JP3007733B2 - Manufacturing method of pressure sensitive adhesive tape - Google Patents
Manufacturing method of pressure sensitive adhesive tapeInfo
- Publication number
- JP3007733B2 JP3007733B2 JP3295216A JP29521691A JP3007733B2 JP 3007733 B2 JP3007733 B2 JP 3007733B2 JP 3295216 A JP3295216 A JP 3295216A JP 29521691 A JP29521691 A JP 29521691A JP 3007733 B2 JP3007733 B2 JP 3007733B2
- Authority
- JP
- Japan
- Prior art keywords
- functional group
- sensitive adhesive
- meth
- pressure
- adhesive tape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000010410 layer Substances 0.000 claims description 86
- 239000000178 monomer Substances 0.000 claims description 60
- 125000000524 functional group Chemical group 0.000 claims description 50
- 239000012790 adhesive layer Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000010030 laminating Methods 0.000 claims description 13
- 229920000058 polyacrylate Polymers 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 125000004069 aziridinyl group Chemical group 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 description 25
- -1 2-ethylhexyl Chemical group 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000003475 lamination Methods 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- KDRBAEZRIDZKRP-UHFFFAOYSA-N 2,2-bis[3-(aziridin-1-yl)propanoyloxymethyl]butyl 3-(aziridin-1-yl)propanoate Chemical compound C1CN1CCC(=O)OCC(COC(=O)CCN1CC1)(CC)COC(=O)CCN1CC1 KDRBAEZRIDZKRP-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
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- 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
- XEZCCHVCBAZAQD-UHFFFAOYSA-N 2-(aziridin-1-yl)ethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCN1CC1 XEZCCHVCBAZAQD-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical class CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- MVYVKSBVZFBBPL-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NC(=O)C=C MVYVKSBVZFBBPL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KSQXVLVXUFHGJQ-UHFFFAOYSA-M Sodium ortho-phenylphenate Chemical compound [Na+].[O-]C1=CC=CC=C1C1=CC=CC=C1 KSQXVLVXUFHGJQ-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OPECTNGATDYLSS-UHFFFAOYSA-N naphthalene-2-sulfonyl chloride Chemical compound C1=CC=CC2=CC(S(=O)(=O)Cl)=CC=C21 OPECTNGATDYLSS-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- UVVUGWBBCDFNSD-UHFFFAOYSA-N tetraisocyanatosilane Chemical class O=C=N[Si](N=C=O)(N=C=O)N=C=O UVVUGWBBCDFNSD-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 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 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐せん断応力にすぐれ
た多層構造の接着剤層を有するアクリル系の感圧性接着
テ―プの製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an acrylic pressure-sensitive adhesive tape having an adhesive layer having a multilayer structure excellent in shear stress.
【０００２】[0002]
【従来の技術】従来から、両面接着テ―プのような感圧
性接着テ―プに対しては、被着体に対する高い濡れ性、
接着性と、高い凝集力という相反する特性をあわせ持つ
ことが要求されてきた。さらに、被着体相互が異なる表
面特性を持つ場合、同一の組成からなる感圧性接着剤で
は、両被着体のいずれに対しても良好な接着特性を発揮
することは難しく、両者の中間的な特性上のバランスを
とる形で処理されていることが多い。2. Description of the Related Art Conventionally, a pressure-sensitive adhesive tape such as a double-sided adhesive tape has a high wettability to an adherend,
It has been required to have the contradictory properties of adhesiveness and high cohesion. Furthermore, when the adherends have different surface characteristics, it is difficult for a pressure-sensitive adhesive having the same composition to exhibit good adhesion characteristics to both of the adherends. It is often processed in a way that balances the characteristics.
【０００３】このような点を改良するため、組成の異な
る２種以上の感圧性接着剤を用いて多層構造とすること
により、異なる被着体や支持体に対する接着性、投錨性
を向上させたり、被着体との強い結合が要求される表面
層と、高い凝集力が要求される内部層との組成および物
性を変え、特性のコントロ―ルを行う試みがある。[0003] In order to improve such a point, a multilayer structure is formed by using two or more kinds of pressure-sensitive adhesives having different compositions to improve the adhesion and anchoring to different adherends and supports. Attempts have been made to control the properties by changing the composition and physical properties of the surface layer, which requires strong bonding with the adherend, and the inner layer, which requires high cohesion.
【０００４】たとえば、特開昭５４−１３９９４６号公
報には、異なるせん断クリ―プコンプライアンスを持つ
２種以上の組成物からなる多層構造の接着剤層を有する
感圧性接着テ―プが開示されており、このテ―プは、被
着体が不規則表面であつてかつ使用時にさまざまな外部
応力が加わるおむつ用テ―プや布表示ラベルの用途に特
に有用であるとされている。For example, Japanese Patent Application Laid-Open No. 54-139946 discloses a pressure-sensitive adhesive tape having a multi-layered adhesive layer composed of two or more compositions having different shear creep compliances. This tape is said to be particularly useful for diaper tapes and cloth labeling in which the adherend has an irregular surface and various external stresses are applied during use.
【０００５】しかるに、接着剤層が上記の如く多層構造
とされた感圧性接着テ―プは、各層間の結合力が弱く、
せん断力などの外部応力に対して層間が剥離しやすいと
いう欠点がある。これは、上記の多層構造が溶液キヤス
ト法などでつくられたフイルム状の接着剤層をただ単に
積層しただけのものであるため、各層間で分子の十分な
混合，浸透，結合がおこりにくく、分子間力，イオン結
合力といつた比較的弱い力によつてのみ、層間が結びつ
けられているためと推定される。However, the pressure-sensitive adhesive tape in which the adhesive layer has a multilayer structure as described above has a weak bonding force between the layers,
There is a disadvantage that the layers are easily separated by an external stress such as a shearing force. This is because the above-mentioned multilayer structure is formed by simply laminating a film-like adhesive layer formed by a solution casting method or the like, so that sufficient mixing, permeation and bonding of molecules between the respective layers hardly occur. It is presumed that the layers are linked only by relatively weak forces such as intermolecular force and ionic bond force.
【０００６】そこで、ジムマ―マンらは、特公平２−６
７９０号公報において、複数の重ね合された層からな
り、少なくとも１つの外層は感圧性接着層であり、隣接
する層はその隣接層間で界面を画成しており、それら層
の各々は光重合した高分子鎖マトリツクスからなり、そ
れら高分子鎖はそれら層の１つのマトリツクスからこの
界面を通して隣接層のマトリツクスの中に延在してお
り、それら高分子鎖は重合前に各隣接層のマトリツクス
から移行してきた重合したモノマ―からなり、かくして
それら層は離層を起こすことができないようになつてい
る感圧性接着テ―プを提案している。Accordingly, Jim Merman et al.
No. 790, the invention comprises a plurality of superposed layers, at least one outer layer being a pressure-sensitive adhesive layer, an adjacent layer defining an interface between the adjacent layers, and each of the layers being photopolymerized. Polymer chains extending from one matrix of the layer through this interface into the matrix of the adjacent layer, and the polymer chains are separated from the matrix of each adjacent layer before polymerization. We propose a pressure-sensitive adhesive tape consisting of a polymerized monomer that has migrated, so that the layers are incapable of delamination.
【０００７】また、村上らは、特開平１−２６３１８２
号公報において、担体上で、アルキル基の炭素数が２〜
１４個の（メタ）アクリル酸アルキルエステル５０〜１
００重量％とこれと共重合可能なビニル系モノマ―５０
〜０重量％とからなるアクリル系モノマ―を、部分重合
させて得たモノマ―残存率が１〜６０重量％の範囲の部
分重合体フイルムの少なくとも２種を、隣接フイルム間
で互いのモノマ―組成が異なるように、積層圧着したう
えで、各フイルム中の残存モノマ―を重合することによ
り、各層間の結合強度を非常に大きくできることを示し
ている。Further, Murakami et al., JP-A-1-263182
In the publication, on the carrier, the carbon number of the alkyl group is 2 to
14 (meth) acrylic acid alkyl esters 50-1
00% by weight and a copolymerizable vinyl monomer 50
At least two kinds of partially polymer films having a residual ratio of 1 to 60% by weight obtained by partially polymerizing an acrylic monomer comprising from 0 to 0% by weight of at least two monomers between adjacent films. It is shown that the bonding strength between the layers can be extremely increased by polymerizing the remaining monomers in each film after the layers are pressure-bonded so that the compositions are different.
【０００８】[0008]
【発明が解決しようとする課題】しかるに、ジムマ―マ
ンらの方法では、モノマ―を含有する塗被可能な組成物
を多層状に遂次コ―テイングする必要があり、その際層
間で機械的な混合が生じる問題がある。このため、ジム
マ―マンらは、特開平１−１２１３８６号公報で、同時
押出しにより多層に並行的にコ―テイングする方法を提
案しているが、やはり層間での混合を防ぐには、組成物
の粘度に制約が必要であるうえ、コ―テイング装置が高
価になる問題がある。また、村上らの方法では、部分重
合体フイルムの機械的強度が弱いため、積層工程の作業
性が悪くなる問題がある。However, according to the method of Jim Merman et al., It is necessary to coat a coatable composition containing a monomer in a multi-layered form, in which case a mechanical coating is applied between the layers. There is a problem that mixing occurs. For this reason, Jim Merman et al., In Japanese Patent Application Laid-Open No. 1-112386, have proposed a method of coating in multiple layers in parallel by coextrusion. In addition, there is a problem that the viscosity is required to be restricted and the coating apparatus is expensive. Further, the method of Murakami et al. Has a problem that the workability of the laminating step is deteriorated because the mechanical strength of the partial polymer film is weak.
【０００９】このような問題を解決するには、予め重合
された２層を積層する方法が考えられるが、ただ単に貼
り合わすだけでは、層間で十分な結合強度を得ることは
困難である。一般に、層間の結合強度を改善するため
に、下塗り剤を用いることは公知であるが（たとえば、
特公昭５０−２０１０８号、同３９−３００５４号など
の公報）、溶剤を使用することや処理工程が増えるなど
の問題が新たに生じるため、決して好ましい方法とは言
えない。In order to solve such a problem, a method of laminating two layers polymerized in advance can be considered, but it is difficult to obtain a sufficient bonding strength between the layers simply by laminating. In general, it is known to use a primer to improve the bond strength between layers (for example,
Japanese Patent Publication Nos. 50-20108 and 39-30054), and the use of a solvent and an increase in the number of processing steps cause new problems.
【００１０】本発明は、上記従来の事情に鑑み、層間の
結合強度にすぐれた多層構造の接着剤層を有する感圧性
接着テ―プを、層間の混合を生じることなく、作業性お
よび経済性良好に製造できる方法を提供することを目的
としている。In view of the above-mentioned conventional circumstances, the present invention provides a pressure-sensitive adhesive tape having a multi-layered adhesive layer having an excellent bonding strength between layers without causing mixing between the layers, thereby improving workability and economy. It is an object of the present invention to provide a method that can be favorably manufactured.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、上記の目
的を達成するために鋭意検討した結果、予め光重合させ
て得た少なくとも２種の接着剤層を、ラミネ―トロ―ル
などで積層したのち、各層を構成するポリマ―分子の官
能基相互の橋かけ反応により、隣接層同士を化学的に結
合させるようにしたとき、層間の結合強度にすぐれた多
層構造の接着剤層を有する感圧性接着テ―プが、層間で
の乱れを生じることなく、作業性および経済性良好に得
られることを知り、本発明をなすに至つた。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that at least two kinds of adhesive layers obtained by photopolymerization in advance can be used, such as laminating trolley. After laminating the layers, when the adjacent layers are chemically bonded by a cross-linking reaction between the functional groups of the polymer molecules constituting each layer, an adhesive layer having a multilayer structure with excellent bonding strength between the layers is formed. The present inventors have found that the pressure-sensitive adhesive tape can be obtained with good workability and economical efficiency without causing disturbance between the layers, and have led to the present invention.
【００１２】すなわち、本発明は、多層構造の接着剤層
を有するアクリル系の感圧性接着テ―プの製法におい
て、（メタ）アクリル酸アルキルエステルと光重合開始
剤とを含む組成物を光重合させて得た少なくとも２種の
接着剤層を、隣接層間でその組成が異なるように積層し
たのち、隣接層の一方の層を構成する（メタ）アクリル
酸アルキルエステル系ポリマ―の分子内に導入された反
応性官能基と、他方の層を構成する（メタ）アクリル酸
アルキルエステル系ポリマ―の分子内に導入された活性
水素含有の官能基との反応により、隣接層同士を化学的
に結合させるようにしたことを特徴とする感圧性接着テ
―プの製法に係るものである。That is, the present invention relates to a method for producing an acrylic pressure-sensitive adhesive tape having an adhesive layer having a multilayer structure, wherein a composition containing an alkyl (meth) acrylate and a photopolymerization initiator is photopolymerized. After laminating at least two kinds of adhesive layers obtained so as to have different compositions between adjacent layers, the adhesive layers are introduced into the molecules of the alkyl (meth) acrylate-based polymer constituting one of the adjacent layers. Reaction between the reactive functional group and the active hydrogen-containing functional group introduced into the molecule of the alkyl (meth) acrylate-based polymer constituting the other layer chemically bonds the adjacent layers. The present invention relates to a method for producing a pressure-sensitive adhesive tape, wherein
【００１３】[0013]
【発明の構成・作用】本発明においては、まず、（メ
タ）アクリル酸アルキルエステルと光重合開始剤とを含
む組成物を光重合させて、少なくとも２種のアクリル系
の接着剤層を形成する。この接着剤層のひとつは、光重
合により得られる（メタ）アクリル酸アルキルエステル
系ポリマ―の分子内に反応性官能基が導入され、他のひ
とつは、光重合により得られる（メタ）アクリル酸アル
キルエステル系ポリマ―の分子内に活性水素含有の官能
基が導入される。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, first, a composition containing an alkyl (meth) acrylate and a photopolymerization initiator is photopolymerized to form at least two types of acrylic adhesive layers. . One of the adhesive layers has a reactive functional group introduced into the molecule of a (meth) acrylic acid alkyl ester polymer obtained by photopolymerization, and the other has (meth) acrylic acid obtained by photopolymerization. An active hydrogen-containing functional group is introduced into the molecule of the alkyl ester polymer.
【００１４】なお、以下、（メタ）アクリル酸アルキル
エステル系ポリマ―は、単にアクリル系ポリマ―と言
い、このアクリル系ポリマ―の分子内に反応性官能基が
導入される接着剤層を第１の層、また活性水素含有の官
能基が導入される接着剤層を第２の層、とそれぞれ称す
ることにする。Hereinafter, the (meth) acrylic acid alkyl ester-based polymer is simply referred to as an acrylic polymer, and an adhesive layer in which a reactive functional group is introduced into the molecule of the acrylic polymer is a first polymer. And the adhesive layer into which the active hydrogen-containing functional group is introduced will be referred to as a second layer.
【００１５】第１の層は、（メタ）アクリル酸アルキル
エステルを含むモノマ―に光重合開始剤と必要によりそ
の他の添加剤を加えた組成物を、光重合することにより
得られる。ここで、得られるアクリル系ポリマ―の分子
内に反応性官能基を導入するには、モノマ―のひとつに
反応性官能基を含むモノマ―を用いるか、あるいはモノ
マ―のひとつに活性水素含有の官能基を含むモノマ―を
用いて、かつこの活性水素含有の官能基に多官能性架橋
剤を反応させればよい。The first layer is obtained by photopolymerizing a composition comprising a monomer containing an alkyl (meth) acrylate and a photopolymerization initiator and, if necessary, other additives. Here, in order to introduce a reactive functional group into the molecule of the obtained acrylic polymer, a monomer containing a reactive functional group is used as one of the monomers, or an active hydrogen-containing monomer is used as one of the monomers. What is necessary is just to use a monomer containing a functional group and to react a polyfunctional crosslinking agent with the active hydrogen-containing functional group.
【００１６】（メタ）アクリル酸アルキルエステルとし
ては、（メタ）アクリル酸メチル、（メタ）アクリル酸
ｎ−ブチル、（メタ）アクリル酸２−エチルヘキシル、
（メタ）アクリル酸イソオクチル、（メタ）アクリル酸
イソノニルなどのアルキル基の炭素数が１〜１４の範囲
にあるものが、好ましく用いられる。Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Those in which the alkyl group has 1 to 14 carbon atoms, such as isooctyl (meth) acrylate and isononyl (meth) acrylate, are preferably used.
【００１７】このような（メタ）アクリル酸アルキルエ
ステルとともに、一般のアクリル系感圧性接着剤の改質
用モノマ―として知られる、酢酸ビニル、スチレンなど
の各種のビニル系モノマ―を、モノマ―全体の５０重量
％以下、好ましくは３０重量％以下の割合で使用しても
よい。Along with such an alkyl (meth) acrylate, various vinyl monomers such as vinyl acetate and styrene, which are known as modifiers for general acrylic pressure-sensitive adhesives, are combined with the monomer as a whole. May be used in a proportion of 50% by weight or less, preferably 30% by weight or less.
【００１８】反応性官能基を含むモノマ―としては、反
応性官能基がイソシアネ―ト基、エポキシ基またはアジ
リジン基であるモノエチレン系不飽和モノマ―が用いら
れ、その例としては、イソシアネ―トエチルメタクリレ
―トなどのイソシアネ―ト基含有モノマ―、グリシジル
アクリレ―ト、グリシジルメタクリレ―トなどのグリシ
ジル基含有モノマ―、２−（１−アジリジニル）エチル
メタクリレ―トなどのアジリジン基含有モノマ―を挙げ
ることができる。As the monomer containing a reactive functional group, a monoethylenically unsaturated monomer whose reactive functional group is an isocyanate group, an epoxy group or an aziridine group is used. Isocyanate group-containing monomers such as ethyl methacrylate, glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, and aziridine groups such as 2- (1-aziridinyl) ethyl methacrylate Containing monomers can be mentioned.
【００１９】このような反応性官能基を含むモノマ―を
用いて、アクリル系ポリマ―の分子内に反応性官能基を
導入する場合、このモノマ―の使用量は、通常モノマ―
全体の０．００１〜１０重量％、好ましくは０．０１〜
２重量％の範囲内とするのがよい。過少では層間の化学
結合が不十分となり、十分な層間接着性が得られず、ま
た過多となると架橋が進みすぎて十分な粘着特性が得ら
れなくなる。When a reactive functional group is introduced into the molecule of an acrylic polymer using a monomer containing such a reactive functional group, the amount of the monomer used is usually
0.001 to 10% by weight of the whole, preferably 0.01 to
The content is preferably in the range of 2% by weight. If the amount is too small, the chemical bonding between the layers becomes insufficient, so that sufficient interlayer adhesion cannot be obtained. If the amount is too large, crosslinking proceeds excessively and sufficient adhesive properties cannot be obtained.
【００２０】活性水素含有の官能基を含むモノマ―とし
ては、活性水素含有の官能基が水酸基またはカルボキシ
ル基であるモノエチレン系不飽和モノマ―が好ましく用
いられ、その例としては、（メタ）アクリル酸、イタコ
ン酸などのカルボキシル基含有モノマ―、２−ヒドロキ
シエチル（メタ）アクリレ―ト、２−ヒドロキシプロピ
ル（メタ）アクリレ―トなどの水酸基含有モノマ―が挙
げられる。また、活性水素含有の官能基がスルホン酸基
である２−アクリルアミドプロパンスルホン酸などや、
その他上記官能基がメチロ―ル基、アミノ基、シラノ―
ル基などであるモノエチレン系不飽和モノマ―を使用す
ることもできる。As the monomer containing an active hydrogen-containing functional group, a monoethylenically unsaturated monomer in which the active hydrogen-containing functional group is a hydroxyl group or a carboxyl group is preferably used. Examples thereof include carboxyl group-containing monomers such as acid and itaconic acid, and hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Also, such as 2-acrylamidopropanesulfonic acid whose active hydrogen-containing functional group is a sulfonic acid group,
In addition, the above functional groups are methylol groups, amino groups, silano-
A monoethylenically unsaturated monomer such as a methyl group may also be used.
【００２１】この活性水素含有の官能基を含むモノマ―
は、既述のように、その活性水素含有の官能基に多官能
性架橋剤を反応させることによつて、アクリル系ポリマ
―の分子内に反応性官能基を導入させるためのモノマ―
として機能させるが、同時に極性基含有のモノマ―とし
てそれ自体が接着特性の向上に寄与する成分としても機
能する。したがつて、この活性水素含有の官能基を含む
モノマ―は、前記の反応性官能基を含むモノマ―を用い
る場合でも、このモノマ―とともに使用してよいもので
ある。The monomer containing the active hydrogen-containing functional group
As described above, a monomer for introducing a reactive functional group into a molecule of an acrylic polymer by reacting a polyfunctional crosslinking agent with the active hydrogen-containing functional group, as described above.
, But at the same time, as a monomer containing a polar group, itself functions as a component contributing to the improvement of adhesive properties. Therefore, the monomer containing the active hydrogen-containing functional group may be used together with the monomer even when the monomer containing the reactive functional group is used.
【００２２】このような活性水素含有の官能基を含むモ
ノマ―の使用量は、上記の機能を考慮して、通常モノマ
―全体の１〜３０重量％、好ましくは２〜２０重量％の
範囲内とするのがよい。この範囲外では、十分な層間接
着性が得られなかつたり、接着特性が損なわれることが
あるため、好ましくない。The amount of such a monomer containing an active hydrogen-containing functional group is usually in the range of 1 to 30% by weight, preferably 2 to 20% by weight of the entire monomer in consideration of the above functions. It is good to do. Outside this range, it is not preferable because sufficient interlayer adhesion cannot be obtained or the adhesive properties may be impaired.
【００２３】第１の層に用いるモノマ―としては、他
に、層内での重合体の橋かけ密度を制御する目的で、１
分子内にモノエチレン系不飽和基を２個以上有する架橋
性モノマ―を使用してもよい。この架橋性モノマ―とし
ては、ポリエチレングリコ―ルジ（メタ）アクリレ―
ト、ペンタエリスリト―ルジ（メタ）アクリレ―ト、ト
リメチロ―ルプロパントリ（メタ）アクリレ―ト、ヘキ
サンジオ―ルジ（メタ）アクリレ―ト、エポキシアクリ
レ―ト、ウレタンアクリレ―トなどが挙げられる。使用
量は、モノマ―全体の１重量％以下とするのがよく、あ
まり多すぎると、架橋過多となつて接着特性を却つて損
なう結果となる。Other monomers used for the first layer include, for the purpose of controlling the crosslinking density of the polymer in the layer, 1
A crosslinkable monomer having two or more monoethylenically unsaturated groups in the molecule may be used. As this crosslinkable monomer, polyethylene glycol di (meth) acrylate
And pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, epoxy acrylate and urethane acrylate. The amount to be used is preferably not more than 1% by weight of the whole monomer, and if it is too much, it results in excessive crosslinking and impairs the adhesive properties.
【００２４】このようなモノマ―混合物に加える光重合
開始剤には、ベンゾインメチルエ―テル、ベンゾインイ
ソプロピルエ―テルなどのベンゾインエ―テル類、アニ
ゾインメチルエ―テルなどの置換ベンゾインエ―テル
類、２・２−ジエトキシアセトフエノン、２・２−ジメ
トキシ−２−フエノンアセトフエノンなどの置換アセト
フエノン類、２−メチル−２−ヒドロキシプロピオフエ
ノンなどの置換−α−ケト―ル類、２−ナフタレンスル
ホニルクロリドなどの芳香族スルホニルクロリド類およ
び１−フエノン−１・１−プロパンジオン−２−（ｏ−
エトキシカルボニル）オキシムなどの光活性オキシム類
がある。これらの光重合開始剤は、前記のモノマ―混合
物１００重量部に対して、通常０．０１〜４重量部の範
囲、好ましくは０．１〜３重量部の範囲で用いられる。The photopolymerization initiator added to such a monomer mixture includes benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether, and substituted benzoin ethers such as anisoin methyl ether. Substituted acetophenones such as 2,2-diethoxyacetophenone, 2.2-dimethoxy-2-phenoneacetophenone, and substituted α-ketoles such as 2-methyl-2-hydroxypropiophenone , 2-naphthalenesulfonyl chloride and other aromatic sulfonyl chlorides and 1-phenone-1-1-propanedione-2- (o-
There are photoactive oximes such as (ethoxycarbonyl) oxime. These photopolymerization initiators are used in an amount of usually 0.01 to 4 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the monomer mixture.
【００２５】第１の層における光重合用の組成物には、
上記のモノマ―混合物および光重合開始剤のほかに、必
要により、連鎖移動剤、増粘剤、チキソトロ―プ剤、充
てん剤などの各種の添加剤を適宜加えることができる。
連鎖移動剤としては、アルキルメルカプタン、チオグリ
コ―ル酸、ジフエニルサルフアイドなどが、増粘剤とし
てはクロロプレンゴム、アクリルゴムなどがある。充て
ん剤としては、炭酸カルシウム、クレ―、シリカなどの
無機系充てん剤、ガラスバル―ン、シラスバル―ンなど
の無機中空体、アクリルバル―ン、塩化ビニリデンバル
―ンなどの有機中空体、プラスチツクビ―ズなどが挙げ
られる。これらの添加剤は、前記のモノマ―混合物に対
してその目的の範囲で使用するのがよい。The composition for photopolymerization in the first layer includes:
In addition to the monomer mixture and the photopolymerization initiator, various additives such as a chain transfer agent, a thickener, a thixotropic agent, and a filler can be appropriately added as needed.
Examples of the chain transfer agent include alkyl mercaptan, thioglycolic acid, and diphenyl sulfide, and examples of the thickener include chloroprene rubber and acrylic rubber. Examples of the filler include inorganic fillers such as calcium carbonate, clay, and silica; inorganic hollow bodies such as glass balloon and silas balloon; organic hollow bodies such as acrylic balloon and vinylidene balloon; -And the like. These additives are preferably used for the above-mentioned monomer mixture within the range of the purpose.
【００２６】このような種々の成分を含む組成物を、部
分的または全体的に光重合させたのち、用いた活性水素
含有の官能基を有するモノマ―の上記官能基にさらに多
官能性架橋剤を反応させて、アクリル系ポリマ―の分子
内に反応性官能基を導入させる場合には、この多官能性
架橋剤として、分子中に２個以上のイソシアネ―ト基、
エポキシ基またはアジリジン基を有する多官能性架橋剤
が用いられる。After partially or wholly photopolymerizing a composition containing such various components, a polyfunctional crosslinking agent is further added to the above-mentioned functional group of the monomer having a functional group containing an active hydrogen used. When a reactive functional group is introduced into the molecule of the acrylic polymer by reacting the above, two or more isocyanate groups,
A polyfunctional crosslinking agent having an epoxy group or an aziridine group is used.
【００２７】イソシアネ―ト基を有する多官能性架橋剤
としては、ジメチルシリルジイソシアネ―ト、メチルシ
リルトリイソシアネ―ト、テトライソシアネ―トシラ
ン、フエニルシリルトリイソシアネ―ト、エトキシシラ
ントリイソシアネ―トなどのケイ素イソシアネ―ト化合
物、２・４−トリレンジイソシアネ―ト、パラフエニレ
ンジイソシアネ―ト、１・６−ヘキサメチレンジイソシ
アネ―ト、イソホロンジイソシアネ―トなどのジイソシ
アネ―ト化合物や、ブロツク型イソシアネ―ト〔たとえ
ば、日本ポリウレタン工業（株）製のコロネ―ト２５０
７、同２５１３、同２５１５など〕が挙げられる。Examples of the polyfunctional crosslinking agent having an isocyanate group include dimethylsilyl diisocyanate, methylsilyl triisocyanate, tetraisocyanate silane, phenylsilyl triisocyanate, and ethoxy silane. Silicon isocyanate compounds such as triisocyanate, 2,4-tolylene diisocyanate, paraphenylene diisocyanate, 1.6-hexamethylene diisocyanate, isophorone diisocyanate Such as diisocyanate compounds and block-type isocyanates [for example, Coronate 250 manufactured by Nippon Polyurethane Industry Co., Ltd.]
7, 2513, 2515, etc.].
【００２８】エポキシ基を有する多官能性架橋剤として
は、１・３−ビス（Ｎ・Ｎ−ジグリシジルアミノメチ
ル）シクロヘキサノン、ジグリシジルオルソトルイジ
ン、Ｎ・Ｎ・Ｎ´・Ｎ´−テトラグリシジルｍ−キシレ
ンジアミンなどのグリシジルアミン化合物、ネオペンチ
ルグリコ―ルジグリシジルエ―テル、１・６−ヘキサン
ジオ―ルジグリシジルエ―テルなどのグリシジルエ―テ
ル化合物が挙げられる。Examples of the polyfunctional crosslinking agent having an epoxy group include 1,3-bis (NN-diglycidylaminomethyl) cyclohexanone, diglycidyl orthotoluidine, NNNN'N'-tetraglycidylm Glycidylamine compounds such as xylene diamine; glycidyl ether compounds such as neopentyl glycol diglycidyl ether and 1.6-hexanediol diglycidyl ether.
【００２９】アジリジン基を有する多官能性架橋剤とし
ては、トリメチロ―ルプロパントリス〔３−（１−アジ
リジニル）プロピオネ―ト〕、トリメチロ―ルプロパン
トリス〔３−（１−（２−メチル）アジリジニルプロピ
オネ―ト）〕などのアジリジン化合物が挙げられる。Examples of the polyfunctional crosslinking agent having an aziridine group include trimethylolpropane tris [3- (1-aziridinyl) propionate] and trimethylolpropane tris [3- (1- (2-methyl) azi Aziridine compounds such as lysinylpropionate)].
【００３０】これらの多官能性架橋剤の使用量は、前記
のモノマ―混合物１００重量部に対して、通常０．００
１〜５重量部の範囲、好ましくは０．０１〜２重量部の
割合で用いられる。添加量が過少では、層間の化学結合
が不十分となり、十分な層間接着性が得られず、過多と
なると、得られる重合物の架橋が進みすぎ十分な粘着特
性が得られなくなる。The amount of the polyfunctional crosslinking agent used is usually 0.001 part by weight based on 100 parts by weight of the monomer mixture.
It is used in the range of 1 to 5 parts by weight, preferably 0.01 to 2 parts by weight. If the amount is too small, the chemical bonding between the layers will be insufficient, and sufficient interlayer adhesion will not be obtained. If the amount is too large, crosslinking of the resulting polymer will proceed too much and sufficient adhesive properties will not be obtained.
【００３１】第２の層は、上記第１の層の場合と同様
に、（メタ）アクリル酸アルキルエステルを含むモノマ
―に光重合開始剤と必要によりその他の添加剤を加えた
組成物を、光重合することにより得られ、その際モノマ
―のひとつに活性水素含有の官能基を含むモノマ―を用
いることにより、得られるアクリル系ポリマ―の分子内
に活性水素含有の官能基を導入させることができる。ま
た、第１の層と同様に反応性官能基を含むモノマ―や多
官能性架橋剤を添加し、反応性官能基を導入してもよ
い。As in the case of the above-mentioned first layer, the second layer is made of a composition comprising a monomer containing an alkyl (meth) acrylate and a photopolymerization initiator and, if necessary, other additives. Obtaining a functional group containing an active hydrogen into the molecule of the acrylic polymer obtained by using a monomer obtained by photopolymerization and having a functional group containing an active hydrogen as one of the monomers. Can be. Further, similarly to the first layer, a monomer containing a reactive functional group or a polyfunctional crosslinking agent may be added to introduce the reactive functional group.
【００３２】モノマ―の種類や各モノマ―の使用量など
については、上記第１の層の場合と同じであり、これに
加える光重合開始剤および添加剤の種類や使用量も特に
異なるところはない。もちろん、第１の層とは、用いる
モノマ―組成などが異なり、それにより異なる接着特性
が得られるように、上記各成分の種類や使用量などが適
宜選択されるものであることは言うまでもない。The types of monomers and the amount of each monomer used are the same as in the case of the first layer, and the types and amounts of the photopolymerization initiator and the additives to be added are particularly different. Absent. It goes without saying that the first layer differs from the first layer in the monomer composition and the like, and the types and amounts of the above components are appropriately selected so as to obtain different adhesive properties.
【００３３】なお、第１の層または第２の層には、積層
後の橋かけ反応、つまり両層のアクリル系ポリマ―の分
子内に導入された反応性官能基と活性水素含有の官能基
との反応をすみやかに行うため、触媒を加えることがで
きる。この触媒としては、トリエチルアミン、トリエチ
レンジアミン、ジメチルアミノニチルアクリレ―ト、ジ
エチルアミノエチルアクリレ―トなどのアミン類、塩化
第２スズ、塩化第２鉄、三塩化アンチモンなどの金属塩
類、ジブチルチンジウラレ―ト、テトラ（２−エチルヘ
キシル）チタネ―ト、ナトリウムオルトフエニルフエネ
―トなどの有機金属化合物が挙げられる。The first layer or the second layer has a crosslinking reaction after lamination, that is, a reactive functional group introduced into the molecules of the acrylic polymer of both layers and a functional group containing active hydrogen. A catalyst can be added in order to promptly react with the catalyst. Examples of the catalyst include amines such as triethylamine, triethylenediamine, dimethylaminonityl acrylate, diethylaminoethyl acrylate, metal salts such as stannic chloride, ferric chloride, and antimony trichloride; And organic metal compounds such as lalate, tetra (2-ethylhexyl) titanate and sodium orthophenyl phenate.
【００３４】これら触媒の使用量としては、前記のモノ
マ―混合物１００重量部に対して、通常０．０１〜５重
量部の範囲とするのがよい。また、これらの触媒は、第
１の層または第２の層のいずれにも添加することが可能
であるが、好ましくは第２の層に添加するのがよい。The amount of these catalysts to be used is generally preferably in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the monomer mixture. In addition, these catalysts can be added to either the first layer or the second layer, but are preferably added to the second layer.
【００３５】第１の層および第２の層を得るには、上記
の光重合用の組成物をそれぞれ被着体上に直接塗工する
か、または一旦剥離紙上に塗工したうえで、４００〜
２，０００mj／cm2 程度の紫外線を照射して光重合させ
る。その際、塗工を容易に行うため、上記の光重合用の
組成物に予め少量の紫外線を照射し、その一部を重合す
ることにより増粘することができる。In order to obtain the first layer and the second layer, the above-mentioned photopolymerization composition is applied directly to an adherend, or is applied once to a release paper and then applied to a release paper. ~
Irradiation of ultraviolet rays of about 2,000 mj / cm 2 causes photopolymerization. At that time, in order to easily perform the coating, the composition for photopolymerization may be irradiated with a small amount of ultraviolet light in advance, and the viscosity may be increased by polymerizing a part thereof.
【００３６】このようにして得られる第１の層および第
２の層の重合率は、その保形性の面より、７０重量％以
上、好ましくは９０重量％以上であるのがよい。また、
重合率がこれらの値以下であつても、熱乾燥などの手段
で固形分濃度（ポリマ―ベ―ス）を、７０重量％以上、
好適には９０重量％以上にしておくのが望ましい。この
固形分濃度が低すぎると、第１の層および第２の層の取
り扱いが難しく、以後の工程における作業性が悪くなる
という問題が生じる。The polymerization rates of the first layer and the second layer thus obtained are preferably 70% by weight or more, and more preferably 90% by weight or more, in view of the shape retention. Also,
Even when the polymerization rate is less than these values, the solid content concentration (polymer base) is increased to 70% by weight or more by means such as heat drying.
Preferably, it is 90% by weight or more. If the solid content concentration is too low, the first layer and the second layer are difficult to handle, resulting in a problem that workability in subsequent steps is deteriorated.
【００３７】本発明においては、ついで、上記の如くし
て得た第１の層と第２の層とを、通常のラミネ―トロ―
ルなどを用いて、積層する。このとき、熱を加えながら
圧着すると、層間の結合強度がより強くなるため、好ま
しい。また、この積層物にさらに追加の層を積層するこ
とにより、特別な装置を必要とすることなく、３層以上
の多層構造の感圧接着テ―プの製造が可能となる。In the present invention, the first layer and the second layer obtained as described above are then combined with an ordinary laminator
It is laminated using a tool or the like. At this time, it is preferable to perform pressure bonding while applying heat because the bonding strength between the layers is further increased. Further, by laminating an additional layer on the laminate, a pressure-sensitive adhesive tape having a multilayer structure of three or more layers can be manufactured without requiring a special device.
【００３８】このような積層物中に残存するモノマ―
は、熱乾燥などの手段によつて、最終的には一定の値以
下に除去される。この熱乾燥は、積層前に行つてもよい
が、反応性官能基を積層前に失わないこと、また積層後
に熱により橋かけ反応を十分に進行させる観点から、積
層後に行うのが望ましい。目標とすべき最終的な残存モ
ノマ―量は、感圧接着テ―プに要求される特性により異
なるが、一般には、５重量％以下、好ましくは１重量％
以下である。Monomers remaining in such a laminate
Is finally removed to a certain value or less by means such as heat drying. This heat drying may be performed before the lamination, but is preferably performed after the lamination from the viewpoint of not losing the reactive functional group before the lamination and sufficiently promoting the crosslinking reaction by heat after the lamination. The final amount of residual monomer to be targeted depends on the properties required for the pressure-sensitive adhesive tape, but is generally 5% by weight or less, preferably 1% by weight.
It is as follows.
【００３９】本発明においては、上記の熱乾燥を経たの
ち、あるいは特に経ることなく、隣接層間の橋かけ反応
を確実に進行させるため、積層物に対して、常温または
加熱下でエ―ジングを行うことができる。In the present invention, after the above-mentioned thermal drying or without any particular treatment, the aging of the laminate is carried out at room temperature or under heating to ensure that the crosslinking reaction between adjacent layers proceeds. It can be carried out.
【００４０】このようにして得られる多層構造の接着剤
層を有するアクリル系の感圧性接着テ―プは、隣接する
接着剤層同士が、各層を構成するアクリル系ポリマ―に
導入された反応性官能基と活性水素含有の官能基との橋
かけ反応によつて、化学的に強固に結合されているた
め、層間で容易に剥がれることのない、すぐれた耐せん
断応力を発揮する。The thus obtained acrylic pressure-sensitive adhesive tape having a multi-layered adhesive layer is characterized in that the adjacent adhesive layers are formed by reacting the reactive polymer introduced into the acrylic polymer constituting each layer. Since it is chemically bonded strongly by a crosslinking reaction between the functional group and the functional group containing active hydrogen, it exhibits excellent shear stress that does not easily peel off between layers.
【００４１】[0041]
【発明の効果】以上のように、本発明の方法によれば、
積層するべき各接着剤層は予め光重合され十分な保形性
を有しているため、積層に際して、層間での乱れが生じ
ず、簡単な装置で容易に積層することができ、３層以上
の多層体に対しても特別な装置を必要とせず、作業性も
良好なものである。As described above, according to the method of the present invention,
Since each adhesive layer to be laminated is photopolymerized in advance and has a sufficient shape-retaining property, there is no disorder between layers during lamination, and it can be easily laminated with a simple device, and three or more layers can be laminated. No special equipment is required for the multilayer body, and the workability is good.
【００４２】また、このように積層したのち、一方の層
のアクリル系ポリマ―の分子内に導入された反応性官能
基と他方の層のアクリル系ポリマ―の分子内に導入され
た活性水素含有の官能基との橋かけ反応により、隣接層
同士を化学的に結合させるようにしたことにより、層間
で容易に剥がれることのない、結合強度の大きな多層構
造の感圧接着テ―プを、作業性および経済性良好に製造
できる。特に、橋かけ反応の触媒として、たとえば、３
級アミン類などを添加することにより、上記反応を加速
できるため、生産性をより一段と高めることができる。After lamination in this manner, the reactive functional group introduced into the molecule of the acrylic polymer in one layer and the active hydrogen contained in the molecule of the acrylic polymer in the other layer are contained. Adhesive layers are chemically bonded to each other by a cross-linking reaction with a functional group, so that a multi-layer pressure-sensitive adhesive tape with a large bonding strength that does not easily peel off between layers can be manufactured. It can be manufactured with good efficiency and economy. Particularly, as a catalyst for the crosslinking reaction, for example, 3
By adding a secondary amine or the like, the above reaction can be accelerated, so that the productivity can be further enhanced.
【００４３】[0043]
【実施例】つぎに、本発明の実施例を記載してより具体
的に説明する。なお、以下において部とあるのは重量部
を意味する。また、接着力およびせん断保持力は、以下
に示す方法で測定したものである。Next, an embodiment of the present invention will be described in more detail. In the following, “parts” means “parts by weight”. The adhesive force and the shear holding force were measured by the following methods.
【００４４】＜接着力＞ＪＩＳ Ｚ−１５２２に準じ、
被着体として、ステンレス板およびポリプロピレン板を
用いて測定した。単位はｇ／２０mm幅である。<Adhesive force> According to JIS Z-1522,
The measurement was performed using a stainless steel plate and a polypropylene plate as the adherend. The unit is g / 20 mm width.
【００４５】＜せん断保持力＞両面接着テ―プを１０mm
×１０mmの大きさに切断し、２枚のアルミニウム板の他
端同士をこの接着テ―プで貼り合わせる。一方のアルミ
ニウム板を固定し、もう一方のアルミニウム板に接着テ
―プの水平方向に５００ｇの荷重をかけて、４０℃の雰
囲気中で放置し、アルミニウム板が落下するまでの時間
を測定した。<Shear retention force> 10 mm double-sided adhesive tape
It is cut into a size of × 10 mm, and the other ends of the two aluminum plates are bonded together with this adhesive tape. One aluminum plate was fixed, and a load of 500 g was applied to the other aluminum plate in the horizontal direction of the adhesive tape. The aluminum plate was left in an atmosphere of 40 ° C., and the time until the aluminum plate dropped was measured.
【００４６】実施例１ アクリル酸ブチル１００部、アクリル酸３部、酢酸ビニ
ル５部、２・２−ジメトキシ−２−フエニルアセトフエ
ノン（光重合開始剤）０．２部からなる重合原料に、高
圧水銀灯にて紫外線を照射して、一部光重合させた。こ
れに、多官能性架橋剤としてポリイソシアネ―ト化合物
〔日本ポリウレタン工業（株）製の商品名コロネ―ト
Ｌ〕１．０部と、架橋性モノマ―としてトリメチロ―ル
プロパントリアクリレ―ト０．１部とを混合し、離型処
理したプラスチツクフイルム上に塗工し、さらに窒素ガ
ス雰囲気下で紫外線を照射して光重合させることによ
り、ポリマ―ベ―スが９６重量％、厚みが２５μｍであ
る、本発明の接着剤層における第１の層に相当する重合
体フイルムＡを得た。Example 1 A polymerization raw material comprising 100 parts of butyl acrylate, 3 parts of acrylic acid, 5 parts of vinyl acetate, and 0.2 part of 2,2-dimethoxy-2-phenylacetophenone (photopolymerization initiator) was used. UV light was irradiated from a high pressure mercury lamp to partially photopolymerize. 1.0 part of a polyisocyanate compound [Coronate L (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.)] as a polyfunctional crosslinking agent and trimethylolpropane triacrylate 0 as a crosslinking monomer. 1 part, mixed and coated on a release-treated plastic film, and then irradiated with ultraviolet light in a nitrogen gas atmosphere to carry out photopolymerization, whereby the polymer base was 96% by weight and the thickness was 25 μm. A polymer film A corresponding to the first layer in the adhesive layer of the present invention was obtained.
【００４７】一方、アクリル酸２−エチルヘキシル９０
部、アクリル酸１０部、２−ヒドロキシルエチルアクリ
レ―ト２部、２・２−ジメトキシ−２−フエニルアセト
フエノン０．２部からなる重合原料を、離型処理したプ
ラスチツクフイルム上に塗工し、窒素ガス雰囲気下で高
圧水銀灯にて紫外線を照射して光重合することにより、
ポリマ―ベ―スが９８．５重量％、厚みが２５μｍであ
る、本発明の接着剤層における第２の層に相当する重合
体フイルムＢを得た。On the other hand, 2-ethylhexyl acrylate 90
, 10 parts of acrylic acid, 2 parts of 2-hydroxylethyl acrylate, and 0.2 parts of 2,2-dimethoxy-2-phenylacetophenone were coated on a release-treated plastic film. By photoirradiation with ultraviolet light from a high-pressure mercury lamp under a nitrogen gas atmosphere.
A polymer film B having a polymer base of 98.5% by weight and a thickness of 25 μm corresponding to the second layer in the adhesive layer of the present invention was obtained.
【００４８】このようにして得た重合体フイルムＡおよ
びＢを、ラミネ―トロ―ルを用いて積層圧着したのち、
１００℃にて２時間エ―ジングを行い、２層構造の接着
剤層を有する感圧性接着テ―プを得た。以下の測定試験
において、重合体フイルムＡ側を第１面、重合体フイル
ムＢ側を第２面とした。The polymer films A and B thus obtained are laminated and pressed using a laminating roll.
Aging was performed at 100 ° C. for 2 hours to obtain a pressure-sensitive adhesive tape having an adhesive layer having a two-layer structure. In the following measurement tests, the side of the polymer film A was designated as the first surface, and the side of the polymer film B was designated as the second surface.
【００４９】実施例２ アクリル酸ブチル１００部、アクリル酸３部、酢酸ビニ
ル５部、２・２−ジメトキシ−２−フエニルアセトフエ
ノン０．２部からなる重合原料に、高圧水銀灯にて紫外
線を照射して、一部光重合させた。これに、反応性官能
基を含むモノマ―としてグリシジルメタクリレ―ト２部
と、架橋性モノマ―としてトリメチロ―ルプロパントリ
アクリレ―ト０．１部とを混合し、離型処理したプラス
チツクフイルム上に塗工し、さらに窒素ガス雰囲気下で
紫外線を照射して光重合させることにより、ポリマ―ベ
―スが９５重量％、厚みが２５μｍである、本発明の接
着剤層における第１の層に相当する重合体フイルムＣを
得た。Example 2 A polymerization raw material comprising 100 parts of butyl acrylate, 3 parts of acrylic acid, 5 parts of vinyl acetate, and 0.2 parts of 2,2-dimethoxy-2-phenylacetophenone was irradiated with ultraviolet light by a high-pressure mercury lamp. And partially photopolymerized. This was mixed with 2 parts of glycidyl methacrylate as a monomer containing a reactive functional group and 0.1 parts of trimethylolpropane triacrylate as a crosslinkable monomer, and was subjected to a release treatment. The first layer in the adhesive layer of the present invention having a polymer base of 95% by weight and a thickness of 25 μm by being coated on top and further subjected to photopolymerization by irradiation with ultraviolet rays in a nitrogen gas atmosphere. Was obtained.
【００５０】一方、アクリル酸イソデシル９０部、アク
リル酸１０部、２−ヒドロキシルエチルアクリレ―ト２
部、２・２−ジメトキシ−２−フエニルアセトフエノン
０．２部からなる重合原料に、高圧水銀灯にて紫外線を
照射し、一部光重合させた。これに、橋かけ反応の触媒
として、ジメチルアミノエチルアクリレ―ト２部を添加
混合し、さらに窒素ガス雰囲気下で紫外線を照射して光
重合させることにより、ポリマ―ベ―スが９９．０重量
％、厚みが２５μｍである、本発明の接着剤層における
第２の層に相当する重合体フイルムＤを得た。On the other hand, 90 parts of isodecyl acrylate, 10 parts of acrylic acid, 2-hydroxylethyl acrylate 2
Parts of 2,2-dimethoxy-2-phenylacetophenone was irradiated with ultraviolet light from a high-pressure mercury lamp to partially photopolymerize. To this, 2 parts of dimethylaminoethyl acrylate was added and mixed as a catalyst for the crosslinking reaction, followed by irradiating ultraviolet rays under a nitrogen gas atmosphere to carry out photopolymerization, whereby the polymer base was 99.0. A polymer film D having a weight percentage of 25 μm and corresponding to the second layer of the adhesive layer of the present invention was obtained.
【００５１】このようにして得た重合体フイルムＣおよ
びＤを、ラミネ―トロ―ルを用いて積層圧着したのち、
常温にて２４時間エ―ジングを行い、２層構造の接着剤
層を有する感圧性接着テ―プを得た。以下の測定試験に
おいて、重合体フイルムＣ側を第１面、重合体フイルム
Ｄ側を第２面とした。The polymer films C and D thus obtained are laminated and pressed by using a laminating roll.
Aging was performed at room temperature for 24 hours to obtain a pressure-sensitive adhesive tape having a two-layered adhesive layer. In the following measurement tests, the polymer film C side was defined as a first surface, and the polymer film D side was defined as a second surface.
【００５２】比較例１ アクリル酸ブチル１００部、アクリル酸３部、酢酸ビニ
ル５部、２・２−ジメトキシ−２−フエニルアセトフエ
ノン０．２部からなる重合原料に、高圧水銀灯にて紫外
線を照射し、一部光重合させた。これに、架橋性モノマ
―としてトリメチロ―ルプロパントリアクリレ―ト０．
２部を混合し、離型処理したプラスチツクフイルム上に
塗工し、さらに窒素ガス雰囲気下で紫外線を照射して光
重合させることにより、ポリマ―ベ―スが９９．０重量
％、厚みが２５μｍの重合体フイルムＥを得た。Comparative Example 1 A polymerization raw material comprising 100 parts of butyl acrylate, 3 parts of acrylic acid, 5 parts of vinyl acetate, and 0.2 parts of 2,2-dimethoxy-2-phenylacetophenone was irradiated with ultraviolet light by a high-pressure mercury lamp. And partially photopolymerized. In addition, trimethylolpropane triacrylate 0.1.
The two parts were mixed, coated on a release-treated plastic film, and irradiated with ultraviolet rays in a nitrogen gas atmosphere to carry out photopolymerization, whereby the polymer base was 99.0% by weight and the thickness was 25 μm. A polymer film E was obtained.
【００５３】つぎに、上記の重合体フイルムＥおよび実
施例１で得た重合体フイルムＢを、ラミネ―トロ―ルを
用いて積層圧着したのち、１００℃にて２時間エ―ジン
グを行い、２層構造の接着剤層を有する感圧性接着テ―
プを得た。以下の測定試験において、重合体フイルムＥ
側を第１面、重合体フイルムＢ側を第２面とした。Next, the above-mentioned polymer film E and the polymer film B obtained in Example 1 were laminated and pressed by using a laminating roll, and then subjected to aging at 100 ° C. for 2 hours. Pressure-sensitive adhesive tape with two-layer adhesive layer
Got In the following measurement test, the polymer film E was used.
The side was defined as a first surface, and the polymer film B side was defined as a second surface.
【００５４】比較例２ 厚さを５０μｍに変更した以外は、実施例１における重
合体フイルムＡと同一配合，同一製法により、単層構造
の感圧性接着テ―プを得た。Comparative Example 2 A pressure-sensitive adhesive tape having a single-layer structure was obtained by the same composition and the same production method as in the polymer film A in Example 1, except that the thickness was changed to 50 μm.
【００５５】比較例３ 厚さを５０μｍに変更した以外は、実施例２における重
合体フイルムＣと同一配合，同一製法により、単層構造
の感圧性接着テ―プを得た。Comparative Example 3 A pressure-sensitive adhesive tape having a single layer structure was obtained by the same composition and the same production method as those of the polymer film C in Example 2, except that the thickness was changed to 50 μm.
【００５６】比較例４ 厚さを５０μｍに変更した以外は、実施例１における重
合体フイルムＢと同一配合，同一製法により、単層構造
の感圧性接着テ―プを得た。Comparative Example 4 A pressure-sensitive adhesive tape having a single-layer structure was obtained by the same blending and the same manufacturing method as in the polymer film B in Example 1, except that the thickness was changed to 50 μm.
【００５７】比較例５ 厚さを５０μｍに変更した以外は、実施例２における重
合体フイルムＤと同一配合，同一製法により、単層構造
の感圧性接着テ―プを得た。Comparative Example 5 A pressure-sensitive adhesive tape having a single-layer structure was obtained by the same formulation and the same manufacturing method as for the polymer film D in Example 2, except that the thickness was changed to 50 μm.
【００５８】上記の実施例１，２および比較例１〜５で
製造した感圧性接着テ―プにつき、接着力およびせん断
保持力を調べた。その結果を、下記の表１に示す。な
お、実施例１，２および比較例１で示した２層構造の接
着剤層を有する感圧性接着テ―プについては、第１面お
よび第２面の接着力を記した。With respect to the pressure-sensitive adhesive tapes produced in Examples 1 and 2 and Comparative Examples 1 to 5, the adhesive force and the shear holding force were examined. The results are shown in Table 1 below. For the pressure-sensitive adhesive tapes having the two-layered adhesive layer shown in Examples 1 and 2 and Comparative Example 1, the adhesive strengths on the first and second surfaces are described.
【００５９】[0059]
【表１】 [Table 1]
【００６０】上記の表１の結果より、たとえば、ステン
レス板とポリプロピレン板を接着するためには、本発明
の実施例１，２に示す２層構造の接着剤層を有する感圧
性接着テ―プを用い、ステンレス板側にその第２面、ポ
リプロピレン板側にその第１面を配することにより、比
較例２〜５に示す単層構造の感圧性接着テ―プに比べ
て、より良好な接着特性が得られるものであることが明
らかである。また、この本発明の感圧性接着テ―プは、
比較例１に示す２層構造の接着剤層を有する感圧性接着
テ―プに比べて、接着剤層間の結合強度が格段に強いた
め、すぐれたせん断保持力を示すことも明らかである。From the results shown in Table 1 above, for example, in order to bond a stainless steel plate and a polypropylene plate, a pressure-sensitive adhesive tape having a two-layered adhesive layer as shown in Examples 1 and 2 of the present invention. By arranging the second surface on the stainless steel plate side and the first surface on the polypropylene plate side, a better pressure-sensitive adhesive tape having a single-layer structure shown in Comparative Examples 2 to 5 is used. It is clear that the adhesive properties are obtained. Further, the pressure-sensitive adhesive tape of the present invention
Compared to the pressure-sensitive adhesive tape having the two-layered adhesive layer shown in Comparative Example 1, the bonding strength between the adhesive layers is much higher, so that it is also apparent that the adhesive tape exhibits excellent shear holding power.
【００６１】実施例３ アクリル酸ブチル１００部、アクリル酸３部、酢酸ビニ
ル５部、１−ヒドロキシシクロヘキシルフエニルケトン
（光重合開始剤）０．１部からなる重合原料に、高圧水
銀灯にて紫外線を照射して、一部光重合させた。これ
に、多官能性架橋剤としてトリメチロ―ルプロパントリ
ス〔３−（１−アジリジニル）プロピオネ―ト〕０．０
５部と、架橋性モノマ―としてトリメチロ―ルプロパン
トリアクリレ―ト０．０５部とを混合し、離型処理した
プラスチツクフイルム上に塗工し、さらに窒素ガス雰囲
気下で紫外線を照射して光重合させることにより、ポリ
マ―ベ―スが９７重量％、厚みが２０μｍである、本発
明の接着剤層における第１の層に相当する重合体フイル
ムＦを得た。Example 3 A polymerization raw material consisting of 100 parts of butyl acrylate, 3 parts of acrylic acid, 5 parts of vinyl acetate and 0.1 part of 1-hydroxycyclohexylphenyl ketone (photopolymerization initiator) was irradiated with ultraviolet light by a high-pressure mercury lamp. And partially photopolymerized. In addition, trimethylolpropane tris [3- (1-aziridinyl) propionate] 0.0 is used as a polyfunctional crosslinking agent.
5 parts and 0.05 parts of trimethylolpropane triacrylate as a crosslinkable monomer were mixed, applied to a release-treated plastic film, and further irradiated with ultraviolet rays in a nitrogen gas atmosphere. By photopolymerization, a polymer film F corresponding to the first layer of the adhesive layer of the present invention having a polymer base of 97% by weight and a thickness of 20 μm was obtained.
【００６２】一方、アクリル酸イソデシル９０部、アク
リル酸１０部、１−ヒドロキシシクロヘキシルフエニル
ケトン（光重合開始剤）０．１部からなる重合原料を、
離型処理したプラスチツクフイルム上に塗工し、窒素ガ
ス雰囲気下で高圧水銀灯にて紫外線を照射して光重合す
ることにより、ポリマ―ベ―スが９８．５重量％、厚み
が２５μｍである、本発明の接着剤層における第２の層
に相当する重合体フイルムＧを得た。On the other hand, a polymerization raw material comprising 90 parts of isodecyl acrylate, 10 parts of acrylic acid, and 0.1 part of 1-hydroxycyclohexylphenyl ketone (photopolymerization initiator) was used.
The polymer base is 98.5% by weight and the thickness is 25 μm by applying onto the release-treated plastic film and irradiating it with ultraviolet light from a high-pressure mercury lamp under a nitrogen gas atmosphere to carry out photopolymerization. A polymer film G corresponding to the second layer in the adhesive layer of the present invention was obtained.
【００６３】このようにして得た重合体フイルムＦおよ
びＧを、ラミネ―トロ―ルを用いて積層圧着したのち、
１３０℃にて２時間エ―ジングを行い、２層構造の接着
剤層を有する感圧性接着テ―プを得た。以下の測定試験
において、重合体フイルムＦ側を第１面、重合体フイル
ムＧ側を第２面とした。The polymer films F and G thus obtained are laminated and pressed by using a laminating roll.
Aging was performed at 130 ° C. for 2 hours to obtain a pressure-sensitive adhesive tape having an adhesive layer having a two-layer structure. In the following measurement tests, the polymer film F side was defined as a first surface, and the polymer film G side was defined as a second surface.
【００６４】上記の実施例３で製造した感圧性接着テ―
プについて、接着力およびせん断保持力を調べた。その
結果を、下記の表２に示す。なお、接着力は、第１面お
よび第２面について測定した。The pressure-sensitive adhesive tape manufactured in Example 3 above.
The adhesive strength and the shear retention force of the tape were examined. The results are shown in Table 2 below. In addition, the adhesive force was measured for the first surface and the second surface.
【００６５】[0065]
【表２】 [Table 2]
【００６６】上記の表２の結果より、前記の実施例１，
２の場合と同様に、たとえば、ステンレス板とポリプロ
ピレン板を接着するにあたり、本発明の実施例３に示す
２層構造の接着剤層を有する感圧性接着テ―プを用い、
ステンレス板側にその第２面、ポリプロピレン板側にそ
の第１面を配することにより、非常に良好な接着特性が
得られるとともに、接着剤層間の結合強度が格段に強い
ため、すぐれたせん断保持力を示すことも明らかであ
る。From the results in Table 2 above, it can be seen from Examples 1 and 2 described above.
As in the case of 2, for example, in bonding a stainless steel plate and a polypropylene plate, a pressure-sensitive adhesive tape having an adhesive layer having a two-layer structure shown in Example 3 of the present invention was used.
By arranging the second surface on the stainless steel plate side and the first surface on the polypropylene plate side, very good adhesive properties can be obtained, and the bond strength between the adhesive layers is remarkably strong, so excellent shear retention It is also clear that it shows power.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C09J 7/02 C09J 7/00 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C09J 7/02 C09J 7/00
Claims (5)
の感圧性接着テ―プの製法において、（メタ）アクリル
酸アルキルエステルと光重合開始剤とを含む組成物を光
重合させて得た少なくとも２種の接着剤層を、隣接層間
でその組成が異なるように積層したのち、隣接層の一方
の層を構成する（メタ）アクリル酸アルキルエステル系
ポリマ―の分子内に導入された反応性官能基と、他方の
層を構成する（メタ）アクリル酸アルキルエステル系ポ
リマ―の分子内に導入された活性水素含有の官能基との
反応により、隣接層同士を化学的に結合させるようにし
たことを特徴とする感圧性接着テ―プの製法。1. A method for producing an acrylic pressure-sensitive adhesive tape having an adhesive layer having a multilayer structure, obtained by photopolymerizing a composition containing an alkyl (meth) acrylate and a photopolymerization initiator. After laminating at least two types of adhesive layers such that the composition differs between adjacent layers, the reactivity introduced into the molecules of the alkyl (meth) acrylate based polymer constituting one of the adjacent layers The reaction between the functional group and the functional group containing active hydrogen introduced into the molecule of the alkyl (meth) acrylate-based polymer constituting the other layer causes the adjacent layers to be chemically bonded to each other. A method for producing a pressure-sensitive adhesive tape, characterized in that:
ポリマ―の分子内に導入された反応性官能基が、光重合
用の組成物に添加された反応性官能基を含むモノマ―に
由来するものである請求項１に記載の感圧性接着テ―プ
の製法。2. A polymer in which a reactive functional group introduced into a molecule of an alkyl (meth) acrylate-based polymer is derived from a monomer containing a reactive functional group added to a composition for photopolymerization. The method for producing a pressure-sensitive adhesive tape according to claim 1, wherein
ポリマ―の分子内に導入された反応性官能基が、光重合
用の組成物に添加された活性水素含有の官能基を含むモ
ノマ―の上記官能基に多官能性架橋剤を反応させて導入
されたものである請求項１に記載の感圧性接着テ―プの
製法。3. The monomer of claim 1, wherein the reactive functional group introduced into the molecule of the (meth) acrylic acid alkyl ester polymer contains an active hydrogen-containing functional group added to a composition for photopolymerization. The method for producing a pressure-sensitive adhesive tape according to claim 1, wherein the functional group is introduced by reacting a polyfunctional crosslinking agent with the functional group.
ポリマ―の分子内に導入された反応性官能基が、イソシ
アネ―ト基、エポキシ基またはアジリジン基である請求
項１〜３のいずれかに記載の感圧性接着テ―プの製法。4. The method according to claim 1, wherein the reactive functional group introduced into the molecule of the alkyl (meth) acrylate polymer is an isocyanate group, an epoxy group or an aziridine group. Pressure-sensitive adhesive tape manufacturing method.
ポリマ―の分子内に導入された活性水素含有の官能基
が、水酸基またはカルボキシル基である請求項１〜４の
いずれかに記載の感圧性接着テ―プの製法。5. The pressure-sensitive adhesive according to claim 1, wherein the active hydrogen-containing functional group introduced into the molecule of the (meth) acrylic acid alkyl ester-based polymer is a hydroxyl group or a carboxyl group. Tape manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3295216A JP3007733B2 (en) | 1991-10-14 | 1991-10-14 | Manufacturing method of pressure sensitive adhesive tape |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3295216A JP3007733B2 (en) | 1991-10-14 | 1991-10-14 | Manufacturing method of pressure sensitive adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05105851A JPH05105851A (en) | 1993-04-27 |
| JP3007733B2 true JP3007733B2 (en) | 2000-02-07 |
Family
ID=17817707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3295216A Expired - Lifetime JP3007733B2 (en) | 1991-10-14 | 1991-10-14 | Manufacturing method of pressure sensitive adhesive tape |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3007733B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086985A (en) * | 1998-09-11 | 2000-03-28 | Sekisui Chem Co Ltd | Jointing part material |
| JP2008111046A (en) * | 2006-10-30 | 2008-05-15 | Soken Chem & Eng Co Ltd | Adhesive sheet for bonding different members to each other, and laminated form |
| US7393901B1 (en) * | 2007-02-16 | 2008-07-01 | 3M Innovative Properties Company | Acrylate adhesives containing silica nanoparticles crosslinked with polyfunctional aziridines |
| JP5405758B2 (en) * | 2008-03-25 | 2014-02-05 | 三菱樹脂株式会社 | Adhesive sheet |
| US20120113361A1 (en) * | 2010-11-10 | 2012-05-10 | Tpk Touch Solutions Inc. | Optical Level Composite Pressure-Sensitive Adhesive and an Apparatus Therewith |
| JP2013014662A (en) * | 2011-07-01 | 2013-01-24 | Nitto Denko Corp | Multilayer adhesive article and adhesive sheet |
| JP2013014665A (en) * | 2011-07-01 | 2013-01-24 | Nitto Denko Corp | Multilayer adhesive article and adhesive sheet |
| JP2013014664A (en) * | 2011-07-01 | 2013-01-24 | Nitto Denko Corp | Multilayer adhesive article and adhesive sheet |
| US20140127503A1 (en) * | 2011-07-01 | 2014-05-08 | Nitto Denko Corporation | Multi-layered pressure-sensitive adhesive article and pressure-sensitive adhesive sheet |
| AR094694A1 (en) * | 2013-03-04 | 2015-08-19 | Rohm & Haas | SENSITIVE ADHESIVE TO MULTIPLE LAYER PRESSURE |
| KR101900545B1 (en) * | 2015-12-11 | 2018-09-19 | 삼성전자주식회사 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
-
1991
- 1991-10-14 JP JP3295216A patent/JP3007733B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05105851A (en) | 1993-04-27 |
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