive layer, and the plurality of primary particles are taken out from the temperature-sensitive adhesive tape.
(v)燒成所得之初粒體而得到陶瓷粒體，於陶瓷粒體之端面形成外部電極以得到積層陶瓷電容器。 (v) The obtained primary particles are fired to obtain ceramic particles, and external electrodes are formed on the end faces of the ceramic particles to obtain a multilayer ceramic capacitor.
上述之(i)至(v)之步驟中，(i)及(ii)之步驟係所謂之積層步驟，(iii)之步驟係所謂之裁切步驟，(iv)之步驟係所謂之分離步驟。若依本實施形態，因使用發揮優異之黏著性及剝離性的上述感溫性黏著膠帶，故可確實地進 行(i)至(v)之步驟，結果，可良率佳地得到陶瓷構件及積層陶瓷電容器。 Among the above steps (i) to (v), the steps (i) and (ii) are so-called lamination steps, the step (iii) is a so-called cutting step, and the step (iv) is a so-called separation step . According to this embodiment, since the above-mentioned temperature-sensitive adhesive tape exhibiting excellent adhesiveness and releasability is used, it can be reliably advanced. By performing steps (i) to (v), as a result, a ceramic member and a multilayer ceramic capacitor can be obtained with good yield.
又，(i)之步驟中的陶瓷生胚片積層體係使陶瓷粉末之漿液以刮刀薄化延伸，形成陶瓷生胚片，於此陶瓷生胚片之表面印刷複數之電極後，使複數之陶瓷生胚片積層一體化而得到。 In addition, the ceramic green sheet lamination system in the step (i) enables the ceramic powder slurry to be thinned and extended by a doctor blade to form a ceramic green sheet. After printing a plurality of electrodes on the surface of the ceramic green sheet, a plurality of ceramics are made. The green slabs are laminated and integrated.
(ii)之步驟中於基座上之固定方法係無特別限定，可舉例如採用：於感溫性黏著膠帶之基材、及基座之間介入特定之黏著劑或接著劑而固定之方法、或具備吸附機構等之固定手段的基座之方法等。又，感溫性黏著膠帶之構成於基材薄膜之兩面設有黏著劑層之兩面膠帶時，係亦可隔著與貼黏陶瓷生胚片積層體之單面黏著劑層相反之另一面之黏著劑層，固定於基座上。 The method of fixing on the base in the step of (ii) is not particularly limited, and for example, a method of fixing between the base material of the thermosensitive adhesive tape and a specific adhesive or adhesive between the base may be used. Or a pedestal having a fixing means such as an adsorption mechanism. In addition, when the temperature-sensitive adhesive tape is composed of a two-sided adhesive tape having adhesive layers on both sides of the base film, it may be on the other side opposite to the one-sided adhesive layer of the laminated ceramic green sheet laminate. An adhesive layer is fixed on the base.
(iii)之步驟中之切斷係可為以切割刀之裁切，亦可為以旋轉刀之裁斷。 The cutting in the step (iii) may be cutting with a cutting knife or cutting with a rotary knife.
本實施形態之陶瓷構件之製造方法係除上述積層陶瓷電容器之外，亦可適用於有關例如陶瓷電感器、陶瓷變阻器等之其他陶瓷構件。 In addition to the multilayer ceramic capacitor described above, the manufacturing method of the ceramic component of this embodiment can also be applied to other ceramic components such as ceramic inductors and ceramic varistors.
以下，舉出合成例及實施例而詳細說明本發明，但本發明係並非僅限定於以下之合成例及實施例。又，以下之說明中「份」係意指重量份。 Hereinafter, the present invention will be described in detail by taking synthesis examples and examples, but the present invention is not limited to the following synthesis examples and examples. In addition, "part" in the following description means a weight part.
以日油公司製之丙烯酸二十二烷基酯45份、日本觸媒 公司製之丙烯酸甲酯49份、丙烯酸5份、改質聚二甲基矽氧烷化合物1份、及作為聚合開始劑之日油公司製的「Perbutyl ND」0.2份之比率分別加入於乙酸乙酯230份中並混合，以55℃攪拌4小時，使此等之單體聚合。所得之共聚物之重量平均分子量為58萬，融點為56℃。又，所使用之改質聚二甲基矽氧烷化合物係如下述。 45 parts of behenyl acrylate manufactured by Nippon Oil Co., Ltd. A ratio of 49 parts of methyl acrylate, 5 parts of acrylic acid, 1 part of modified polydimethylsiloxane compound, and 0.2 parts of "Perbutyl ND" made by Nippon Oil Co., Ltd. as polymerization initiators were added to ethyl acetate 230 parts of the ester were mixed, and stirred at 55 ° C for 4 hours to polymerize these monomers. The obtained copolymer had a weight average molecular weight of 580,000 and a melting point of 56 ° C. The modified polydimethylsiloxane compound used is as follows.
改質聚二甲基矽氧烷化合物：上述之以通式(I)所示之信越化学工業(股)製之單末端反應性聚矽氧油「KF-2012」 Modified polydimethylsiloxane compound: Single-end reactive polysiloxane oil "KF-2012" manufactured by Shin-Etsu Chemical Industry Co., Ltd. represented by the above general formula (I)
除使丙烯酸二十二烷基酯為45份、丙烯酸甲酯為46份、丙烯酸為5份、改質聚二甲基矽氧烷化合物為4份以外，其餘係與合成例1同様之方式，使此等之單體聚合。所得之共聚物之重量平均分子量為63萬、融點為55℃。 Except that 45 parts of behenyl acrylate, 46 parts of methyl acrylate, 5 parts of acrylic acid, and 4 parts of modified polydimethylsiloxane compound were used, the rest were the same as in Synthesis Example 1. These monomers are polymerized. The obtained copolymer had a weight-average molecular weight of 630,000 and a melting point of 55 ° C.
除使丙烯酸二十二烷基酯為45份、丙烯酸甲酯為45份、丙烯酸為5份、改質聚二甲基矽氧烷化合物為5份以外，其餘係與合成例1同様之方式，使此等之單體聚合。所得之共聚物之重量平均分子量為60萬、融點為55℃。 Except that 45 parts of behenyl acrylate, 45 parts of methyl acrylate, 5 parts of acrylic acid, and 5 parts of modified polydimethylsiloxane compound were used, the rest were the same as in Synthesis Example 1. These monomers are polymerized. The obtained copolymer had a weight average molecular weight of 600,000 and a melting point of 55 ° C.
除使丙烯酸二十二烷基酯為45份、丙烯酸甲酯為41份、丙烯酸為5份、改質聚二甲基矽氧烷化合物為9份以 外，其餘係與合成例1同様之方式，使此等之單體聚合。所得之共聚物之重量平均分子量為64萬、融點為56℃。 Except for 45 parts of behenyl acrylate, 41 parts of methyl acrylate, 5 parts of acrylic acid, and 9 parts of modified polydimethylsiloxane compound. In addition, the rest were polymerized in the same manner as in Synthesis Example 1. The obtained copolymer had a weight average molecular weight of 640,000 and a melting point of 56 ° C.
除使丙烯酸二十二烷基酯為45份、丙烯酸甲酯為50份、丙烯酸為5份，且不添加改質聚二甲基矽氧烷化合物以外，其餘係與合成例1同様之方式，使此等之單體聚合。所得之共聚物之重量平均分子量為62萬、融點為56℃。 Except that 45 parts of behenyl acrylate, 50 parts of methyl acrylate, and 5 parts of acrylic acid were not added, and the modified polydimethylsiloxane compound was not added, the rest was the same as in Synthesis Example 1. These monomers are polymerized. The obtained copolymer had a weight average molecular weight of 620,000 and a melting point of 56 ° C.
除使丙烯酸二十二烷基酯為45份、丙烯酸甲酯為40份、丙烯酸為5份，改質聚二甲基矽氧烷化合物為10份以外，其餘係與合成例1同様之方式，使此等之單體聚合。所得之共聚物之重量平均分子量為66萬、融點為56℃。 Except that 45 parts of behenyl acrylate, 40 parts of methyl acrylate, 5 parts of acrylic acid, and 10 parts of modified polydimethylsiloxane compound were used, the rest were the same as in Synthesis Example 1. These monomers are polymerized. The obtained copolymer had a weight average molecular weight of 660,000 and a melting point of 56 ° C.
將合成例1至4及比較合成例1至2之共聚物表示於表1。又，重量平均分子量係使共聚物以GPC測定，將所得之測定值藉由聚苯乙烯換算而得。融點係使共聚物以DSC以10℃/分之測定條件測定而得。 The copolymers of Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 2 are shown in Table 1. The weight-average molecular weight is determined by measuring the copolymer by GPC, and the obtained measured value is obtained by converting polystyrene. The melting point is obtained by measuring the copolymer under DSC measurement conditions of 10 ° C / min.
首先，將合成例1至4及比較合成例1至2所得之各共聚物藉由乙酸乙酯而調整成固形分為30重量%，得到塗布液。其次，將塗布液塗佈於厚度100μm之聚對苯二甲酸乙二酯所構成之薄膜狀之基材之單面並乾燥，形成有厚度10μm之黏著劑層的感溫性黏著膠帶。 First, each copolymer obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 2 was adjusted to have a solid content of 30% by weight with ethyl acetate to obtain a coating liquid. Next, the coating solution was coated on one side of a film-shaped substrate made of polyethylene terephthalate having a thickness of 100 μm and dried to form a temperature-sensitive adhesive tape having an adhesive layer having a thickness of 10 μm.
對於所得之感溫性黏著膠帶，評價180°剝離強度。將評價方法表示如下，同時其結果表示於表2。 The obtained thermosensitive adhesive tape was evaluated for 180 ° peel strength. The evaluation methods are shown below, and the results are shown in Table 2.
對於所得之感溫性黏著膠帶，依據JIS Z0237而測定在80℃及23℃之各環境溫度中對於聚對苯二甲酸乙二酯薄膜之180°剝離強度。具體地係依以下之條件將感溫性黏著膠帶貼黏於聚對苯二甲酸乙二酯薄膜後，使用負載器(load cell)以300mm/分之速度進行180°剝離。 The 180 ° peeling strength of the obtained thermosensitive adhesive tape with respect to a polyethylene terephthalate film at each of ambient temperatures of 80 ° C. and 23 ° C. was measured in accordance with JIS Z0237. Specifically, the temperature-sensitive adhesive tape was adhered to a polyethylene terephthalate film under the following conditions, and then peeled at a speed of 300 ° / min using a load cell at a speed of 300 mm / min.
以80℃之環境溫度將感溫性黏著膠帶貼黏於聚對苯二甲酸乙二酯薄膜並靜置20分鐘後，進行180°剝離。 The temperature-sensitive adhesive tape was stuck to a polyethylene terephthalate film at an ambient temperature of 80 ° C., and left for 20 minutes, and then peeled at 180 °.
以80℃之環境溫度將感溫性黏著膠帶貼黏於聚對苯二甲酸乙二酯薄膜並靜置20分鐘後，將環境溫度下降至23℃，以此環境溫度靜置20分鐘後，進行180°剝離。 The temperature-sensitive adhesive tape was stuck to a polyethylene terephthalate film at an ambient temperature of 80 ° C, and the mixture was allowed to stand for 20 minutes, and then the ambient temperature was lowered to 23 ° C. 180 ° peel.
又，聚對苯二甲酸乙二酯薄膜係使用厚度25μm之未處理者。又，對於聚對苯二甲酸乙二酯薄膜之感溫性黏著膠帶之貼著係於感溫性黏著膠帶之上使2kg之滾輪往返5次。 As the polyethylene terephthalate film, an untreated film having a thickness of 25 μm was used. In addition, the adhesion of the thermosensitive adhesive tape to the polyethylene terephthalate film was tied to the thermosensitive adhesive tape, and a 2 kg roller was reciprocated 5 times.
從表2明顯可知，實施例1至4係在80℃及23℃之各環境溫度中之180°剝離強度顯示良好的結果。 It is clear from Table 2 that the peeling strengths of Examples 1 to 4 at 180 ° C at respective ambient temperatures of 80 ° C and 23 ° C show good results.
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| JP2017179004A (en) * | 2016-03-28 | 2017-10-05 | ニッタ株式会社 | Temperature-sensitive adhesive |
| JP6754609B2 (en) * | 2016-05-17 | 2020-09-16 | ニッタ株式会社 | Temperature sensitive adhesive |
| JP6789001B2 (en) * | 2016-05-17 | 2020-11-25 | ニッタ株式会社 | Temperature sensitive adhesive |
| JP7058405B2 (en) * | 2016-06-23 | 2022-04-22 | ニッタ株式会社 | Temperature Sensitive Resin, Temperature Sensitive Adhesive and Thermosensitive Adhesive Composition |
| KR102235979B1 (en) * | 2018-03-28 | 2021-04-02 | 주식회사 엘지화학 | Adhesive film and manufacturing method of adhesive film |
| KR102256784B1 (en) * | 2018-03-28 | 2021-05-26 | 주식회사 엘지화학 | Adhesive film and manufacturing method of adhesive film |
| KR102293551B1 (en) * | 2018-07-27 | 2021-08-24 | 주식회사 엘지화학 | Adhesive composition, adhesive film using same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
| KR102293935B1 (en) * | 2018-07-27 | 2021-08-24 | 주식회사 엘지화학 | Adhesive composition, adhesive film using same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
| KR102290639B1 (en) * | 2018-07-27 | 2021-08-17 | 주식회사 엘지화학 | Adhesive composition, adhesive film using same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
| KR102290629B1 (en) * | 2018-07-27 | 2021-08-17 | 주식회사 엘지화학 | Adhesive composition, adhesive film using same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
| KR102290643B1 (en) * | 2018-07-27 | 2021-08-17 | 주식회사 엘지화학 | Adhesive composition, adhesive film using same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
| KR102293549B1 (en) * | 2018-07-27 | 2021-08-24 | 주식회사 엘지화학 | Adhesive composition, adhesive film using same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
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| KR102290640B1 (en) * | 2018-07-27 | 2021-08-17 | 주식회사 엘지화학 | Adhesive composition, adhesive film using same, backplate film comprising adhesive film and plastic organic light emitting display comprising adhesive film |
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