CN119463726A - Reinforced film, method for manufacturing device, and reinforced method - Google Patents
Reinforced film, method for manufacturing device, and reinforced method Download PDFInfo
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- CN119463726A CN119463726A CN202411089753.4A CN202411089753A CN119463726A CN 119463726 A CN119463726 A CN 119463726A CN 202411089753 A CN202411089753 A CN 202411089753A CN 119463726 A CN119463726 A CN 119463726A
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- Prior art keywords
- adhesive layer
- meth
- acrylate
- film
- weight
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 177
- 239000012790 adhesive layer Substances 0.000 claims abstract description 144
- 238000000016 photochemical curing Methods 0.000 claims abstract description 140
- 229920005601 base polymer Polymers 0.000 claims abstract description 91
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 38
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims description 112
- 230000001070 adhesive effect Effects 0.000 claims description 112
- 230000003014 reinforcing effect Effects 0.000 claims description 107
- 239000000178 monomer Substances 0.000 claims description 73
- 239000003431 cross linking reagent Substances 0.000 claims description 52
- -1 (methyl) acryloyl group Chemical group 0.000 claims description 46
- 238000003860 storage Methods 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 19
- 230000001965 increasing effect Effects 0.000 claims description 18
- 229920001721 polyimide Polymers 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 13
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 claims description 3
- GNBCKKSGQPLTRW-UHFFFAOYSA-N C(C=C)(=O)OC.C(N)(O)=O Chemical compound C(C=C)(=O)OC.C(N)(O)=O GNBCKKSGQPLTRW-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 14
- 230000002787 reinforcement Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 54
- 239000000463 material Substances 0.000 description 44
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 43
- 125000000217 alkyl group Chemical group 0.000 description 39
- 239000005056 polyisocyanate Substances 0.000 description 18
- 229920001228 polyisocyanate Polymers 0.000 description 18
- 125000005702 oxyalkylene group Chemical group 0.000 description 17
- 230000009477 glass transition Effects 0.000 description 16
- 239000000470 constituent Substances 0.000 description 15
- 238000004132 cross linking Methods 0.000 description 14
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 14
- 229920000058 polyacrylate Polymers 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 238000011109 contamination Methods 0.000 description 11
- 230000001976 improved effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 125000006545 (C1-C9) alkyl group Chemical group 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- KANZWHBYRHQMKZ-UHFFFAOYSA-N 2-ethenylpyrazine Chemical compound C=CC1=CN=CC=N1 KANZWHBYRHQMKZ-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
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- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
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- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 1
- YEUIMZOJSJEGFM-UHFFFAOYSA-N 1-cyclohexyl-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CCCCC1)CC1CO1 YEUIMZOJSJEGFM-UHFFFAOYSA-N 0.000 description 1
- UBPXWZDJZFZKGH-UHFFFAOYSA-N 1-ethenyl-3-methylpyrrolidin-2-one Chemical compound CC1CCN(C=C)C1=O UBPXWZDJZFZKGH-UHFFFAOYSA-N 0.000 description 1
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- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
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- 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
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- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
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- G—PHYSICS
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- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- Engineering & Computer Science (AREA)
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- Adhesives Or Adhesive Processes (AREA)
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- Laminated Bodies (AREA)
Abstract
一种增强膜(10)、器件的制造方法以及增强方法，增强膜(10)具备固着层叠于膜基材(1)的一个主面上的粘合剂层(2)。粘合剂层由包含具有交联结构的丙烯酸系基础聚合物、光固化剂和光聚合引发剂的光固化性组合物形成。丙烯酸系基础聚合物的重均分子量为160万以上。光固化性组合物包含不具有氨基甲酸酯键的多官能(甲基)丙烯酸酯和氨基甲酸酯(甲基)丙烯酸酯作为光固化剂。
A reinforcement film (10), a method for manufacturing a device, and a reinforcement method, wherein the reinforcement film (10) comprises an adhesive layer (2) fixedly laminated on one main surface of a film substrate (1). The adhesive layer is formed by a photocurable composition comprising an acrylic base polymer having a cross-linked structure, a photocuring agent, and a photopolymerization initiator. The weight average molecular weight of the acrylic base polymer is greater than 1.6 million. The photocurable composition comprises a multifunctional (meth)acrylate having no urethane bond and a urethane (meth)acrylate as a photocuring agent.
Description
Technical Field
The present invention relates to a reinforced film obtained by fixedly laminating a film base material and a photocurable adhesive layer. The present invention further relates to a method for manufacturing a device having a reinforcing film bonded to the surface thereof, and a method for reinforcing a laminate reinforcing film by fixing the reinforcing film to the surface of an adherend.
Background
For the purpose of surface protection, impact resistance, and the like, an adhesive film may be attached to the surface of an optical device such as a display or an electronic device. Such an adhesive film is generally formed by laminating an adhesive layer on the main surface of a film base material, and bonding the adhesive layer to the device surface via the adhesive layer.
In a state before use such as assembly, processing, and transportation of the device, the adhesive film is temporarily fixed to the surface of the device or the device constituent member, whereby damage and breakage of the adherend can be suppressed. Patent document 1 discloses a reinforced film comprising a photocurable adhesive layer comprising an acrylic base polymer, a polyfunctional (meth) acrylate as a photocuring agent, and a photopolymerization initiator on a film substrate.
The reinforcing film has low adhesion immediately after bonding to an adherend, and is therefore easily peeled from the adherend. Therefore, reworking from the adherend is possible, and the reinforcing film can also be selectively peeled off and removed from the site where reinforcing of the adherend is not required. Since the adhesive of the reinforcing film is firmly bonded to the adherend by photo-curing, the film base material is permanently bonded to the surface of the adherend, and thus the adhesive can be used as a reinforcing material for supporting surface protection of devices and the like.
Prior art literature
Patent literature
Patent document 1 International publication No. 2022/050009
Disclosure of Invention
Problems to be solved by the invention
The reinforcing film attached to the surface of the device is required to have high adhesion after the adhesive layer is photo-cured, and not to be peeled from the adherend even when the device is deformed such as bent or the temperature is changed. Patent document 1 describes that by using an acrylic polymer having a low glass transition temperature as a base polymer constituting a photocurable adhesive, the adhesive layer has a low storage elastic modulus and a high relaxation of stress strain, and thus peeling of the adhesive layer at the bending portion of the device can be suppressed, and the adhesive reliability is excellent.
However, the adhesive of the reinforcing film disclosed in patent document 1 has a small adhesive force at a high temperature after photo-curing, and the adhesive reliability is insufficient. In view of the above problems, an object of the present invention is to provide a reinforcing film having high adhesion at high temperature and excellent adhesion reliability.
Solution for solving the problem
The reinforcing film of the present invention comprises an adhesive layer fixedly laminated on one main surface of a film base material. The adhesive layer is formed from a photocurable composition containing an acrylic base polymer having a crosslinked structure, a photocuring agent, and a photopolymerization initiator.
The acrylic base polymer contains, as a monomer component, at least one selected from the group consisting of hydroxyl group-containing monomers and carboxyl group-containing monomers, and has a weight average molecular weight of 160 ten thousand or more. The acrylic base polymer may contain a nitrogen atom-containing monomer as a monomer component.
The acrylic base polymer has a crosslinked structure. The crosslinking agent is preferably used in an amount of 0.05 to 1.0 parts by weight based on 100 parts by weight of the polymer to introduce a crosslinked structure. Examples of the crosslinking agent include isocyanate-based crosslinking agents and epoxy-based crosslinking agents.
The photocurable composition constituting the adhesive layer contains a multifunctional (meth) acrylate having no urethane bond and a urethane (meth) acrylate as a photocurable agent. The amount of the polyfunctional (meth) acrylate having no urethane bond is preferably 3 to 30 parts by weight based on 100 parts by weight of the acrylic base polymer. The amount of the urethane (meth) acrylate is preferably 0.03 to 5 parts by weight relative to 100 parts by weight of the acrylic base polymer.
The functional group equivalent of the (meth) acryl of the multifunctional (meth) acrylate having no urethane bond may be 80 to 500g/eq. The functional group equivalent of the (meth) acryloyl group of the urethane (meth) acrylate may be 80 to 5000g/eq. The urethane (meth) acrylate may have 4 or more (meth) acryl groups in one molecule.
The adhesive layer preferably has an adhesion F 0 to the polyimide film at 25 ℃ or less before photo-curing of 0.4N/25mm or less. Preferably, the adhesive layer has an adhesive force F 1 at 25 ℃ of 3.0N/25mm or more and an adhesive force F 3 at 85 ℃ of 1.0N/25mm or more to the polyimide film after photo-curing. The shear storage elastic modulus of the adhesive layer after photo-curing at a temperature of 25 ℃ is preferably 100kPa or less.
After the reinforcing film is attached to the surface of the device as an adherend and temporarily fixed, the adhesive layer is photo-cured, thereby obtaining a device with a reinforcing film. The device may be a flexible device capable of bending, and the adherend (reinforcing object) of the reinforcing film may be an image display element capable of bending.
After temporarily fixing the reinforcing film to the adherend and before photo-curing the pressure-sensitive adhesive layer, the reinforcing film temporarily fixed to the adherend may be cut off, and the reinforcing film may be peeled off from a part of the area (non-reinforcing target area) on the adherend.
Effects of the invention
The pressure-sensitive adhesive layer of the reinforcing film of the present invention is formed of a photocurable composition, and after the pressure-sensitive adhesive layer is adhered to an adherend, the pressure-sensitive adhesive layer is cured by light, thereby enhancing the adhesion to the adherend. The adhesive layer has a small adhesion to the adherend before photo-curing, and is easily peeled from the adherend. The adhesive after photo-curing has high adhesion even at high temperature and excellent adhesion reliability.
Drawings
Fig. 1 is a cross-sectional view showing a laminated structure of reinforcing films.
Fig. 2 is a cross-sectional view showing a laminated structure of the reinforcing film.
Fig. 3 is a cross-sectional view showing a device to which a reinforcing film is attached.
Description of the reference numerals
1 Film substrate, 2 adhesive layer, 10 reinforcing film, 5 release liner, 20 adherend.
Detailed Description
FIG. 1 is a cross-sectional view showing one embodiment of a reinforced membrane. The reinforcing film 10 includes an adhesive layer 2 on one main surface of the film base material 1. The adhesive layer 2 is fixedly laminated on one main surface of the film base material 1. The pressure-sensitive adhesive layer 2 is a photocurable pressure-sensitive adhesive formed of a photocurable composition, and is cured by irradiation with active light such as ultraviolet rays, and has an increased adhesion to an adherend.
Fig. 2 is a cross-sectional view of a reinforcing film in which a release liner 5 is temporarily fixed to a main surface of an adhesive layer 2. Fig. 3 is a cross-sectional view showing a state in which the reinforcing film 10 is attached to the surface of the device 20.
The release liner 5 is peeled off from the surface of the adhesive layer 2, and the exposed surface of the adhesive layer 2 is bonded to the surface of the device 20, whereby the reinforcing film 10 is bonded to the surface of the device 20. In this state, the pressure-sensitive adhesive layer 2 is in a state where the reinforcing film 10 (pressure-sensitive adhesive layer 2) is temporarily fixed to the device 20 before the light curing. By photocuring the adhesive layer 2, the adhesion force at the interface of the device 20 and the adhesive layer 2 increases, and the device 20 and the reinforcing film 10 are fixed.
"Fixed" refers to a state in which two layers stacked are firmly bonded, and peeling at the interface between the two layers is impossible or difficult. The term "temporary fixation" refers to a state in which the adhesion between two layers of a laminate is small and can be easily peeled off at the interface between the two layers.
In the reinforced film shown in fig. 2, the film base material 1 is fixed to the adhesive layer 2, and the release liner 5 is temporarily fixed to the adhesive layer 2. When the film base material 1 and the release liner 5 are peeled off, peeling occurs at the interface between the adhesive layer 2 and the release liner 5, and the adhesive layer 2 is kept fixed to the film base material 1. No adhesive remains on the release liner 5 after release.
The device with the reinforcing film 10 shown in fig. 3 is in a temporary fixation state with the adhesive layer 2 before the light curing of the adhesive layer 2. When the film base material 1 is peeled off from the device 20, peeling occurs at the interface between the adhesive layer 2 and the device 20, and the adhesive layer 2 is kept fixed to the film base material 1. Since no adhesive remains on the device 20, reworking is easy. Since the adhesive force between the adhesive layer 2 and the device 20 increases after the adhesive layer 2 is photo-cured, it is difficult to peel the reinforcing film 10 from the device 20, and there is a case where the adhesive layer 2 is broken by aggregation when the both are peeled.
[ Constitution of reinforcing film ]
< Film substrate >
As the film base material 1, a plastic film was used. In order to fix the film base material 1 and the adhesive layer 2, it is preferable that the adhesive layer 2-attaching surface of the film base material 1 is not subjected to a release treatment.
The thickness of the film base material 1 is, for example, about 4 to 500 μm. The thickness of the film base material 1 is preferably 12 μm or more, more preferably 30 μm or more, and even more preferably 45 μm or more, from the viewpoint of reinforcing the device by imparting rigidity, relaxing impact, or the like. The thickness of the film base material 1 is preferably 300 μm or less, more preferably 200 μm or less, from the viewpoint of improving the handleability by imparting flexibility to the reinforced film. In order to impart flexibility to the reinforced film and enable folding, the thickness of the film base material 1 is preferably 125 μm or less, more preferably 100 μm or less. From the viewpoint of both mechanical strength and flexibility, the film base material 1 preferably has a compressive strength of 100 to 3000kg/cm 2, more preferably 200 to 2900kg/cm 2, still more preferably 300 to 2800kg/cm 2, and particularly preferably 400 to 2700kg/cm 2.
Examples of the plastic material constituting the film base material 1 include polyester-based resins, polyolefin-based resins, cyclic polyolefin-based resins, polyamide-based resins, polyimide-based resins, polyether ether ketone resins, and the like. In the reinforcing film for an optical device such as a display, the film base material 1 is preferably a transparent film. In the case where the adhesive layer 2 is photo-cured by irradiation of the active light from the film base material 1 side, the film base material 1 preferably has transparency to the active light used for curing the adhesive layer. In view of both mechanical strength and transparency, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are preferably used. In the case where the pressure-sensitive adhesive layer is cured by irradiation with the active light from the adherend side, the film base material 1 may be opaque to the active light as long as the adherend has transparency to the active light.
The surface of the film base material 1 may be provided with functional coatings such as an easy-to-adhere layer, an easy-to-slip layer, a release layer, an antistatic layer, a hard coat layer, an antireflection layer, and the like. In order to fix the film base material 1 to the pressure-sensitive adhesive layer 2 as described above, it is preferable that a release layer is not provided on the pressure-sensitive adhesive layer 2-attaching surface of the film base material 1.
< Adhesive layer >
The adhesive layer 2 fixedly laminated on the film base material 1 is formed of a photocurable composition containing a base polymer, a photocurable agent, and a photopolymerization initiator. The adhesive layer 2 has a small adhesion force to an adherend such as a device or a device member before photocuring, and is therefore easily peeled off. Since the adhesive layer 2 is cured by light to improve the adhesion to the adherend, the reinforcing film is less likely to peel off from the device surface even when the device is used, and the adhesion reliability is excellent.
The photocurable adhesive is hardly cured in a normal storage environment, and is cured by irradiation of active light such as ultraviolet rays. Therefore, the reinforcing film of the present invention has advantages that the timing of curing the adhesive layer 2 can be arbitrarily set, the lead time (lead time) of the process can be flexibly dealt with, and the like.
The thickness of the pressure-sensitive adhesive layer 2 is, for example, about 1 to 300 μm. The greater the thickness of the pressure-sensitive adhesive layer 2, the more the adhesion to the adherend tends to be improved. On the other hand, when the thickness of the adhesive layer 2 is too large, fluidity before photo-curing may be high, and handling may be difficult. Therefore, the thickness of the pressure-sensitive adhesive layer 2 is preferably 3 to 100. Mu.m, more preferably 5 to 50. Mu.m, still more preferably 6 to 40. Mu.m, particularly preferably 8 to 30. Mu.m. From the viewpoint of thinning, the thickness of the adhesive layer 2 may be 25 μm or less, 20 μm or less, or 18 μm or less.
In the case where the reinforcing film is used for an optical device such as a display, the total light transmittance of the adhesive layer 2 is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The haze of the pressure-sensitive adhesive layer 2 is preferably 2% or less, more preferably 1% or less, further preferably 0.7% or less, and particularly preferably 0.5% or less.
Hereinafter, preferred modes of the respective components of the photocurable composition constituting the pressure-sensitive adhesive layer 2 will be described in order.
(Base Polymer)
The base polymer is a main component of the adhesive composition, and is a main element determining the adhesion of the adhesive layer. The adhesive composition contains an acrylic polymer as a base polymer. Preferably, 50% by weight or more of the adhesive composition is an acrylic polymer. The acrylic base polymer is excellent in optical transparency and adhesion, and the adhesion is easily controlled.
As the acrylic polymer, an acrylic polymer containing an alkyl (meth) acrylate as a main monomer component is preferably used. In the present specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid.
The alkyl (meth) acrylate is preferably one in which the alkyl group has 1 to 20 carbon atoms. The alkyl (meth) acrylate may have a branched alkyl group or a cyclic alkyl group (alicyclic alkyl group).
Specific examples of the alkyl (meth) acrylate having a chain alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, isotridecyl (meth) acrylate, tetradecyl (meth) acrylate, isotetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and nonadecyl (meth) acrylate.
Specific examples of the alkyl (meth) acrylate having an alicyclic alkyl group include (meth) acrylic acid esters having a bicyclic aliphatic hydrocarbon ring such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, and the like, (meth) acrylic acid esters having a tricyclic aliphatic hydrocarbon ring such as isobornyl (meth) acrylate, tetrahydrodicyclopentadiene oxy ethyl (meth) acrylate, tetrahydrodicyclopentadiene oxy ester (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and the like, (meth) acrylic acid esters having an aliphatic hydrocarbon ring having a tricyclic or higher ring. The alkyl (meth) acrylate having an alicyclic alkyl group may be an alkyl (meth) acrylate having a substituent on the ring such as 3, 5-trimethylcyclohexyl (meth) acrylate. The alkyl (meth) acrylate having an alicyclic alkyl group may be a (meth) acrylate having a condensed ring structure including an alicyclic structure and a ring structure having an unsaturated bond, such as dicyclopentenyl (meth) acrylate.
The content of the alkyl (meth) acrylate is preferably 50 parts by weight or more, more preferably 60 parts by weight or more, or 70 parts by weight or more, 80 parts by weight or more, 90 parts by weight or more, or 95 parts by weight or more, based on 100 parts by weight of the total amount of the monomer components constituting the polymer.
The alkyl group of the alkyl (meth) acrylate is preferably a chain alkyl group from the viewpoints of lowering the glass transition temperature (Tg) of the acrylic base polymer and improving the adhesion in a wide temperature range. The chain alkyl group may be straight or branched.
Among the exemplified alkyl (meth) acrylates, C 1－9 alkyl (meth) acrylates having 1 to 9 carbon atoms in the alkyl group are preferred from the viewpoint of lowering Tg of the base polymer. The alkyl (meth) acrylate preferably has a homopolymer glass transition temperature of-50 ℃ or lower, and among these, a C 6－9 alkyl (meth) acrylate having 6 to 9 carbon atoms as an alkyl group is preferable.
Specific examples of the C 6－9 alkyl (meth) acrylate having a glass transition temperature of-50 ℃ or lower include 2-ethylhexyl acrylate (Tg: -70 ℃), n-hexyl acrylate (Tg: -65 ℃), n-octyl acrylate (Tg: -65 ℃), isononyl acrylate (Tg: -60 ℃) and n-nonyl acrylate (Tg: -58 ℃) and isooctyl acrylate (Tg: -58 ℃). Among these, 2-ethylhexyl acrylate and n-octyl acrylate are preferable in that Tg is low and the binder can be molded into a low energy storage elastic modulus.
The acrylic base polymer preferably has the greatest amount of monomer (main monomer) in the constituent monomers being C 6－9 alkyl (meth) acrylate. The amount of the C 6－9 alkyl (meth) acrylate is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, or may be 55 parts by weight or more, 60 parts by weight or more, or 65 parts by weight or more, based on 100 parts by weight of the total amount of constituent monomer components of the polymer.
The acrylic base polymer may contain two or more kinds of alkyl (meth) acrylates as monomer components, and may also contain C 1－9 alkyl (meth) acrylate and C 10－20 alkyl (meth) acrylate. Homopolymers of alkyl (meth) acrylates having a long-chain alkyl group of 10 or more carbon atoms have a temperature region (plateau region) in which the temperature dependence of viscoelasticity is small at a temperature higher than Tg. Therefore, when the base polymer contains a C 10－20 alkyl (meth) acrylate as a monomer component, the temperature dependence of the storage elastic modulus becomes small, and warpage of the adherend and peeling of the reinforcing film from the adherend due to temperature change may be suppressed.
Of the C 10－20 chain alkyl (meth) acrylates, C 12－18 alkyl (meth) acrylates are preferred because of the wide temperature range in the plateau region and the small storage elastic modulus in the plateau region. Among them, dodecyl (meth) acrylate and isostearyl (meth) acrylate are preferable, and dodecyl acrylate (lauryl acrylate) is particularly preferable.
When the acrylic base polymer contains a C 10－20 alkyl (meth) acrylate as a monomer component, the amount of the C 10－20 alkyl (meth) acrylate is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, still more preferably 3 to 25 parts by weight, and may be 4 to 20 parts by weight or 5 to 15 parts by weight, based on 100 parts by weight of the total amount of the constituent monomer components of the polymer.
The acrylic base polymer contains a hydroxyl group-containing monomer and/or a carboxyl group-containing monomer as a constituent monomer component in addition to the alkyl (meth) acrylate. The hydroxyl group and carboxyl group of the base polymer serve as reaction points with a crosslinking agent to be described later. For example, when an isocyanate-based crosslinking agent is used, a hydroxyl group-containing monomer is preferably contained as a monomer component of the base polymer. When an epoxy-based crosslinking agent is used, a carboxyl group-containing monomer is preferably contained as a monomer component of the base polymer. By introducing a crosslinked structure into the base polymer, the cohesive force tends to be improved, and the peelability of the adhesive layer 2 from the adherend before photo-curing tends to be improved.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate. Among these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferable from the viewpoint of a large contribution to the improvement of the adhesive strength of the adhesive after photocuring.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Among them, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable, in view of the easiness of improving the adhesive force and the adhesive holding force by increasing the cohesiveness of the adhesive.
From the viewpoint of properly introducing a crosslinked structure formed by a crosslinking agent such as an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent, the total amount of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, and may be 0.7 parts by weight or more or 1.0 part by weight or more, relative to 100 parts by weight of the total amount of the constituent monomer components of the acrylic base polymer.
Since hydroxyl groups and carboxyl groups have high polarity, when the amount of the hydroxyl group-containing monomer and the carboxyl group-containing monomer in the constituent monomer components of the acrylic base polymer is large, the cohesive force of the polymer tends to be high, and the energy storage elastic modulus of the pressure-sensitive adhesive layer after photocuring tends to be high. From the viewpoint of reducing the energy storage elastic modulus of the adhesive layer 2, the total amount of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, or 7 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the total amount of the constituent monomer components of the acrylic base polymer.
The acrylic base polymer may contain a nitrogen atom-containing monomer as a constituent monomer component. Since the nitrogen atom-containing monomer has high polarity and high cohesive force and the glass transition temperature of the homopolymer is high, the acrylic base polymer contains the nitrogen atom-containing monomer as a monomer component, and thus the adhesive strength at high temperature and the adhesive strength at low-speed peeling of the adhesive layer after photo-curing tend to be improved.
Examples of the nitrogen atom-containing monomer include N-vinylpyrrolidone, methyl vinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyridine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-acryloylmorpholine, N-vinylcarboxylic acid amide, N-vinylcaprolactam and the like. Among them, N-vinylpyrrolidone is particularly preferred because of its high cohesive force and its large contribution to the improvement of adhesion at high temperature.
When the acrylic base polymer contains a nitrogen atom-containing monomer as a monomer component, the amount of the nitrogen atom-containing monomer is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, and may be 0.7 parts by weight or more, based on 100 parts by weight of the total amount of the constituent monomer components of the polymer, from the viewpoint of improving the adhesion of the pressure-sensitive adhesive layer after photocuring at a high temperature. Even a small amount of the nitrogen atom-containing monomer can contribute to the improvement of the adhesion at high temperatures.
When the amount of the nitrogen atom-containing monomer in the constituent monomer component of the acrylic base polymer is large, the cohesive force of the base polymer tends to be high, and the glass transition temperature of the adhesive layer tends to be high, and the energy storage elastic modulus of the adhesive layer after photo-curing tends to be high. In addition, when the amount of the nitrogen atom-containing monomer is large, the adhesive force of the adhesive layer 2 before photo-curing is high, and peeling of the reinforcing film from the adherend tends to be difficult. From the viewpoints of a decrease in the adhesive strength of the adhesive before photocuring and a decrease in the storage elastic modulus of the adhesive after photocuring, the amount of the nitrogen atom-containing monomer is preferably 10 parts by weight or less, more preferably 7 parts by weight or less, and may be 5 parts by weight or less or 3 parts by weight or less, relative to 100 parts by weight of the total amount of the constituent monomer components of the acrylic base polymer.
The acrylic base polymer may contain a monomer component other than the above. The acrylic base polymer may contain, for example, a vinyl ester monomer, an aromatic vinyl monomer, an epoxy group-containing monomer, a vinyl ether monomer, a sulfo group-containing monomer, a phosphoric acid group-containing monomer, an anhydride group-containing monomer, or the like as a monomer component.
The glass transition temperature of the acrylic base polymer is preferably-30 ℃ or lower, more preferably-40 ℃ or lower, still more preferably-50 ℃ or lower, and may be-55 ℃ or lower or-60 ℃ or lower, from the viewpoint of providing excellent adhesion to the adhesive. The glass transition temperature of the acrylic base polymer is usually-100 ℃ or higher, but may be-80 ℃ or higher or-70 ℃ or higher.
The glass transition temperature (Tg) is a temperature at which the loss tangent tan δ reaches a maximum (peak top temperature) in the viscoelasticity measurement. Instead of the glass transition temperature based on the viscoelasticity measurement, the theoretical glass transition temperature can also be applied. The theoretical Tg is calculated from the glass transition temperature Tg i of the homopolymer of the constituent monomer components of the polymer and the weight fraction W i of each monomer component by the following Fox formula.
1/Tg=Σ(Wi/Tgi)
Tg is the theoretical glass transition temperature (unit: K) of the polymer, W i is the weight fraction (weight basis copolymerization ratio) of the monomer component i, and Tg i is the glass transition temperature (unit: K) of the homopolymer of the monomer component i. As glass transition temperature of the homopolymer, the values described in Polymer Handbook, third edition (John Wiley & Sons, inc., 1989) can be used. The glass transition temperature of the homopolymer of the monomer not described in the above document may be the peak top temperature of tan δ measured based on dynamic viscoelasticity.
The acrylic polymer as the base polymer is obtained by polymerizing the above monomer components by various known methods such as solution polymerization, emulsion polymerization, and bulk polymerization. The solution polymerization method is preferable from the viewpoints of balance of properties such as adhesion and holding power of the adhesive, cost and the like. As the solvent for the solution polymerization, ethyl acetate, toluene, or the like can be used. The concentration of the solution is usually about 20 to 80% by weight. As the polymerization initiator used in the solution polymerization, various known polymerization initiators such as azo-based and peroxide-based can be used. In order to adjust the molecular weight, a chain transfer agent may be used. The reaction temperature is usually about 50 to 80 ℃, and the reaction time is usually about 1 to 8 hours.
The weight average molecular weight of the acrylic base polymer is 160 ten thousand or more. The base polymer has a large weight average molecular weight, and thus the adhesive strength at high temperature tends to be improved. The weight average molecular weight of the acrylic base polymer may be 170 ten thousand or more.
When the weight average molecular weight of the base polymer is too large, the storage elastic modulus of the adhesive tends to be large, and the adhesive force and flexibility tend to be low. Accordingly, the weight average molecular weight of the acrylic base polymer is preferably 300 ten thousand or less, more preferably 250 ten thousand or less, and may be 220 ten thousand or less or 200 ten thousand or less. In the case where a crosslinked structure is introduced into the base polymer, the molecular weight of the base polymer means the molecular weight before the crosslinked structure is introduced.
(Crosslinking agent)
The cross-linked structure is preferably introduced into the base polymer from the viewpoint of imparting an appropriate cohesive force to the adhesive, exhibiting adhesive force, and ensuring peelability of the adhesive layer from the adherend before photo-curing. For example, a crosslinking agent is added to a solution obtained by polymerizing a base polymer, and the solution is heated as needed, thereby introducing a crosslinked structure. The crosslinking agent has 2 or more crosslinkable functional groups in one molecule. The crosslinking agent may have 3 or more crosslinkable functional groups in one molecule.
Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, carbodiimide-based crosslinking agents, and metal chelate-based crosslinking agents. These crosslinking agents react with functional groups such as hydroxyl groups and carboxyl groups introduced into the acrylic base polymer to form a crosslinked structure. The isocyanate-based crosslinking agent and the epoxy-based crosslinking agent are preferable in terms of high reactivity with hydroxyl groups and carboxyl groups of the acrylic base polymer and easiness of introducing a crosslinked structure.
As the isocyanate-based crosslinking agent, a polyisocyanate having 2 or more isocyanate groups in one molecule is used. The isocyanate-based crosslinking agent may have 3 or more isocyanate groups in one molecule. Examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, aromatic isocyanates such as 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate, and isocyanate adducts such as trimethylolpropane/toluene diisocyanate trimer adducts (for example, "TAKENATE D E" by Mitsui chemical Co., ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adducts (for example, "CORONATE HL by Tosoh Co., ltd.), trimethylolpropane adducts of xylylene diisocyanate (for example," TAKENATE D N "by Mitsui chemical Co., ltd.), and isocyanurate adducts of hexamethylene diisocyanate (for example," CORONATE "by Tosoh Co., ltd.). As the isocyanate-based crosslinking agent, an isocyanate compound having a biuret group (for example, "DURANATE A-100" manufactured by Asahi chemical Co., ltd.) or an isocyanate compound having an allophanate group can be used.
As the epoxy-based crosslinking agent, a polyfunctional epoxy compound having 2 or more epoxy groups in one molecule can be used. The epoxy-based crosslinking agent may have 3 or more or 4 or more epoxy groups in one molecule. The epoxy group of the epoxy-based crosslinking agent may be a glycidyl group. Examples of the epoxy-based crosslinking agent include N, N, N ', N' -tetraglycidyl-m-xylylenediamine, diglycidyl aniline, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and the like. As the epoxy-based crosslinking agent, commercially available products such as "Denacol" manufactured by NagasChemteX and "TETRAD X" and "TETRAD C" manufactured by Mitsubishi gas chemical corporation can be used.
The amount of the crosslinking agent to be used is appropriately adjusted depending on the composition, molecular weight, etc. of the acrylic base polymer, and is preferably about 0.01 to 3 parts by weight based on 100 parts by weight of the acrylic base polymer. The higher the amount of the crosslinking agent, the higher the crosslinking density of the base polymer, the higher the storage elastic modulus and the appropriate hardness are given to the pressure-sensitive adhesive layer before photocuring, and the tendency is that the residual adhesive on the adherend is suppressed when the reinforcing film is peeled from the adherend. On the other hand, if the amount of the crosslinking agent is too large, the cohesive force at the adhesive interface tends to be smaller than that of the main body portion in the adhesive layer after photo-curing, and the adhesive force tends to be lower particularly at high temperatures. From the viewpoint of the low adhesion (light releasability) of the adhesive layer before photo-curing and the high adhesion of the adhesive layer after photo-curing, the amount of the crosslinking agent is more preferably 0.05 to 1.0 parts by weight, still more preferably 0.1 to 0.7 parts by weight, and may be 0.15 to 0.6 parts by weight, 0.2 to 0.5 parts by weight, or 0.25 to 0.4 parts by weight, relative to 100 parts by weight of the acrylic base polymer.
(Photo-curing agent)
The adhesive composition constituting the adhesive layer 2 contains, in addition to the base polymer, a compound having 2 or more photopolymerizable functional groups in one molecule as a photocuring agent. The adhesive composition containing the photo-curing agent has photo-curing property, and when the adhesive composition is bonded to an adherend and then photo-cured, the adhesion to the adherend is improved.
From the viewpoint of compatibility with the base polymer, the photocurable agent is preferably liquid at ordinary temperature. The photopolymerizable functional group of the photocurable agent preferably has polymerizability based on a photoradical reaction. As the photo-curing agent, a compound having 2 or more ethylenic unsaturated bonds in one molecule is preferable, and a polyfunctional (meth) acrylate is preferable in view of exhibiting appropriate compatibility with the acrylic base polymer.
In the present invention, as the photo-curing agent, a multifunctional (meth) acrylate having no urethane bond and a multifunctional (meth) acrylate having a urethane bond are used in combination. That is, the photocurable composition constituting the adhesive layer 2 contains a polyfunctional (meth) acrylate having no urethane bond and a polyfunctional (meth) acrylate having a urethane bond. Hereinafter, the polyfunctional (meth) acrylate having a urethane bond is referred to as "urethane (meth) acrylate". In addition, a multifunctional (meth) acrylate having no urethane bond is sometimes abbreviated as "multifunctional (meth) acrylate".
Examples of the polyfunctional (meth) acrylate having no urethane bond include compounds having a (meth) acryloyl group at both ends of a polyoxyalkylene chain such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate, and esters of a (meth) acrylic acid with a polyhydric alcohol such as bisphenol A di (meth) acrylate, alkylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, isocyanuric acid tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and epoxy (meth) acrylate.
The multifunctional (meth) acrylate having no urethane bond may be an ester of an oxyalkylene-modified polyol with (meth) acrylic acid. Examples of the ester of an alkylene oxide-modified polyol with (meth) acrylic acid include bisphenol A alkylene oxide-modified di (meth) acrylate, isocyanurate alkylene oxide-modified tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, pentaerythritol alkylene oxide-modified di (meth) acrylate, pentaerythritol alkylene oxide-modified tri (meth) acrylate, dipentaerythritol alkylene oxide-modified poly (meth) acrylate, and the like.
Among the above, from the viewpoints of reducing the adhesive strength of the adhesive layer before photocuring and easily peeling, and improving the adhesive strength of the adhesive layer after photocuring, a polyfunctional (meth) acrylate having an oxyalkylene chain is preferable. Examples of the polyfunctional (meth) acrylate having an oxyalkylene chain include compounds having (meth) acryloyl groups at both ends of the polyoxyalkylene chain, such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate, and esters of the polyoxyalkylene-modified polyol and (meth) acrylic acid.
Among the polyfunctional (meth) acrylates containing an oxyalkylene chain, as the oxyalkylene group, (poly) oxyethylene or (poly) oxypropylene is preferable, and (poly) oxyethylene is particularly preferable. The chain length (number of repeating units of the oxyalkylene group) n of the oxyalkylene group is about 1 to 15. When a plurality of oxyalkylene chains are contained in one molecule, the average chain length n is preferably 1 to 15. The (average) chain length n of the oxyalkylene chain may be 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. By adjusting the kind and chain length of the oxyalkylene group, the compatibility with the acrylic base polymer can be adjusted.
The alkylene oxide is preferably (poly) ethylene oxide or (poly) propylene oxide, and the chain length (number of repeating units: n) of the alkylene oxide is preferably about 1 to 15. When a plurality of oxyalkylene chains are contained in one molecule, the average chain length n is preferably 1 to 15. The (average) chain length n of the oxyalkylene chain may be 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, or 3 or less. By adjusting the kind and chain length of the oxyalkylene group, the compatibility with the acrylic base polymer can be adjusted.
As the photo-curing agent, two or more kinds of polyfunctional (meth) acrylates having no urethane bond may be used in combination. For example, a multifunctional (meth) acrylate having relatively low compatibility with the acrylic base polymer and a multifunctional (meth) acrylate having relatively high compatibility with the acrylic base polymer may be used in combination. For example, a polyfunctional (meth) acrylate having no oxyalkylene chain has a higher compatibility with an acrylic base polymer than a polyfunctional (meth) acrylate having an oxyalkylene chain.
From the viewpoint of compatibility with the acrylic base polymer, the molecular weight of the polyfunctional (meth) acrylate as the photo-curing agent is preferably 1500 or less, more preferably 1000 or less, and may be 800 or less, 500 or 400 or less. From the viewpoint of both compatibility with the acrylic base polymer and improvement in adhesion after photocuring, the functional group equivalent (g/eq) of the multifunctional (meth) acrylate is preferably 500 or less, more preferably 400 or less, still more preferably 300 or less, particularly preferably 200 or less, and may be 180 or 160 or less.
On the other hand, when the functional group equivalent of the polyfunctional (meth) acrylate is too small, the crosslinking point density of the pressure-sensitive adhesive layer after photocuring may become high, and the adhesiveness may be lowered. Therefore, the functional group equivalent of the multifunctional (meth) acrylate is preferably 80 or more, more preferably 100 or more, and may be 120 or more or 130 or more.
By containing a polyfunctional (meth) acrylate having an oxyalkylene chain and a urethane (meth) acrylate as a photo-curing agent, there is a tendency that the adhesive force (initial adhesive force) of the adhesive layer before photo-curing becomes smaller. Further, by containing urethane (meth) acrylate as a photo-curing agent, the adhesive force of the adhesive layer after photo-curing, particularly the adhesive force at high temperature and the adhesive force at low-speed peeling, tends to be large.
The urethane (meth) acrylate is a compound having 1 or more urethane bonds and 2 or more (meth) acryl groups in one molecule, and preferably contains 2 or more urethane bonds in one molecule. Urethane (meth) acrylates having 2 or more urethane bonds are obtained, for example, by reacting a polyisocyanate with a (meth) acrylic compound having a hydroxyl group, and the isocyanate group of the polyisocyanate is bonded to the hydroxyl group of the (meth) acrylic compound to form a urethane bond.
The polyisocyanate may be any one of aromatic polyisocyanate, alicyclic polyisocyanate and alicyclic polyisocyanate. Among them, aromatic polyisocyanates and aliphatic polyisocyanates are preferable. Toluene Diisocyanate (TDI) is particularly preferred as the aromatic polyisocyanate. The toluene diisocyanate may be either one of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, or may be a mixture of both. As aliphatic polyisocyanates, hexamethylene Diisocyanate (HDI) is particularly preferred.
The polyisocyanate may be a trifunctional isocyanate having a cyanuric acid skeleton. Examples of the trifunctional isocyanate having a cyanuric acid skeleton include TDI trimer and HDI trimer. The polyisocyanate may also be a polyisocyanate having biuret groups and allophanate groups.
The polyisocyanate may be an isocyanate-terminated urethane prepolymer obtained by the reaction of a polyol with a polyisocyanate. The isocyanate-terminated urethane prepolymer may be a high molecular weight product obtained by reacting a high molecular weight polyol such as a polyester polyol, a polycarbonate polyol, or a polyether polyol with a polyisocyanate.
Examples of the (meth) acrylic compound having a hydroxyl group include compounds having 1 hydroxyl group and 1 (meth) acryloyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxymethacrylamide, and hydroxyethylacrylamide, and compounds having 1 hydroxyl group and 2 or more (meth) acryloyl groups such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane di (meth) acrylate, and isocyanuric acid di (meth) acrylate.
Among them, the (meth) acrylic compound having a hydroxyl group is preferably a compound having 1 hydroxyl group and 2 or more (meth) acryloyl groups, and specific examples thereof include compounds having a pentaerythritol skeleton such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Urethane (meth) acrylate obtained by reacting diisocyanate with a (meth) acrylic compound having 1 hydroxyl group and 2 or more (meth) acryloyl groups in one molecule has 2 urethane bonds and 4 or more (meth) acryloyl groups in one molecule. The number of (meth) acryloyl groups in the urethane (meth) acrylate may be 6 or more or 8 or more or 12 or less or 10 or less.
As the urethane (meth) acrylate, those commercially available from Kyowa chemical, xinzhongcun chemical, mitsubishi chemical, daicel-Allnex, resonac, etc. can be used.
From the viewpoints of compatibility with the acrylic base polymer and adjustment of adhesion of the adhesive layer, the molecular weight of the urethane (meth) acrylate is preferably 300 to 10000, more preferably 500 to 2000, and may be 600 to 1500 or 700 to 1200. From the same viewpoint, the functional group equivalent (g/eq) of the (meth) acryloyl group of the urethane (meth) acrylate is preferably 80 to 5000, more preferably 90 to 1000, still more preferably 100 to 300, and may be 110 to 250 or 120 to 200.
The content of the photo-curing agent (the sum of the multifunctional (meth) acrylate having no urethane bond and the urethane (meth) acrylate) in the adhesive composition is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, still more preferably 7 parts by weight or more, and may be 8 parts by weight or more or 10 parts by weight or more, based on 100 parts by weight of the acrylic base polymer. When the blending amount of the photo-curing agent is within the above range, the photo-curing agent can be easily peeled off from the adherend before curing, and a reinforcing film which can be firmly bonded to the adherend by photo-curing can be obtained.
The greater the amount of the photo-curing agent, the smaller the adhesion between the adhesive before photo-curing and the adherend tends to be, and the releasability is excellent. On the other hand, when the amount of the photo-curing agent is too large, the photo-curing agent is likely to bleed out, and when the reinforcing film is peeled off from the adherend, the bleeding component may be transferred to the adherend, which may cause contamination. In addition, when the amount of the photo-curing agent is too large, the tackiness of the adhesive after photo-curing tends to be low, and the adhesive force and flexibility tend to be insufficient. Therefore, the content of the photo-curing agent is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 25 parts by weight or less, and may be 20 parts by weight or less or 15 parts by weight or less, based on 100 parts by weight of the base polymer.
The content of the polyfunctional (meth) acrylate having no urethane bond is preferably 3 to 30 parts by weight, more preferably 4 to 25 parts by weight, still more preferably 5 to 20 parts by weight, and may be 6 to 15 parts by weight, 7 to 13 parts by weight, or 8 to 12 parts by weight based on 100 parts by weight of the acrylic base polymer, from the viewpoint of adjusting the adhesiveness between the adhesive layer before and after photocuring and the adherend to an appropriate range.
From the viewpoint of adjusting the adhesiveness between the pressure-sensitive adhesive layer before and after photocuring and the adherend to an appropriate range, the content of urethane (meth) acrylate is preferably 0.03 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, still more preferably 0.08 to 3 parts by weight, and may be 0.1 to 2.5 parts by weight or 0.15 to 2 parts by weight, relative to 100 parts by weight of the acrylic base polymer.
The compatibility of urethane (meth) acrylates with acrylic base polymers is low. Therefore, the urethane (meth) acrylate tends to be biased to the surface of the adhesive layer (near the adhesive interface with the adherend). In addition, the polyfunctional (meth) acrylate having an oxyalkylene chain has low compatibility with the acrylic base polymer as compared with the polyfunctional (meth) acrylate having no oxyalkylene chain. These photocuring agents tend to be biased toward the surface of the pressure-sensitive adhesive layer (near the bonding interface with the adherend), and the photocuring agents biased toward the bonding interface with the adherend tend to form a bonding barrier layer (Weak Boundary Layer; WBL).
When WBL is formed, the liquid property of the surface (bonding interface) is enhanced while maintaining the overall properties such as the storage elastic modulus of the adhesive layer, and thus the bonding force with the adherend tends to be reduced. Therefore, the adhesive layer before photo-curing is easily peeled from the adherend. When the photo-curing agent is biased near the adhesive interface with the adherend and the WBL-formed adhesive layer is photo-cured, the curing reaction of the photo-curing agent is likely to proceed near the adhesive interface where the photo-curing agent is present at a high density, and therefore the cohesive force near the adhesive interface is likely to increase and the adhesive force is likely to rise. In addition, when WBL is formed, the increase in storage elastic modulus, which is a main characteristic, tends to be suppressed in the adhesive after photo-curing.
By including urethane (meth) acrylate as the photo-curing agent, the adhesive force of the adhesive layer before photo-curing tends to be reduced. As one of the reasons, it is considered that WBL formation promoting effect is generated by using a urethane (meth) acrylate and a polyfunctional (meth) acrylate having no urethane bond in combination.
In the pressure-sensitive adhesive layer after photocuring, it is considered that the polymer network is formed by the acrylic base polymer having a crosslinked structure and the polymer formed by curing with the photocuring agent, and the cohesive force is improved by the interaction between the polar group of the acrylic base polymer and the polar group of the urethane (meth) acrylate, so that the adhesive force is improved. Further, as described above, when the light curing is performed in a state where WBL is formed, the cohesive force in the vicinity of the adhesive interface is likely to be increased, and therefore, it is considered that the adhesive force and the high-temperature adhesive force at the interface are likely to be increased.
(Photopolymerization initiator)
The photopolymerization initiator generates an active species by irradiation with an active light ray, and accelerates the curing reaction of the photocuring agent. As the photopolymerization initiator, a photo radical polymerization initiator (photo radical generator) is preferably used.
The photo radical polymerization initiator is preferably a photo radical polymerization initiator which generates a radical by irradiation of visible light or ultraviolet light having a wavelength shorter than 450nm, and examples thereof include hydroxyketones, benzildimethylketals, aminoketones, acylphosphinoxides, benzophenones, and triazine derivatives containing a trichloromethyl group. The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the adhesive layer 2 is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, and even more preferably 0.03 to 2 parts by weight, relative to 100 parts by weight of the base polymer. The content of the photopolymerization initiator in the adhesive layer 2 is preferably 0.02 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and even more preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the photocurable agent.
< Other ingredients >
As described above, the photocurable adhesive composition constituting the adhesive layer 2 contains the acrylic base polymer, the photocuring agent, and the photopolymerization initiator. The adhesive composition may contain ingredients other than these.
For example, the adhesive composition may comprise an oligomer having a lower molecular weight than the base polymer. For example, the adhesive composition may contain an acrylic oligomer having a weight average molecular weight of about 1000 to 30000 in addition to the acrylic base polymer.
The pressure-sensitive adhesive composition may contain additives such as a silane coupling agent, a tackifier, a crosslinking accelerator, a crosslinking retarder, a plasticizer, a softener, an antioxidant, a deterioration inhibitor, a filler, a colorant, an ultraviolet absorber surfactant, and an antistatic agent in addition to the above components within a range that does not impair the characteristics of the present invention.
Examples of the crosslinking accelerator (crosslinking catalyst) include organometallic compounds such as organometallic complexes (chelates), compounds of metals and alkoxy groups, and compounds of metals and acyloxy groups, and tertiary amines. The organometallic compound is preferable from the viewpoint of suppressing the progress of the crosslinking reaction in the state of a solution at normal temperature and securing the pot life of the adhesive composition. In addition, from the viewpoint of facilitating introduction of a uniform crosslinked structure throughout the thickness direction of the adhesive layer, an organometallic compound that is liquid at ordinary temperature is preferable as the crosslinking accelerator. Examples of the metal of the organometallic compound include iron, tin, aluminum, zirconium, zinc, titanium, lead, cobalt, zinc, and the like.
Examples of the crosslinking retarder include beta-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oil acetoacetate, lauryl acetoacetate, stearyl acetoacetate, beta-diketones such as acetylacetone, 2, 4-hexanedione, benzoylacetone, and alcohols such as t-butanol.
[ Production of reinforced film ]
By laminating the photocurable adhesive layer 2 on the film base material 1, a reinforced film can be obtained. The adhesive layer 2 may be formed directly on the film base material 1, or an adhesive layer formed in a sheet shape on another base material may be transferred onto the film base material 1.
The adhesive composition is applied to a substrate by roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, blade coating, air knife coating, curtain coating, lip coating, die coating, or the like, and the solvent is removed by drying as needed, thereby forming an adhesive layer. As the drying method, an appropriate method can be suitably employed. The heating and drying temperature is preferably 40 to 200 ℃, more preferably 50 to 180 ℃, and even more preferably 70 to 170 ℃. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and still more preferably 10 seconds to 10 minutes.
In the case where the adhesive composition contains a crosslinking agent, it is preferable to crosslink by heating or aging at the same time as or after the solvent drying. The heating temperature and heating time are set appropriately according to the type of the crosslinking agent used, and crosslinking is usually performed by heating at 20 to 160 ℃ for about 1 minute to 7 days. The heating for drying to remove the solvent may also be used as the heating for crosslinking.
After the cross-linking structure is introduced into the polymer by the cross-linking agent, the photo-curing agent is also maintained in an unreacted state. Therefore, the adhesive layer 2 is formed of a photocurable adhesive composition containing an acrylic base polymer having a crosslinked structure introduced therein, a photocuring agent, and a photopolymerization initiator. When the pressure-sensitive adhesive layer 2 is formed on the film base material 1, a release liner 5 is preferably attached to the pressure-sensitive adhesive layer 2 for the purpose of protecting the pressure-sensitive adhesive layer 2 and the like. The release liner 5 may be attached to the pressure-sensitive adhesive layer 2 and then crosslinked.
In the case of forming the adhesive layer 2 on another substrate, the solvent is dried, and then the adhesive layer 2 is transferred onto the film substrate 1, thereby obtaining a reinforced film. The substrate used in the formation of the adhesive layer may be directly used as the release liner 5.
As the release liner 5, a plastic film such as polyethylene, polypropylene, polyethylene terephthalate, or polyester film is preferably used. The thickness of the release liner is usually 3 to 200. Mu.m, preferably about 10 to 100. Mu.m. The contact surface of the release liner 5 with the pressure-sensitive adhesive layer 2 is preferably subjected to a release treatment using a release agent such as a silicon-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based release agent, or a silica powder. When the release liner 5 is released from the film base material 1 by releasing the surface of the release liner 5, the release occurs at the interface between the adhesive layer 2 and the release liner 5, and the adhesive layer 2 is kept fixed to the film base material 1. The release liner 5 may be antistatic treated on either or both of the release treated surface and the non-treated surface. By applying the antistatic treatment to the release liner 5, electrification at the time of releasing the release liner from the adhesive layer can be suppressed.
[ Properties of reinforced film and use of reinforced film ]
The reinforcing film of the present invention is used by being attached to a device or a device constituent member. The pressure-sensitive adhesive layer 2 of the reinforcing film 10 is fixed to the film base material 1, and has a small adhesion to an adherend before photocuring after bonding to the adherend. Therefore, the reinforcing film is easily peeled from the adherend before photocuring.
The adherend to which the reinforcing film is attached is not particularly limited, and various electronic devices, optical devices, constituent members thereof, and the like can be exemplified. In one embodiment, the reinforcement film is attached to the surface of the flexible device that is capable of being bent. The bendable device has a hinge portion about which the device can be bent. The bending angle may be set arbitrarily, or may be capable of bending (folding) 180 °. In the case where the device is a display device, the reinforcing film may be bonded to the front surface on the screen side or may be bonded to the rear surface (case). In a flexible device having a predetermined portion such as a hinge portion and capable of being bent, bending and stretching are repeatedly performed at the same portion in a use state.
The reinforcing film may be bonded to the entire surface of the adherend, or may be selectively bonded only to a portion (reinforcing target region) to be reinforced. After the reinforcing film is integrally bonded to the portion (reinforcing target region) to be reinforced and the region (non-reinforcing target region) to be reinforced, the reinforcing film is cut and peeled off from the non-reinforcing target region, whereby a device having the reinforcing film bonded only to the reinforcing target region can be produced. If the adhesive is before photo-curing, the reinforcing film is temporarily fixed to the surface of the adherend, and the adhesive force is small, so that the reinforcing film can be easily peeled off from the surface of the adherend.
Since appropriate rigidity can be imparted by attaching the reinforcing film, the effect of improving operability and preventing breakage can be expected for a member having a small thickness such as a flexible device. In the device manufacturing process, when the reinforcing film is bonded to the semi-finished product, the reinforcing film may be bonded to a large-sized semi-finished product before being cut into the product size. The reinforcement film may be applied in a roll-to-roll fashion on a parent roll of a device manufactured by a roll-to-roll process.
For example, after the reinforcing film is bonded to the parent roll of the device or the semi-finished product thereof in a roll-to-roll manner, the parent roll to which the reinforcing film is bonded is cut and separated into individual products, and only the reinforcing film is cut by half-cutting, and the reinforcing film in the non-reinforcing target region is peeled off, whereby the device to which the reinforcing film is bonded in the reinforcing target region is obtained. The cutting method is not particularly limited, and an appropriate cutting method such as a rotary cutter, a press-in cutter (for example, thomson cutter), and a laser cutter may be used.
Before the reinforcing film is attached, the surface of the adherend may be subjected to an activation treatment for the purpose of cleaning or the like. The surface activation treatment includes plasma treatment, corona treatment, glow discharge treatment, and the like.
The adhesion force (initial adhesion force) between the pressure-sensitive adhesive layer 2 before photo-curing and the adherend is preferably 0.4N/25mm or less, more preferably 0.3N/25mm or less, and may be 0.25N/25mm or less or 0.2N/25mm or less, from the viewpoint of easy detachment from the adherend and prevention of residual glue on the adherend after detachment of the reinforcing film. From the viewpoint of preventing peeling of the reinforcing film during storage and handling, the adhesion force between the adhesive layer 2 and the adherend before photo-curing is preferably 0.005N/25mm or more, more preferably 0.01N/25mm or more.
The adhesion was obtained by a peel test using a polyimide film as an adherend and a tensile speed of 300 mm/min and a peel angle of 180 °. Unless otherwise specified, the adhesion is a measured value at 25 ℃. The adhesion between the adhesive layer before photocuring and the adherend was measured using a sample that was left to stand at 25 ℃ for 30 minutes after bonding.
The shear storage elastic modulus (hereinafter, abbreviated as "storage elastic modulus") of the pressure-sensitive adhesive layer 2 before photocuring at a temperature of 25 ℃ is preferably 15kPa or more, more preferably 20kPa or more, and may be 25kPa or more or 30kPa or more. The greater the storage elastic modulus at ordinary temperature of the pressure-sensitive adhesive layer before photocuring, the greater the cutting workability, and the tendency is that the residual adhesive on the adherend is suppressed when the reinforcing film is peeled from the adherend.
On the other hand, when the storage elastic modulus of the adhesive layer before photo-curing is too high at ordinary temperature, the storage elastic modulus of the adhesive layer after photo-curing tends to be high, and the adhesion to an adherend and impact resistance may be insufficient. In addition, when the storage elastic modulus of the adhesive layer before photocuring is large, the storage elastic modulus of the adhesive layer after photocuring tends to be also increased, and when applied to a foldable device, the adhesive layer cannot absorb strain at the bending portion and the periphery thereof, and the reinforcing film is easily peeled from the device. Therefore, the storage elastic modulus of the adhesive layer before photo-curing at a temperature of 25 ℃ is preferably 50kPa or less, more preferably 45kPa or less, and further preferably 40kPa or less.
The storage elastic modulus of the adhesive layer was obtained by reading the value at a predetermined temperature when measured at a temperature rise rate of 5 ℃ per minute in the range of-70 to 200 ℃ under the condition of a frequency of 1Hz according to the method described in JIS K7244-1 "test method of plastic-dynamic mechanical properties". In the present specification, the storage elastic modulus is a value at a temperature of 25 ℃ unless otherwise specified.
After the reinforcing film is attached to the adherend, the adhesive layer 2 is irradiated with an activating ray, whereby the adhesive layer is photo-cured. As the active light rays, ultraviolet rays are preferable. The irradiation intensity and irradiation time of the active light may be appropriately set according to the composition, thickness, and the like of the adhesive layer 2. The irradiation of the adhesive layer 2 with the active light may be performed from either one of the film base material 1 side and the adherend side, or may be performed from both sides.
When the pressure-sensitive adhesive layer 2 is cured by light, the curing reaction of the light-curing agent proceeds, and the adhesion with the adherend increases. From the viewpoint of bonding reliability in the device in use, the bonding force F 1 between the photo-cured adhesive layer and the adherend at a temperature of 25℃is preferably 3N/25mm or more, more preferably 5N/25mm or more, and may be 7N/25mm or more, 9N/25mm or more, or 10N/25mm or more. The adhesion force F 1 between the adhesive layer after photo-curing and the adherend is preferably 10 times or more, more preferably 15 times or more, still more preferably 20 times or more, and may be 30 times or more or 50 times or more the adhesion force F 0 between the adhesive layer before photo-curing and the adherend.
The low-speed peel force F 2, which is obtained by a peel test at a peel angle of 180 DEG at a stretching speed of 10 mm/min at 25 ℃ using a polyimide film as an adherend, is preferably 2.5N/25mm or more, more preferably 3N/25mm or more, but may be 3.5N/25mm or more, 4N/25mm or more, 4.5N/25mm or more, 5N/25mm or more, 5.5N/25mm or more, or 6N/25mm or more.
The peel strength (peel force) in a 180 ° peel test for peeling the reinforcing film 10, which is a laminate of the film base material 1 and the adhesive layer 2, from an adherend can be decomposed into 3 elements, that is, the force required for deformation of the film base material at the time of peeling, the force required for deformation of the adhesive layer, and the force required for peeling both at the adhesion interface of the adherend and the adhesive layer. In general, the greater the stretching speed (peeling speed), the greater the test force (peeling strength). This is because the larger the stretching speed is, the larger the force required for deformation of the film base material and deformation of the adhesive layer is.
In low-speed peeling at a low stretching speed, the force required for deformation of the film base material and deformation of the adhesive layer is small, and therefore the influence of the force required for peeling at the adhesive interface (hereinafter, sometimes referred to as "interface force") is relatively large. Therefore, the test force (low-speed peeling force) F 2 at a low-speed peeling speed of 10 mm/min has a smaller influence on the main body than the test force F 1 at a high-speed peeling speed of 300 mm/min, and tends to reflect the adhesion force at the interface between the pressure-sensitive adhesive layer and the adherend more accurately.
The peeling of the pressure-sensitive adhesive layer tends to be suppressed as the low-speed peeling force F 2 becomes larger, when the adherend is deformed. The foldable device is held in a closed state (flexed state) when the device is not in use, and in an open state (extended state) when the device is in use. At this time, peeling of the reinforcing film accompanying deformation is likely to occur at the hinge portion and the vicinity thereof, but the peeling accompanying such deformation tends to be suppressed by making the low-speed peeling force F 2 of the adhesive layer large.
The adhesion force F 3 between the photocurable pressure-sensitive adhesive layer and the adherend at a temperature of 85 ℃ is preferably 1N/25mm or more, more preferably 2N/25mm or more, still more preferably 3N/25mm or more, but may be 4N/25mm or more, 5N/25mm or more, or 6N/25mm or more.
As described above, since the acrylic base polymer constituting the adhesive composition has a large molecular weight and contains urethane (meth) acrylate as a photo-curing agent, the cohesive force at the adhesive interface is increased, and the low-speed peel force F 2 and the adhesive force F 3 at high temperature tend to be increased.
The storage elastic modulus of the pressure-sensitive adhesive layer after photocuring at a temperature of 25 ℃ is preferably 40kPa or more, more preferably 50kPa or more, and may be 55kPa or more or 60kPa or more, from the viewpoint of achieving high adhesion to an adherend after photocuring. On the other hand, when the storage elastic modulus of the pressure-sensitive adhesive layer after photocuring is too high, the adhesion to an adherend and the impact-attenuating effect (cushioning property) tend to be lowered. In addition, in the case where the storage elastic modulus of the adhesive layer after photo-curing is excessively large, the reinforcing film is easily peeled off from the device at the bending portion and the periphery thereof when applied to the foldable device. Therefore, the storage elastic modulus of the pressure-sensitive adhesive layer after photocuring at a temperature of 25 ℃ is preferably 100kPa or less, more preferably 90kPa or less, and further preferably 80kPa or less.
The amount of the crosslinking agent tends to be smaller, and the storage elastic modulus of the pressure-sensitive adhesive layer after photocuring tends to be smaller, and the amount of the photocuring agent tends to be smaller, so that the increase in the storage elastic modulus of the pressure-sensitive adhesive layer due to photocuring tends to be smaller. Further, by including a polyfunctional (meth) acrylate having no urethane bond and a urethane (meth) acrylate as a photo-curing agent, there is a tendency that the increase in storage elastic modulus of the adhesive layer due to photo-curing is suppressed and the adhesion to the adherend is improved.
By attaching the reinforcing film, appropriate rigidity is imparted to the adherend, and the stress is relaxed and dispersed, so that various defects possibly occurring in the manufacturing process can be suppressed, the production efficiency can be improved, and the yield can be improved.
The pressure-sensitive adhesive layer 2 of the reinforcing film of the present invention is photocurable, and the timing of curing can be arbitrarily set. The reinforcing film of the present invention has a small adhesion force to the surface-treated adherend before photocuring the adhesive layer, and therefore is easy to peel from the adherend, and is easy to rework even when lamination or lamination failure occurs. Further, processing such as selectively removing the reinforcing film from the non-reinforcing target region is also easy.
After the adhesive layer is cured by light, the adhesive layer shows high adhesion to an adherend and also has high adhesion at high temperature, so that the reinforcing film is less likely to peel off from the device surface. In the device with the reinforcing film, in which the reinforcing film of the present invention is bonded to the flexible device using the resin substrate, peeling of the reinforcing film is less likely to occur even when the device is in a stretched state after the device is kept in a bent state, and the bonding reliability is excellent.
Examples (example)
The following examples and comparative examples are given for further illustration, but the present invention is not limited to these examples.
[ Preparation of base Polymer ]
< Polymer A >
Into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 20 parts by weight of Butyl Acrylate (BA), 70 parts by weight of 2-ethylhexyl acrylate (2 EHA), 8 parts by weight of Lauryl Acrylate (LA), 1 part by weight of 4-hydroxybutyl acrylate (4 HBA) and 1 part by weight of N-vinyl-2-pyrrolidone (NVP), 0.1 part by weight of Azobisisobutyronitrile (AIBN) as a thermal polymerization initiator, and 233 parts by weight of ethyl acetate as a solvent were charged, and nitrogen was introduced and nitrogen was substituted for about 1 hour while stirring. Then, the mixture was heated to 60℃and reacted for 7 hours to obtain a solution of the acrylic polymer A having a weight average molecular weight of 180 ten thousand.
< Polymer B >
A solution of an acrylic polymer B having a weight average molecular weight of 55 ten thousand was obtained in the same manner as in the polymerization of the polymer a except that the amount of the thermal polymerization initiator (AIBN) was changed to 0.2 parts by weight.
< Polymers C to F >
The amount of monomer charged was changed as shown in Table 1. Otherwise, a solution of polymers C to F was obtained in the same manner as in the polymerization of the polymer A, B. In the polymerization of the polymer C, E, 0.1 part by weight of a thermal polymerization initiator was used, and in the polymerization of the polymer D, F, 0.2 part by weight of a thermal polymerization initiator was used.
Table 1 shows the ratio of the monomers charged to acrylic polymers A to F and the weight average molecular weight (Mw) of the polymers. The weight average molecular weight (in terms of polystyrene) was measured using GPC (Tosoh "HLC-8220 GPC") under the following conditions.
Sample concentration 0.2 wt% (tetrahydrofuran solution).
The sample injection amount was 10. Mu.L.
Eluent: THF (tetrahydrofuran).
Flow rate 0.6 mL/min.
The temperature was measured at 40 ℃.
Sample column TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2).
Reference column TSKgel SuperH-RC (1).
In Table 1, the monomers are described in the following abbreviations.
BA, butyl acrylate.
2EHA 2-ethylhexyl acrylate.
NOAA n-octyl acrylate.
LA, lauryl acrylate.
2HEA 2-hydroxyethyl acrylate.
4HBA 4-hydroxybutyl acrylate.
AA, acrylic acid.
NVP N-vinyl-2-pyrrolidone.
TABLE 1
[ Production of reinforced film ]
< Preparation of adhesive composition >
The adhesive compositions shown in table 2 were prepared by adding a crosslinking agent, a polyfunctional acrylate (having no urethane bond) and a urethane acrylate as photocuring agents, and a photopolymerization initiator to a solution of an acrylic polymer, and uniformly mixing them.
As a photopolymerization initiator, 0.3 part by weight of "Omnirad 651" manufactured by IGM RESINS was added to 100 parts by weight of the solid content of the acrylic polymer. The crosslinking agent and the photocuring agent (multifunctional acrylate and urethane acrylate) were added in the amounts shown in table 2. The amount added in table 2 is an amount (parts by weight of solid content) based on 100 parts by weight of the acrylic polymer. Details of the crosslinking agent and the photocuring agent are as follows.
(Crosslinking agent)
C/HX isocyanurate of hexamethylene diisocyanate (CORONATE HX, tosoh).
T/C1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane (4-functional epoxy compound, "TETRAD C", mitsubishi gas chemical system ").
(Multifunctional acrylate)
A200. NK ester a200 (polyethylene glycol #200 (n=4) diacrylate; molecular weight 308, functional group equivalent 154 g/eq) from Xinzhongcun chemical industry.
M350 trimethylolpropane EO-modified (n=1) triacrylate (functional equivalent 143g/eq, "ARONIX M-350", manufactured by east Asia Synthesis).
ADPHE ethoxylated dipentaerythritol polyacrylate (New Zhongcun chemical industry Co., ltd. "NK ester A-DPH-12E", functional group equivalent of about 200 g/eq).
(Urethane acrylate)
UA 306-pentaerythritol triacrylate-toluene diisocyanate adduct (co-processed chemical "UA-306T", functional equivalent: 128 g/eq).
UA510 dipentaerythritol pentaacrylate hexamethylene diisocyanate adduct (functional equivalent: 181g/eq, co., ltd., chemical Co., ltd. "UA-510H").
UF-X9-83 urethane acrylate having a polycarbonate skeleton (UF-X9-83, manufactured by Co-Kagaku chemical Co., ltd., functional group number of 2 to 3, weight average molecular weight of 8400).
< Coating and crosslinking of adhesive solution >
The adhesive composition was applied to a polyethylene terephthalate film substrate (mitsubishi chemical system "DIAFOILT 100") having a thickness of 50 μm, which was not subjected to surface treatment, using a spray roll (fountain roll) so that the thickness after drying was 15 μm. After drying at 130℃for 1 minute to remove the solvent, a release treated surface of a release liner (a polyethylene terephthalate film having a surface of 25 μm in thickness, which was subjected to a silicone release treatment) was attached to the coated surface of the adhesive. Then, curing treatment was performed under an atmosphere at 25 ℃ for 4 days, and crosslinking was performed to obtain a reinforced film having an adhesive sheet fixedly laminated on a film base material and a release liner temporarily fixed thereon.
[ Evaluation ]
< Adhesion to polyimide film >
(Adhesive force of adhesive layer before photo-curing)
A polyimide film (UBE "UPILEX 25S") having a thickness of 25 μm was attached to a glass plate via a double-sided adhesive tape (Ridong electric product "No. 531") to obtain a polyimide film substrate for measurement. The release liner was peeled off from the surface of the reinforcing film cut into 25mm wide by 100mm long and bonded to the polyimide film substrate for measurement using a hand press roll.
After the sample was left to stand at 25℃for 30 minutes, the end of the film base material of the reinforcing film was held by a chuck, and a 180℃peel test was performed at a tensile speed of 300 mm/min to measure the peel strength (adhesion F 0 of the reinforcing film to the polyimide film).
(Adhesive force of adhesive layer after photo-curing)
After the reinforcing film was attached to the polyimide film substrate for measurement, the adhesive layer was photo-cured by irradiating the reinforcing film side (film base side) with ultraviolet light having a cumulative light amount of 4000mJ/cm 2 using an LED light source having a wavelength of 365 nm. Using this test sample, the adhesive force F 1 based on the 180 ° peel test at a tensile speed of 300 mm/min and the adhesive force (low speed peel force) F 2 based on the 180 ° peel test at a low speed of 10 mm/min were measured at a temperature of 25 ℃ in the same manner as described above. Further, after the test sample after the photo-curing of the adhesive layer was stored in an oven at a temperature of 85 ℃ for 5 minutes, a 180 ° peel test was performed at a tensile speed of 300 mm/min under an environment at a temperature of 85 ℃, and the adhesive force F 3 was measured.
< Storage elastic modulus >
The release liner was coated with the adhesive composition and crosslinked in the same manner as described above to prepare an adhesive sheet (before photo-curing). A release liner was attached to the surface of the adhesive layer of the adhesive sheet before photo-curing, oxygen was blocked, and 4000mJ/cm 2 of ultraviolet light was irradiated with a 365nm LED lamp to photo-cure the adhesive layer. The adhesive sheet before photocuring and the adhesive sheet after photocuring were each laminated to prepare a measurement sample having a thickness of about 1.5mm, and dynamic viscoelasticity was measured using a rotational rheometer (TAInstruments "Discovery-HR 2") under the following conditions, and the value of the shear storage elastic modulus G' at 25 ℃ was read.
(Measurement conditions)
Deformation mode, torsion.
The measurement frequency was 1Hz.
The temperature rise rate was 5℃per minute.
The temperature is measured at-70-200 ℃.
Shape of parallel plates 8.0mm phi.
< Contamination of adherend >
The release liner was peeled off from the surface of the reinforcing film cut into 25mm wide by 100mm long and bonded to the polyimide film substrate for measurement using a hand press roll. After standing at 25℃for 30 minutes or 24 hours, the reinforced film was peeled off from the polyimide film, and the surface of the polyimide film was visually inspected under a fluorescent lamp to confirm the presence or absence of contamination. The contamination of the adherend was evaluated according to the following criteria.
No contamination was observed in the peeled sample after 24 hours of standing.
A contamination was observed in the peeled sample after 24 hours of standing, but no contamination was observed in the peeled sample after 30 minutes of standing.
Contamination was observed in the peeled sample after standing for 30 minutes.
The composition of the adhesive (type of base polymer, amount of crosslinking agent added, type and amount of photo-curing agent added) of each reinforced film is shown in table 2.
TABLE 2
In comparative example 1, in which an adhesive composition comprising 100 parts by weight of polymer A having a weight average molecular weight of 180 ten thousand and 10 parts by weight of a polyfunctional acrylate (M350) as a photo-curing agent was used, the adhesion force F 0 to a polyimide film exceeded 0.5N/25mm, and exhibited a large initial adhesion force.
In example 1 in which 0.15 parts by weight of urethane acrylate (UA 306) was blended as a photo-curing agent in addition to 10 parts by weight of the polyfunctional acrylate (M350), the initial adhesion force F 0 was 1/3 or less of that of comparative example 1, and the low-speed peeling force F 2 and the high-temperature adhesion force F 3 were greatly increased as compared with comparative example 1. In example 1, the adhesive after photo-curing had a storage elastic modulus of 70kPa or less, and had flexibility suitable for use in foldable devices and the like in addition to high adhesive force.
Comparative example 1 using the polymer B having a weight average molecular weight of 55 ten thousand as the base polymer of the adhesive was low in initial adhesion force F 0 as in example 1, and after the adhesive was photo-cured, adhesion force F 1 at normal temperature was increased, but adhesion force F 3 at high temperature was significantly reduced as compared with example 1.
As is clear from comparison of example 18 using polymer C having a weight average molecular weight of 180 ten thousand with comparative example 5 using polymer D having a weight average molecular weight of 55 ten thousand, when the weight average molecular weight of the base polymer is large, the adhesive force F 3 at high temperature of the adhesive layer after photo-curing becomes large. Example 19 using a polymer E having a weight average molecular weight of 180 ten thousand was similar to example 18, and F 3 was higher than 2N/25mm. It is also clear that examples 1, 18 and 19 have a higher low-speed peel force F 2 of the cured adhesive layer and a higher adhesive force at the interface than comparative example 5.
Example 1 using polymer a showed large values for F 2 and F 3 compared to examples 18, 19 using polymer C, E. The polymer a is considered to be excellent in interfacial force and high-temperature adhesion because of containing a nitrogen atom-containing monomer (NVP) having high cohesive force.
Examples 3 to 5, in which the amount of urethane acrylate (UA 306) added was increased as compared with example 1, were similar to example 1 in that the initial adhesion force F 0 to the adherend was small, and the low-speed release force F 2 and the adhesion force F 3 at high temperature of the adhesive layer after photo-curing showed large values. From the comparison of examples 1 to 5, a tendency was observed that the larger the amount of urethane acrylate, the smaller the initial adhesion force F 0, and the larger F 2 and F 3.
Examples 14 and 15 using urethane acrylate different from example 1 were the same as example 1, in which the initial adhesion force F 0 was small, and the low-speed release force F 2 and the adhesion force F 3 at high temperature of the adhesive layer after photo-curing also showed large values. From these results, it is clear that urethane acrylate contributes to a decrease in initial adhesion and an increase in adhesion of the adhesive layer after photo-curing.
In examples 4 and 5 in which the amount of urethane acrylate was increased, the initial adhesion was reduced and the peeling was satisfactory as compared with examples 1 to 3, but contamination of the adherend was observed when the reinforcing film was peeled off before the photo-curing of the adhesive. The excessive amount of the photo-curing agent oozes out on the surface of the adhesive layer and transfers to the adherend, which is considered to be a cause of contamination.
Example 14 using 10 functional urethane acrylate (UA 510) has a smaller initial adhesion force F 0 and a lower peel force F 2 after photo-curing and a greater adhesion force F 3 at high temperature than example 1 using 6 functional urethane acrylate (UA 306). On the other hand, in example 15 using a urethane acrylate of high molecular weight (UF-X9-83), F 0 was large, F 2 and F 3 were small, compared with example 1 and example 14. From these results, it is clear that the larger the number of functional groups and the smaller the equivalent number of functional groups of the urethane acrylate, the greater the effects of lowering the initial adhesion and improving the adhesion.
Examples 16 and 17, in which the type of the multifunctional acrylate having no urethane bond was changed, showed small initial adhesion to the adherend and high values of the low-speed peel force F 2 and the adhesion force F 3 at high temperature of the adhesive layer after photo-curing, as in example 1.
In comparative example 2 in which the amount of the multifunctional acrylate (M350) was 2 parts by weight, the initial adhesion force F 0 was large, and the low-speed release force F 2 after photo-curing and the adhesion force F 3 at high temperature were insufficient. Comparing examples 1, 10, and 11, in which the amount of the multifunctional (meth) acrylate was changed, a tendency was observed that F 0 was smaller and F 2 and F 3 were larger as the amount of the multifunctional acrylate was larger.
On the other hand, in examples 12 and 13 in which the amount of the multifunctional acrylate was further increased than in example 1, as the amount of the multifunctional acrylate was increased, the initial adhesion was decreased, but the adhesion after the photo-curing was also observed to be decreased. In examples 12 and 13, the adhesive layer after photo-curing had a higher storage elastic modulus than that of example 1, and contamination of the adherend was observed when the reinforcing film was peeled off before photo-curing of the adhesive. In comparative example 3 in which the amount of the multifunctional acrylate was further increased, the adhesive force of the adhesive after photo-curing was as low as less than 1N/25mm, and the storage elastic modulus exceeded 150kPa.
From these results, it is found that the initial adhesion is reduced and the adhesion after photocuring tends to be increased by increasing the amount of the photocuring agent, but when the amount of the photocuring agent is too large, the adhesive after photocuring becomes hard and loses tackiness, and thus high adhesion cannot be achieved.
Comparing example 1 with examples 6 to 9, the tendency was observed that the larger the amount of the crosslinking agent, the smaller the adhesion of the adhesive layer before and after photo-curing, and the larger the storage elastic modulus.
From the above results, it was found that the initial adhesion of the reinforcing film having a photocurable adhesive layer comprising a high molecular weight acrylic polymer, a polyfunctional (meth) acrylate having no urethane bond, and a polyfunctional (meth) acrylate having a urethane bond was small, and the adhesive after photocuring showed high adhesion to an adherend, and the adhesive was also high in low-speed peeling force and adhesion at high temperature, and the adhesive reliability was excellent.
Claims (13)
1. A reinforced film comprising a film base and an adhesive layer fixedly laminated on one main surface of the film base,
The adhesive layer is formed from a photocurable composition comprising an acrylic base polymer, a photocurable agent having 2 or more photopolymerizable functional groups, and a photopolymerization initiator,
The acrylic base polymer contains, as a monomer component, at least one selected from the group consisting of hydroxyl group-containing monomers and carboxyl group-containing monomers, and has a weight average molecular weight of 160 ten thousand or more,
The acrylic base polymer is introduced with a crosslinked structure formed by a crosslinking agent bonded to the hydroxyl group and/or the carboxyl group,
The photocurable composition comprises 3-30 parts by weight of a polyfunctional (meth) acrylate having no urethane bond per 100 parts by weight of the acrylic base polymer as the photocuring agent, and 0.03-5 parts by weight of a urethane (meth) acrylate per 100 parts by weight of the acrylic base polymer as the photocuring agent.
2. The reinforced film of claim 1, wherein,
The acrylic base polymer has a crosslinked structure introduced therein using 0.05 to 1.0 parts by weight of a crosslinking agent based on 100 parts by weight of the polymer.
3. The reinforced film of claim 2, wherein,
The cross-linking agent is isocyanate cross-linking agent or epoxy cross-linking agent.
4. The reinforced film of claim 1, wherein,
The functional group equivalent of the (meth) acryloyl group of the multifunctional (meth) acrylate is 80-500 g/eq.
5. The reinforced film of claim 1, wherein,
The functional group equivalent of the (methyl) acryloyl group of the carbamate (methyl) acrylate is 80-5000 g/eq.
6. The reinforced film of claim 1, wherein,
The urethane (meth) acrylate has 4 or more (meth) acryloyl groups in one molecule.
7. The reinforced film of claim 1, wherein,
The acrylic base polymer contains a nitrogen atom-containing monomer as a monomer component.
8. The reinforced film according to any one of claim 1 to 7, wherein,
The adhesive layer has an adhesion F 0 to a polyimide film at a temperature of 25 ℃ of 0.4N/25mm or less before photo-curing,
The adhesive layer has an adhesive force F 1 to a polyimide film at a temperature of 25 ℃ or more of 3.0N/25mm after photo-curing, and the adhesive layer has an adhesive force F 3 to a polyimide film at a temperature of 85 ℃ or more of 1.0N/25mm after photo-curing.
9. The reinforced film according to any one of claim 1 to 7, wherein,
The adhesive layer has a shear storage elastic modulus of 100kPa or less at a temperature of 25 ℃ after photocuring.
10. A method for manufacturing a device having a reinforcing film bonded to a surface thereof, wherein,
After temporarily fixing the adhesive layer of the reinforcing film according to any one of claims 1 to 9 to the surface of an adherend,
The adhesive layer is irradiated with an active light to thereby photocure the adhesive layer, thereby increasing the adhesion between the reinforcing film and the adherend.
11. The method of manufacturing a device according to claim 10, wherein,
After temporarily fixing the reinforcing film to the adherend, the reinforcing film temporarily fixed to the adherend is cut off before photocuring the adhesive layer, and the reinforcing film is peeled off from a part of the area on the adherend.
12. The method for manufacturing a device according to claim 10 or 11, wherein,
The adherend is a bendable image display element.
13. A reinforcing method for bonding a reinforcing film to the surface of an adherend, wherein,
The adhesive layer of the reinforcing film according to any one of claims 1 to 9 is temporarily fixed to the surface of an adherend,
The adhesive layer is irradiated with an active light to thereby photocure the adhesive layer, thereby increasing the adhesion between the reinforcing film and the adherend.
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