JPH0126632B2 - - Google Patents
Info
- Publication number
- JPH0126632B2 JPH0126632B2 JP59281057A JP28105784A JPH0126632B2 JP H0126632 B2 JPH0126632 B2 JP H0126632B2 JP 59281057 A JP59281057 A JP 59281057A JP 28105784 A JP28105784 A JP 28105784A JP H0126632 B2 JPH0126632 B2 JP H0126632B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- monomers
- weight
- meth
- rubbery polymer
- 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
Links
- 239000000178 monomer Substances 0.000 claims description 33
- 229920001971 elastomer Polymers 0.000 claims description 30
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002390 adhesive tape Substances 0.000 claims description 17
- -1 methacryloyl group Chemical group 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- 229920000642 polymer Polymers 0.000 description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 20
- 150000002513 isocyanates Chemical class 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- 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 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 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 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 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
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 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
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Adhesive Tapes (AREA)
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、溶剤を用いずに粘着テープを製造す
る方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method of manufacturing an adhesive tape without using a solvent.
(従来技術)
従来から、粘着テープ類は片面タイプのもので
も或は両面タイプのものでも、溶剤に溶解したポ
リマーを基材に塗布し、溶剤を揮発させてから粘
着層を形成させるか、或はエマルジヨンを用いる
にしても、水を揮発させなければならないことは
同様である。(Prior art) Conventionally, adhesive tapes, whether single-sided or double-sided, have been made by coating a base material with a polymer dissolved in a solvent and forming an adhesive layer after the solvent has evaporated. Even if an emulsion is used, the water must be volatilized.
溶剤の使用は、環境衛生上からも、火災の危険
からも、或はコストの点からも、使用を避ける方
向にあることは言う迄もないが、実際には他に変
る方法がないために止むを得ず続けられているの
が実情である。 It goes without saying that there is a tendency to avoid the use of solvents due to environmental hygiene, fire danger, and cost considerations, but in reality, there is no other option. The reality is that it continues out of necessity.
エマルジヨンを用いる方法は、火災の危険は無
いが、水を揮発させるエネルギーと時間を要する
ことは、この方法の普及を妨げている有力な要因
である。 Although the method using emulsion does not pose a fire risk, the energy and time required to volatilize the water are major factors preventing the spread of this method.
また、エマルジヨンでは要求される性能によつ
ては物性的に溶剤型に及ばない点のあることもあ
げられる。 In addition, emulsions may have physical properties that are not as good as those of solvent-based emulsions, depending on the required performance.
(発明の解決しようとする問題点)
本発明者らは、粘着テープの製造上の問題点を
解決すべく検討を重ねていたが、今迄公知である
(メタ)アクリロイル基を有するモノマー或はオ
リゴマー(以下オリゴアクリレートと略称)など
の光又は電子線照射による硬化では軟かい塗膜は
得られても、実用性のある粘着剤を得ることは困
難であることを知つた。(Problems to be Solved by the Invention) The present inventors have made repeated studies to solve the problems in the production of adhesive tapes, but until now they have used known monomers having (meth)acryloyl groups or It has been found that although a soft coating film can be obtained by curing oligomers (hereinafter abbreviated as oligoacrylate) by light or electron beam irradiation, it is difficult to obtain a practical adhesive.
また、モノマー類をこれらオリゴアクリレート
に混合すると、粘着性を出せる程度の量では、著
しく硬化が遅れ、たとえ空気の不存在下にあつて
も、とても実用性のある重合速度が得られないこ
とも判明した。結局、オリゴアクリレート程度の
分子量、即ち500〜2000程度では困難である。 Furthermore, when monomers are mixed with these oligoacrylates in amounts sufficient to produce tackiness, curing is significantly delayed, and even in the absence of air, very practical polymerization rates may not be obtained. found. In the end, it is difficult to use a molecular weight similar to that of oligoacrylates, that is, about 500 to 2,000.
(問題点の解決手段)
かくして本発明者らは側鎖にウレタン結合を介
してアクリロイル基及び/又はメタクリロイル基
(以下(メタ)アクリロイル基と略称する)を有
する高分子量のゴム状ポリマーを用いることによ
つて目的を達成できることを見出したが、更に、
粘着付与剤を併用することによつて更に製品の幅
を拡大できることを知り、本発明を完成すること
ができた。(Means for solving the problem) Thus, the present inventors used a high molecular weight rubbery polymer having an acryloyl group and/or a methacryloyl group (hereinafter abbreviated as (meth)acryloyl group) in the side chain via a urethane bond. We found that the purpose could be achieved by
We learned that the range of products could be further expanded by using a tackifier in combination, and were able to complete the present invention.
即ち本発明は、側鎖にウレタン結合を介して
(メタ)アクリロイル基を有するゴム状ポリマー
と、該ゴム状ポリマーを溶解するモノマー類と、
前記ゴム状ポリマーと相溶性があり、且つ粘着付
与に有用なオリゴマー類と混合物を基材に塗布
し、空気の不存在下で活性エネルギー線を照射す
ることを特徴とする粘着テープの製造法である。 That is, the present invention provides a rubbery polymer having a (meth)acryloyl group in the side chain via a urethane bond, monomers that dissolve the rubbery polymer,
A method for producing an adhesive tape, which comprises coating a base material with a mixture of oligomers that are compatible with the rubbery polymer and useful for tackification, and irradiating the mixture with active energy rays in the absence of air. be.
(作 用)
本発明において、一成分である側鎖にウレタン
結合を介して(メタ)アクリロイル基を有するゴ
ム状ポリマーを構成するモノマー類は、ポリマー
のガラス転移温度が30℃以下のモノマー類を主体
とし、必要に応じてポリマーのガラス転移温度が
30℃より高いモノマー類、ポリマーに必要なヒド
ロキシル基を導入するためのモノマー、及びポリ
マーのヒドロキシル基と反応して側鎖にウレタン
結合を介して(メタ)アクリロイル基を導入する
ための不飽和イソシアナートである。(Function) In the present invention, monomers constituting a rubbery polymer having a (meth)acryloyl group in a side chain via a urethane bond as one component are monomers whose glass transition temperature is 30°C or lower. The glass transition temperature of the polymer is determined as necessary.
Monomers with a temperature higher than 30℃, monomers for introducing the necessary hydroxyl groups into the polymer, and unsaturated isocyanate for reacting with the hydroxyl groups of the polymer to introduce (meth)acryloyl groups into the side chains via urethane bonds. It's Naat.
側鎖にウレタン結合を介して(メタ)アクリロ
イル基を有するゴム状ポリマーは、最初に前記モ
ノマー類を共重合して側鎖にヒドロキシル基を有
するポリマーを製造し、このポリマーのヒドロキ
シル基に不飽和イソシアナート中のイソシアナー
ト基を反応させることによつて製造される。 Rubbery polymers having (meth)acryloyl groups in their side chains via urethane bonds are produced by first copolymerizing the above monomers to produce a polymer having hydroxyl groups in their side chains, and then adding unsaturation to the hydroxyl groups of this polymer. It is produced by reacting isocyanate groups in isocyanates.
側鎖にヒドロキシル基を有するポリマーを構成
するモノマー類は、要求される粘着性、接着性に
よつても相違するが、一般にポリマーのガラス転
移温度が30℃以下のモノマー類が適している。そ
れらのモノマー類としては、例えばアクリル酸メ
チル、アクリル酸エチル、アクリル酸ブチル、ア
クリル酸2−エチルヘキシル、メタクリル酸n−
ブチル、メタクリル酸イソブチル、メタクリル酸
2−エチルヘキシル、メタクリル酸デシル、メタ
クリル酸ラウリル、エチレン、ブタジエン、酢酸
ビニル等があげられる。 The monomers constituting the polymer having a hydroxyl group in the side chain vary depending on the required tackiness and adhesion, but monomers whose glass transition temperature is 30° C. or lower are generally suitable. Examples of such monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n-methacrylate.
Examples include butyl, isobutyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, ethylene, butadiene, vinyl acetate, and the like.
前記のモノマーには、必要に応じてポリマーの
ガラス転移温度が30℃より高いモノマー類を併用
して共重合させることが、粘着性の調節、強度の
発現の点から実用的であり、ポリマーのガラス転
移温度が30℃より高いモノマー類を単独で用いる
と、粘着剤の粘着性が低下するので好ましくな
い。ポリマーのガラス転移温度が30℃より高いモ
ノマー類としては、例えばスチレン、ビニルトル
エン、アクリロニトリル、メタクリル酸メチル、
メタクリル酸エチル、メタクリル酸シクロヘキシ
ル等があげられる。 It is practical to copolymerize the above-mentioned monomers with monomers whose glass transition temperature is higher than 30°C, if necessary, from the viewpoint of adjusting adhesiveness and developing strength. It is not preferable to use monomers with a glass transition temperature higher than 30° C. alone because the adhesive properties of the adhesive decrease. Examples of monomers whose polymer glass transition temperature is higher than 30°C include styrene, vinyltoluene, acrylonitrile, methyl methacrylate,
Examples include ethyl methacrylate and cyclohexyl methacrylate.
更に、ポリマーに必要なヒドロキシル基を導入
するためのモノマーとしては、2−ヒドロキシエ
チルアクリレート、2−ヒドロキシプロピルアク
リレート、2−ヒドロキシプロピルメタクリレー
ト、2−ヒドロキシエチルメタクリレート等があ
げられる。 Furthermore, examples of monomers for introducing the necessary hydroxyl groups into the polymer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 2-hydroxyethyl methacrylate.
上記のモノマー類を共重合させて得られるヒド
ロキシル基を有するポリマーのヒドロキシル基と
反応して、側鎖にウレタン結合を介して(メタ)
アクリロイル基を導入するための不飽和イソシア
ナートとしては、次式で代表される分子中にイソ
シアナート基と(メタ)アクリロイル基を有する
不飽和イソシアナートが挙げられる。 By reacting with the hydroxyl group of the polymer having hydroxyl groups obtained by copolymerizing the above monomers, (meth)
Examples of the unsaturated isocyanate for introducing an acryloyl group include unsaturated isocyanates having an isocyanate group and a (meth)acryloyl group in the molecule represented by the following formula.
上記(1)の不飽和イソシアナートは、普通、ジイ
ソシアナート1モルに不飽和アルコール1モル以
上加え反応することにより得られる。 The unsaturated isocyanate (1) above is usually obtained by adding 1 mol or more of unsaturated alcohol to 1 mol of diisocyanate and reacting.
ジイソシアナートとしては現在市販されている
種類、例えば、2,4−トリレンジイソシアナー
ト、2,4−トリレンジイソシアナートと2,6
−トリレンジイソシアナートとの混合物、ジフエ
ニルメタンジイソシアナート、キシリレンジイソ
シアナート、1,6−ヘキサメチレンジイソシア
ナート、イソホロンジイソシアナート、などが利
用し得る。 Diisocyanates include currently commercially available types, such as 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
- tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and the like.
不飽和アルコールとしては、例えば2−ヒドロ
キシエチルアクリレート、2−ヒドロキシプロピ
ルアクリレート、2−ヒドロキシエチルメタクリ
レート、2−ヒドロキシプロピルメタクリレート
等があげられる。 Examples of the unsaturated alcohol include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.
側鎖にヒドロキシル基を有するポリマーに不飽
和イソシアナートを反応させた場合、ウレタン結
合を介して(メタ)アクリロイル基がポリマー側
鎖に付加されて下記のタイプのゴム状ポリマーが
得られる。 When a polymer having a hydroxyl group in the side chain is reacted with an unsaturated isocyanate, a (meth)acryloyl group is added to the polymer side chain via a urethane bond, resulting in the following type of rubbery polymer.
側鎖にウレタン結合を介して(メタ)アクリロ
イル基を有するゴム状ポリマーは、側鎖にエステ
ル結合を介して(メタ)アクリロイル基を有する
ポリマーと比較して、合成の容易なこと、光硬化
速度の速やかなこと、また粘着テープにした場合
粘着性、接着力及び保持力が優れていることか
ら、本発明の粘着テープの製造用に最適である。 Rubber-like polymers that have (meth)acryloyl groups in their side chains via urethane bonds are easier to synthesize and have faster photocuring speeds than polymers that have (meth)acryloyl groups in their side chains via ester bonds. It is ideal for producing the adhesive tape of the present invention because it can be quickly applied, and when made into an adhesive tape, it has excellent tackiness, adhesive strength, and holding power.
上記、側鎖に(メタ)アクリロイル基を有する
ゴム状ポリマーは、分子量が10000以上であるこ
とが好ましい。分子量が10000末満では、粘着剤
として強度が不十分である。 The above-mentioned rubbery polymer having a (meth)acryloyl group in its side chain preferably has a molecular weight of 10,000 or more. If the molecular weight is less than 10,000, the strength as an adhesive is insufficient.
側鎖に(メタ)アクリロイル基を有するゴム状
ポリマーの不飽和度は、当然のことながら、要求
される物性により相違するが、粘着テープを対象
とする場合はゴム状ポリマーを構成する全モノマ
ー100(%)の中で不飽和部分として、0.1モル
(%)以上30モル(%)以下が適当であり、普通
2モル(%)以上20モル(%)以下が用いられ
る。 The degree of unsaturation of a rubbery polymer having a (meth)acryloyl group in the side chain naturally varies depending on the required physical properties, but when it is used for adhesive tapes, the degree of unsaturation of the total monomers constituting the rubbery polymer is 100%. (%), the unsaturated portion is suitably 0.1 mole (%) or more and 30 mole (%) or less, and usually 2 mole (%) or more and 20 mole (%) or less is used.
側鎖に(メタ)アクリロイル基を有するゴム状
ポリマーの不飽和度が0.1モル(%)未満では硬
化が遅く、ポリマーとモノマーの成分によつては
相分離して粘着性を損うようになり、一方、ポリ
マーの不飽和度が30モル(%)より多い場合には
粘着テープとしては固くなる傾向を示す。 If the degree of unsaturation of a rubbery polymer with (meth)acryloyl groups in the side chain is less than 0.1 mole (%), curing will be slow, and depending on the components of the polymer and monomer, phase separation may occur and the adhesiveness will be impaired. On the other hand, if the degree of unsaturation of the polymer is more than 30 moles (%), the adhesive tape tends to be hard.
本発明にあつては、側鎖に(メタ)アクリロイ
ル基を有するゴム状ポリマーの粘着性、接着性を
更に向上させるために、該ゴム状ポリマーと相溶
性のあるオリゴマー類(粘着付与剤)を併用する
ことが必要である。本発明に用いる粘着付与に有
用なオリゴマー類としては、
(イ) 反応性を持たず、単に側鎖に(メタ)アクリ
ロイル基を有するゴム状ポリマーに溶解して粘
着性を改良するタイプ、
(ロ) 粘着付与性と共にそれ自身反応性を有してお
り、粘着テープ製造後何らかの方法で反応を行
わせ、硬化させて接着強度の向上、耐熱性の付
与等の物性改良を伴う種類とに大別される。 In the present invention, in order to further improve the tackiness and adhesion of the rubbery polymer having (meth)acryloyl groups in its side chains, oligomers (tackifiers) that are compatible with the rubbery polymer are used. It is necessary to use them together. Oligomers useful for tackification used in the present invention include (a) types that do not have reactivity and simply dissolve in rubbery polymers having (meth)acryloyl groups in their side chains to improve tackiness; ) Adhesive tapes have reactivity as well as tackifying properties, and are roughly divided into types that require some kind of reaction after being produced and are cured to improve physical properties such as increasing adhesive strength and imparting heat resistance. be done.
(イ)に属する反応性を有しない粘着付与に有用な
オリゴマー類としては、例えば飽和のポリエステ
ルが代表的である。 A typical example of non-reactive oligomers useful for tackification belonging to (a) is saturated polyester.
飽和のポリエステルは、多価アルコールと多塩
基酸又はその酸無水物とのエステル化により合成
され、常温で液状のものからシラツプ状、固形状
のものと多彩な形態のものが製造可能であり、目
的に応じて選択可能である。 Saturated polyester is synthesized by esterification of polyhydric alcohol and polybasic acid or its acid anhydride, and can be produced in a variety of forms from liquid to syrup and solid at room temperature. It can be selected depending on the purpose.
(ロ)の反応型のオリゴマー類は、側鎖に(メタ)
アクリロイル基を有するゴム状ポリマーの粘着付
与に有効であると同時に、ゴム状ポリマーの重合
時に共重合させてポリマー成分化するか、或はゴ
ム状ポリマーの重合後に重合に関与せず残留して
粘着付与剤となるが、後で必要に応じて硬化を行
わせ、耐熱性の向上、接着強度の増大に有用なも
のである。 (b) Reactive oligomers have (meta) side chains.
It is effective for adhesion of rubbery polymers having acryloyl groups, and at the same time, it can be copolymerized to form a polymer component during polymerization of rubbery polymers, or it can remain adhesive without participating in the polymerization after polymerization of rubbery polymers. Although it acts as an imparting agent, it is useful for improving heat resistance and increasing adhesive strength by curing it later if necessary.
粘着付与に有用なオリゴマー類の代表例として
は、
(a) α−β不飽和多塩基酸を含み、任意の飽和酸
で変性するか、或はせずに、多価アルコールと
エステル化して得られる不飽和アルキツド、
(b) 液状、シラツプ状、固型状のエポキシ樹脂、
(c) ヒドロキシルポリエステル、ポリエーテル、
の末端ヒドロキシル基をイソシアナート基に変
換したポリイソシアナート、
などがあげられる。 Typical examples of oligomers useful for tackification include: (a) containing α-β unsaturated polybasic acids, obtained by esterification with polyhydric alcohols, with or without modification with any saturated acid; unsaturated alkyds, (b) epoxy resins in liquid, syrup or solid form, (c) hydroxyl polyesters, polyethers,
Examples include polyisocyanate in which the terminal hydroxyl group of is converted to an isocyanate group.
(イ)、(ロ)いづれを用いるかは粘着テープに要求さ
れる性能により定められる。 Which of (a) and (b) to use is determined by the performance required of the adhesive tape.
オリゴマー類の使用量は、側鎖に(メタ)アク
リロイル基を有するゴム状ポリマーとモノマー類
との合計量100重量部に対して、10重量部以上200
重量部以下が適当であり、最も望ましい使用量は
30重量部以上100重量部以下である。 The amount of oligomers to be used is 10 parts by weight or more per 100 parts by weight of the rubbery polymer having a (meth)acryloyl group in the side chain and monomers.
The appropriate amount is less than parts by weight, and the most desirable amount is
The amount is 30 parts by weight or more and 100 parts by weight or less.
オリゴマー類の使用量が10重量部未満では粘着
付与の効果が薄く、200重量部より多い場合には
接着性が低下する傾向がある。 When the amount of oligomers used is less than 10 parts by weight, the tackifying effect is weak, and when it is more than 200 parts by weight, adhesiveness tends to decrease.
次に側鎖に(メタ)アクリロイル基を有するゴ
ム状ポリマーに混合するモノマー類としては、前
記のポリマーのガラス転移温度が30℃以下の常温
で液体のモノマー類が好ましく用いられるが、必
要に応じてはポリマーのガラス転移温度が30℃よ
り高いモノマー類を併用してもよい。 Next, as the monomers to be mixed into the rubbery polymer having a (meth)acryloyl group in the side chain, monomers that are liquid at room temperature and whose glass transition temperature is 30°C or lower are preferably used, but if necessary, In this case, monomers whose polymer glass transition temperature is higher than 30°C may be used in combination.
側鎖に(メタ)アクリロイル基を有するゴム状
ポリマーと、モノマー類との混合割合は、途布に
要求される粘度によつて相違するが、普通塗布す
る温度で数ポイズ〜数百ポイズの間であれば既存
の塗布装置、例えばフローコーター、ロールコー
ター、などが活用することができる点から、側鎖
に(メタ)アクリロイル基を有するゴム状ポリマ
ー濃度は、約5〜60重量(%)、好ましくは10〜
55重量%の範囲内である。 The mixing ratio of the rubbery polymer having a (meth)acryloyl group in the side chain and the monomers varies depending on the viscosity required for the application, but is usually between several poise and several hundred poise at the coating temperature. Since existing coating equipment such as flow coaters and roll coaters can be used, the concentration of the rubbery polymer having a (meth)acryloyl group in the side chain is approximately 5 to 60% by weight. Preferably 10~
It is within the range of 55% by weight.
側鎖に(メタ)アクリロイル基を有するゴム状
ポリマーとオリゴマー類のモノマー溶液を光硬化
させる場合には、通常光増感剤と呼ばれるラジカ
ル発生剤が用いられる。 When photocuring a monomer solution of a rubbery polymer having a (meth)acryloyl group in a side chain and an oligomer, a radical generator called a photosensitizer is usually used.
それらの例は、例えばベンゾインエーテル類、
置換ベンゾフエノン類、並びに3級アミンとの併
用系、アセトフエノン誘導体、ジアルキルベンジ
ルケタール類、ジベンジル等があげられ、これら
は普通0.5〜5重量部(ゴム状ポリマー、モノマ
ー類およびオリゴマー類の混合物100重量部に対
して)用いられる。本発明による混合物には、必
要に応じて着色剤、充てん剤等を併用できること
は勿論である。 Examples of these include, for example, benzoin ethers,
Examples include substituted benzophenones, combination systems with tertiary amines, acetophenone derivatives, dialkylbenzyl ketals, dibenzyl, etc. These are usually 0.5 to 5 parts by weight (100 parts by weight of a mixture of rubbery polymers, monomers, and oligomers). used for) It goes without saying that colorants, fillers, etc. can be used in combination with the mixture according to the present invention, if necessary.
空気の不存在下なる条件は、不活性ガス置換と
いつたこともあるが、このためのコストは無視で
きないものがあり、本発明ではむしろシリコン樹
脂で処理した剥離紙、或はフイルム等を用い、テ
ープの基材となる紙、不織布、プラスチツクフイ
ルム又は剥離紙、剥離フイルムのいづれかに前記
混合物を塗装し、両者を密着、脱泡して実質的に
空気の影響を受けない状態で活性エネルギー線を
照射することが有用である。空気の存在下にエネ
ルギ線を照射した場合には混合物は重合せず、所
望の粘着テープが得られ難い。 The condition of the absence of air is sometimes referred to as inert gas replacement, but the cost for this cannot be ignored, and in the present invention, release paper or film treated with silicone resin is used instead. , the mixture is coated on paper, nonwoven fabric, plastic film, release paper, or release film that serves as the base material of the tape, and both are adhered and degassed, and active energy rays are applied to the base material of the tape in a state substantially unaffected by air. It is useful to irradiate When energy beams are irradiated in the presence of air, the mixture does not polymerize, making it difficult to obtain the desired adhesive tape.
製品に剥離紙又は剥離フイルムを必要としない
場合は、粘着フイルムから剥離し、再使用するこ
とができる。活性エネルギー線の照射といつた点
からは、X線、γ線、紫外線、或は電子線の電離
性放射線が普通であるが、装置のコスト、操作の
簡便さを考えれば、紫外線照射で十分であり、本
発明ではこれを以て代表させる。 If the product does not require a release paper or release film, it can be peeled off from the adhesive film and reused. In terms of irradiation with active energy rays, ionizing radiation such as X-rays, gamma rays, ultraviolet rays, or electron beams are usually used, but considering the cost of the equipment and the ease of operation, ultraviolet irradiation is sufficient. This is representative in the present invention.
(実施例)
以下、実施例によつて本発明を更に詳細に説明
する。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 1
〔側鎖に(メタ)アクリロイル基を有するゴム
状ポリマー(A)の合成〕
(i) 側鎖ヒドロキシル基含有ポリマー(a)の合成
撹拌機、還流コンデンサー、滴下ロート、ガ
ス導入管付温度計を付した1のセパラブルフ
ラスコに、酢酸エチル250g、アクリル酸ブチ
ル250g、2−ヒドロキシエチルアクリレート
23g、メタクリル酸メチル20g、アゾビスイソ
ブチロニトリル1.3g、ラウリルメルカプタン
0.5gを仕込み、窒素気流中酢酸エチルの還流
下で16時間重合させた後、ハイドロキノン0.11
g加え、淡黄色の側鎖ヒドロキシル基含有ポリ
マー(a)の酢酸エチル溶液を得た。Example 1 [Synthesis of rubbery polymer (A) having (meth)acryloyl group in the side chain] (i) Synthesis of polymer (a) containing hydroxyl group in the side chain Equipped with a stirrer, reflux condenser, dropping funnel, and gas introduction tube In a separable flask equipped with a thermometer, add 250 g of ethyl acetate, 250 g of butyl acrylate, and 2-hydroxyethyl acrylate.
23g, methyl methacrylate 20g, azobisisobutyronitrile 1.3g, lauryl mercaptan
After charging 0.5 g of hydroquinone and polymerizing it under refluxing ethyl acetate in a nitrogen stream for 16 hours, 0.11 g of hydroquinone was added.
g to obtain a pale yellow ethyl acetate solution of the side chain hydroxyl group-containing polymer (a).
(ii) 不飽和イソシアナート(b)の合成
撹拌機、ガス導入管付温度計、還流コンデン
サー、滴下ロートを付した1のセパラブルフ
ラスコに、酢酸エチル186g、2,4−トリレ
ンジイソシアナート174g(1モル)を仕込み、
乾燥空気気流中で0.2gのジブチル錫ジラウレ
ートを含む2−ヒドロキシエチルアクリレート
140g(1.2モル)を滴下した。(ii) Synthesis of unsaturated isocyanate (b) In a separable flask equipped with a stirrer, a thermometer with a gas inlet tube, a reflux condenser, and a dropping funnel, add 186 g of ethyl acetate and 174 g of 2,4-tolylene diisocyanate. Prepare (1 mol),
2-Hydroxyethyl acrylate containing 0.2 g dibutyltin dilaurate in a stream of dry air
140 g (1.2 mol) was added dropwise.
温度を60℃に保ち、滴下終了後、3時間反応
させると、赤外分析の結果ヒドロキシル基は消
失したものと判断され、不飽和イソシアナート
(b)の酢酸エチル溶液が淡黄色で得られた。 When the temperature was maintained at 60℃ and the reaction was allowed to proceed for 3 hours after the completion of the dropwise addition, it was determined that the hydroxyl group had disappeared as a result of infrared analysis, and unsaturated isocyanate was formed.
An ethyl acetate solution of (b) was obtained in pale yellow color.
側鎖ヒドロキシル基含有ポリマー(a)(酢酸エチ
ル溶液)498gに、不飽和イソシアナート(b)(酢
酸エチル溶液)125g加え、酢酸エチルの沸点で
6時間反応させると、赤外分析の結果遊離の水酸
基、並びにイソシアナート基は消失したものと判
断された。 125 g of unsaturated isocyanate (b) (ethyl acetate solution) was added to 498 g of side chain hydroxyl group-containing polymer (a) (ethyl acetate solution) and reacted for 6 hours at the boiling point of ethyl acetate. As a result of infrared analysis, free It was determined that the hydroxyl groups and isocyanate groups had disappeared.
次いで、酢酸エチルを約100c.c.溜出させた後、
アクリル酸ブチルを最初200g加え、更に約450mm
Hgの減圧下に酢酸エチルを溜出させ、フラスコ
内が粘稠になるに従つてアクリル酸ブチルを追加
し、最終的にアクリル酸ブチル580g加えた。更
にメタクリル酸メチル50g加え、粘度約50ポイ
ズ、淡黄褐色液状の側鎖に(メタ)アクリロイル
基を有するゴム状ポリマー(A)のモノマー溶液を得
た。GPC法によつて測定したポリマー(A)の分子
量は約50000であつた。 Next, after distilling about 100 c.c. of ethyl acetate,
Add 200g of butyl acrylate first, then add about 450mm
Ethyl acetate was distilled out under reduced pressure of Hg, and as the flask became viscous, more butyl acrylate was added, and finally 580 g of butyl acrylate was added. Furthermore, 50 g of methyl methacrylate was added to obtain a monomer solution of a rubbery polymer (A) having a (meth)acryloyl group in the side chain as a light yellowish brown liquid with a viscosity of about 50 poise. The molecular weight of polymer (A) measured by GPC method was about 50,000.
〔ポリエステル(B)の合成〕
撹拌機、ガス導入管付温度計、分溜コンデンサ
ーを付した2の三ツ口フラスコに、トリメチロ
ールプロパン130g、ジプロピレングリコール520
g、アジピン酸702gを仕込み、窒素ガス気流中
220〜230℃でエステル化を行い、酸価4.6、水酸
価213のヒドロキシルポリエステル(B)を合成した。
得られたヒドロキシポリエステルは、淡黄褐色、
粘稠なシラツプ状であつた。 [Synthesis of polyester (B)] In a three-necked flask equipped with a stirrer, a thermometer with a gas inlet tube, and a fractionating condenser, add 130 g of trimethylolpropane and 520 g of dipropylene glycol.
g, 702 g of adipic acid and placed in a nitrogen gas stream.
Esterification was performed at 220-230°C to synthesize a hydroxyl polyester (B) with an acid value of 4.6 and a hydroxyl value of 213.
The obtained hydroxy polyester has a light yellowish brown color,
It was in the form of a viscous syrup.
〔粘着テープの製造〕
ゴム状ポリマー(A)のモノマー溶液(ポリマー含
量約35重量%)100重量部に、ポリエステル(B)の
含量が50重量%のアクリル酸ブチル溶液80重量
部、ベンゾフエノン2重量部、ジメチルアミノエ
タノール2重量部加え、光硬化型の混合物を得
た。 [Manufacture of adhesive tape] 100 parts by weight of a monomer solution of rubbery polymer (A) (polymer content approximately 35% by weight), 80 parts by weight of a butyl acrylate solution containing 50% by weight of polyester (B), and 2 parts by weight of benzophenone. 1 part by weight, and 2 parts by weight of dimethylaminoethanol were added to obtain a photocurable mixture.
厚さ75μ、幅22cmのポリエチレンテレフタレー
トフイルムの端部1cmづつを厚さ50μのビニルテ
ープを張り、一端に前記の光硬化型の混合物を塗
装し、シリコン剥離紙を圧着させて脱泡と同時に
フイルム全体に混合物を拡げた。これをポリエチ
レンテレフタレートフイルム側を上向にして
50KWの出力をもつ紫外線照射機下20cmを、5
m/分で通過させた。 A polyethylene terephthalate film with a thickness of 75μ and a width of 22cm is covered with 50μ thick vinyl tape on each end 1cm at a time, one end is coated with the above-mentioned photo-curing mixture, and a silicone release paper is crimped to de-air the film. Spread the mixture all over. Place this with the polyethylene terephthalate film side facing up.
20cm below the ultraviolet irradiation machine with an output of 50KW,
Passed at m/min.
シリコン離型紙を剥離すると、粘着テープが得
られ、その物性は次のようであつた。 When the silicon release paper was peeled off, an adhesive tape was obtained, and its physical properties were as follows.
第1表
粘着性:転球法(J.Dow法)15
接着力:180゜剥離、ステンレスパネル1.6Kg/in.
保持力:25mm×100mmの粘着フイルムを25×25mm
だけステンレスパネルに接着、荷重1Kgでおも
りが落下するまでの時間、
5時間、
実施例 2
アクリル酸2−エチルヘキシル75モル(%)、
アクリル酸エチル20モル(%)、2−ヒドロキシ
エチルメタクリレート5モル(%)からなる混合
モノマー250gに、重合開始剤としてアゾビスイ
ソブチロニトリル2gを加え、更に酢酸エチル
250gと共に、撹拌機、還流コンデンサー、ガス
導入管、温度計を付した1セパラブルフラスコ
に仕込み、徐々に昇温させながら酢酸エチルの還
流下で8時間重合した後、更にアゾビスイソブチ
ロニトリル1gを追加し4時間重合を続けた。 Table 1 Adhesion: Rolling ball method (J.Dow method) 15 Adhesion strength: 180° peeling, stainless steel panel 1.6Kg/in. Holding strength: 25mm × 100mm adhesive film to 25 × 25mm
time until the weight falls under a load of 1 kg, 5 hours, Example 2 75 mol (%) of 2-ethylhexyl acrylate,
To 250 g of mixed monomers consisting of 20 moles (%) of ethyl acrylate and 5 moles (%) of 2-hydroxyethyl methacrylate, 2 g of azobisisobutyronitrile was added as a polymerization initiator, and then ethyl acetate was added.
Together with 250g of azobisisobutyronitrile, the mixture was charged into a separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, and polymerized for 8 hours under refluxing ethyl acetate while gradually increasing the temperature. 1 g was added and polymerization was continued for 4 hours.
ハイドロキノン0.05gを加え重合を停止させ
た。 0.05 g of hydroquinone was added to stop the polymerization.
得られた三元共重合体の分子量は約15万であつ
た。 The molecular weight of the obtained terpolymer was approximately 150,000.
次にこれにイソシアナートエチルメタクリレー
トを、200gのポリマー中のヒドロキシル基に相
当するモル数(1.1g)、ジブチル錫ジラウレート
0.7g、を仕込み、60〜65℃に3時間反応すると、
赤外分析の結果、遊離のイソシアナート基は消失
したことが認められた。 Next, add isocyanate ethyl methacrylate to this, the number of moles (1.1 g) corresponding to the hydroxyl groups in 200 g of polymer, and dibutyltin dilaurate.
When 0.7g was charged and reacted at 60-65℃ for 3 hours,
As a result of infrared analysis, it was observed that free isocyanate groups had disappeared.
分溜コンデンサーに変えて約400Torrの減圧下
に酢酸エチル約100g溜出させたのち、アクリル
酸ブチル210g加え、更に酢酸エチルが溜出しな
くなる迄蒸溜した後、アクリロニトリル23g及び
アクリル酸7gを加え、粘度約74ポイズ、淡黄褐
色液状の、側鎖にウレタン結合を介してメタアク
リロイル基を有するポリマー(C)のモノマー溶液を
得た。 After changing to a fractionating condenser and distilling out about 100g of ethyl acetate under reduced pressure of about 400Torr, 210g of butyl acrylate was added, and the mixture was further distilled until no more ethyl acetate was distilled out. Then, 23g of acrylonitrile and 7g of acrylic acid were added. A monomer solution of a polymer (C) having a methacryloyl group in the side chain via a urethane bond was obtained, which was approximately 74 poise and was in the form of a light yellowish brown liquid.
ロジン変性ポリエステル樹脂の製造撹拌機、ガ
ス導入管付温度計、分溜コンデンサーを付した2
の三ツ口フラスコに、トリメチロールプロパン
130g、ジプロピレングリコール520g、WWロジ
ン150g、エンドメチレンテトラヒドロ無水フタ
ル酸752g、フマル酸53gを仕込み、窒素ガス気
流中220〜230℃でエステル化を行い、酸価39.1の
不飽和ポリエステル(D)を合成した。 Production of rosin-modified polyester resin 2 equipped with a stirrer, a thermometer with a gas introduction tube, and a fractionating condenser.
In a three-necked flask, add trimethylolpropane.
130 g, dipropylene glycol 520 g, WW rosin 150 g, endomethylenetetrahydrophthalic anhydride 752 g, and fumaric acid 53 g were charged, and esterification was performed at 220 to 230°C in a nitrogen gas stream to produce unsaturated polyester (D) with an acid value of 39.1. Synthesized.
粘稠さを帯びた黄褐色固体であつた。 It was a yellowish brown solid with viscosity.
ゴム状ポリマー(C)のモノマー溶液100重量部に、
ポリエステル(D)50重量部を加え均一に溶解した
後、この混合樹脂100重量部にメルク社のダロキ
ユア#1173を2重量部、過酸化ベンゾイル0.5部
を加え、光硬化性樹脂とした。
To 100 parts by weight of monomer solution of rubbery polymer (C),
After adding 50 parts by weight of polyester (D) and uniformly dissolving it, 2 parts by weight of Darokyure #1173 manufactured by Merck & Co., Ltd. and 0.5 parts of benzoyl peroxide were added to 100 parts by weight of this mixed resin to obtain a photocurable resin.
厚さ75μ、幅22cmのポリエチレンテレフタレー
トフイルムの端部1cmづつを、厚さ50μのビニル
テープを張り、一端に前記の光硬化型の混合物を
塗装し、シリコン剥離紙を圧着させて脱泡と同時
にフイルム全体に混合物を拡げた。 A 50μ thick vinyl tape is applied to each 1cm end of a polyethylene terephthalate film with a thickness of 75μ and a width of 22cm, and one end is coated with the above-mentioned photocurable mixture, and a silicone release paper is pressed to remove air at the same time. The mixture was spread over the entire film.
これをポリエチレンテレフタレートフイルム側
を上向にして30KWの出力をもつ紫外線照射機下
20cmを2m/分で通過させた。 This was placed under an ultraviolet irradiation machine with an output of 30KW with the polyethylene terephthalate film side facing upward.
20cm was passed at 2m/min.
シリコン離型紙を剥離すると粘着テープが得ら
れ、その物性は次のようであつた。 An adhesive tape was obtained by peeling off the silicone release paper, and its physical properties were as follows.
粘着性;ボールタツク(J.Dow法)9
180゜剥離;ステンレスパネル、1.3Kg/inch
120℃ 30分硬化後、2.1Kg/inch
保持力;25m/m×100m/mの粘着フイルムを
25×25m/mだけステンレスパネルに接着、荷
重1Kgでおもりが落下するまでの時間
5時間以上
〔比較例〕
アクリル酸エチルヘキシル75モル(%)、アク
リル酸エチル20モル(%)、アクリル酸5モル
(%)からなる組成を有するモノマー200g、アゾ
ビスイソブチロニトリル2g、酢酸エチル200g、
の混合物を、撹拌機、還流コンデンサー、温度
計、ガス導入管を付した1セパラブルフラスコ
に仕込み、徐々に昇温させながら酢酸エチルの還
流下8時間還流させた後、アゾビスイソブチロニ
トリル1gを追加して、更に4時間重合した後、
ハイドロキノン0.05g加え重合を停止させた。分
子量約15万であつた。Adhesion: Ball tack (J.Dow method) 9 180° peeling: Stainless steel panel, 1.3Kg/inch After curing for 30 minutes at 120℃, 2.1Kg/inch Holding force: 25m/m x 100m/m adhesive film
Glued to a stainless steel panel by 25 x 25 m/m, time required for the weight to fall under a load of 1 kg: 5 hours or more [Comparative example] Ethylhexyl acrylate 75 mol (%), ethyl acrylate 20 mol (%), acrylic acid 5 mol (%) 200g of monomer, 2g of azobisisobutyronitrile, 200g of ethyl acetate,
The mixture was charged into a separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube, and the mixture was refluxed for 8 hours under refluxing ethyl acetate while gradually increasing the temperature. After adding 1 g and polymerizing for another 4 hours,
0.05 g of hydroquinone was added to stop the polymerization. The molecular weight was approximately 150,000.
次いで、ウンデシルイミダゾールの10%エタノ
ール溶液70g、グリシジルメタクリレート1gと
を加えこの混合物を80〜85℃に6時間撹拌して反
応を完結させた。 Next, 70 g of a 10% ethanol solution of undecyl imidazole and 1 g of glycidyl methacrylate were added, and the mixture was stirred at 80-85° C. for 6 hours to complete the reaction.
このものの固型分100重量部に対して、テルペ
ンフエノール樹脂(商品名「YSハリエスターT
−115;安原油脂製)を25重量部配合して粘着剤
とし、更にダロキユア#1173を2重部加え、ポリ
エチレンテレフタレートフイルムに50μ厚に2回
塗布、乾燥した。 Terpene phenol resin (product name: YS Harrier T
25 parts by weight of ``-115; manufactured by Chesai Oil & Oil Co., Ltd.'' were blended to form an adhesive, and 2 parts of Darokyur #1173 were added thereto, and the mixture was coated twice on a polyethylene terephthalate film to a thickness of 50 .mu.m, and dried.
乾燥粘着剤を更にシリコン樹脂処理した剥離紙
に圧着し、ポリエチレンテレフタレートフイルム
側から出力30KWの紫外線ランプ下20cmを2m/
分で通過させた。 The dry adhesive was further pressed onto release paper treated with silicone resin, and the polyethylene terephthalate film was placed 20cm under an ultraviolet lamp with an output of 30KW for 2m/20cm.
Passed it in minutes.
その粘着テープの物性は次の如くで、本発明に
は及ばなかつた。 The physical properties of the adhesive tape were as follows, and were not as good as the present invention.
粘着性;ボールタツク13 180℃剥離;ステンレスパネル 0.35Kg/inch 120℃ 30分処理後 0.4Kg/inch 保持力;前同 10分以下Adhesiveness; Ball Tack 13 180℃ peeling; stainless steel panel 0.35Kg/inch 0.4Kg/inch after processing at 120℃ for 30 minutes Holding power: Same as before, 10 minutes or less
Claims (1)
及び/又はメタクリロイル基を有するゴム状ポリ
マーと、該ゴム状ポリマーを溶解可能なモノマー
類と、前記ゴム状ポリマーと相溶性があり、且つ
粘着付与に有用なオリゴマー類との混合物を基材
に塗布し、空気の不存在下で活性エネルギー線を
照射することを特徴とする粘着テープの製造方
法。1. A rubbery polymer having an acryloyl group and/or methacryloyl group in the side chain via a urethane bond, monomers that can dissolve the rubbery polymer, and are compatible with the rubbery polymer and useful for tackification. 1. A method for producing an adhesive tape, which comprises coating a base material with a mixture of oligomers and irradiating the mixture with active energy rays in the absence of air.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28105784A JPS61159479A (en) | 1984-12-30 | 1984-12-30 | Production of pressure-sensitive adhesive tape |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28105784A JPS61159479A (en) | 1984-12-30 | 1984-12-30 | Production of pressure-sensitive adhesive tape |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61159479A JPS61159479A (en) | 1986-07-19 |
JPH0126632B2 true JPH0126632B2 (en) | 1989-05-24 |
Family
ID=17633705
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28105784A Granted JPS61159479A (en) | 1984-12-30 | 1984-12-30 | Production of pressure-sensitive adhesive tape |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61159479A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58113280A (en) * | 1981-12-28 | 1983-07-06 | Sony Corp | Pressure-sensitive adhesive tape |
JPS58164668A (en) * | 1982-03-06 | 1983-09-29 | バスフ アクチェン ゲゼルシャフト | Manufacture of self-adhesive film |
-
1984
- 1984-12-30 JP JP28105784A patent/JPS61159479A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58113280A (en) * | 1981-12-28 | 1983-07-06 | Sony Corp | Pressure-sensitive adhesive tape |
JPS58164668A (en) * | 1982-03-06 | 1983-09-29 | バスフ アクチェン ゲゼルシャフト | Manufacture of self-adhesive film |
Also Published As
Publication number | Publication date |
---|---|
JPS61159479A (en) | 1986-07-19 |
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