JP4727839B2 - Medical hygiene pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet using the composition - Google Patents
Medical hygiene pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet using the composition Download PDFInfo
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- JP4727839B2 JP4727839B2 JP2001117003A JP2001117003A JP4727839B2 JP 4727839 B2 JP4727839 B2 JP 4727839B2 JP 2001117003 A JP2001117003 A JP 2001117003A JP 2001117003 A JP2001117003 A JP 2001117003A JP 4727839 B2 JP4727839 B2 JP 4727839B2
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- pressure
- sensitive adhesive
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- adhesive composition
- medical hygiene
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- 239000000203 mixture Substances 0.000 title claims description 69
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 59
- 230000001070 adhesive effect Effects 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 36
- 239000000853 adhesive Substances 0.000 claims description 28
- 230000005865 ionizing radiation Effects 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 230000001954 sterilising effect Effects 0.000 claims description 9
- 238000004659 sterilization and disinfection Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000002390 adhesive tape Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 alkyl acrylate ester Chemical class 0.000 description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 238000010894 electron beam technology 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
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- 239000003505 polymerization initiator Substances 0.000 description 5
- 206010040880 Skin irritation Diseases 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000036556 skin irritation Effects 0.000 description 4
- 231100000475 skin irritation Toxicity 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010052428 Wound Diseases 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920001342 Bakelite® Polymers 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 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
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920006267 polyester film Polymers 0.000 description 1
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- 229920001228 polyisocyanate Polymers 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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Landscapes
- Materials For Medical Uses (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は医療衛生分野で皮膚貼付用途に使用される医療用粘着剤組成物、およびこの組成物を用いてなる粘着テープもしくはシートに関するものである。
【０００２】
【従来の技術】
皮膚貼付用途に用いられる医療衛生用粘着剤組成物は、通常、支持基材の片面に層状に粘着剤層を形成して、医療用または衛生用粘着テープやシートとし、これを適用すべき皮膚面などに貼着して使用している。
【０００３】
このようにして形成される粘着剤層は、一般に皮膚面に対して強固に接着固定する必要があると共に、層内の凝集力や支持基材との投錨力といった所謂、接着特性に優れたものでなければならない。
【０００４】
また、皮膚貼付用途として用いるので、貼付する皮膚面に対して無刺激性でなければならないと共に、皮膚面からの剥離時に物理的痛みを与えて皮膚刺激性を発現させてはならず、皮膚低刺激性という特性も要求されるのである。
【０００５】
従来から、医療用粘着剤組成物としては、アクリル酸アルキルエステルを主成分としたアクリル系粘着剤組成物や、合成ゴムや天然ゴムを主成分とするゴム系粘着剤組成物が一般的に用いられている。しかしながら、ゴム系粘着剤は粘着特性の調整が難しく、天然ゴムでは不純物としてのタンパク質などに起因するアレルギーの発現の可能性など、取り扱いの面でやや難点があり、重合方法や重合組成、配合などで粘着特性の調整が容易なアクリル系粘着剤組成物の検討が比較的多く行われるようになっている。
【０００６】
上記したように、アクリル系粘着剤組成物は粘着特性の調整が比較的容易であり、バランスのとれた粘着剤を提供できるものではあるが、皮膚接着力や保持力（内部凝集力）の点で、未だ改良すべき余地は多く残されており、種々の検討がなされているのが実状である。
【０００７】
例えば、皮膚接着力を向上させるためには、皮膚接着性付与成分としてのアルキル基の炭素数が４〜１２程度のアクリル酸アルキルエステルの共重合量を増やしたり、アルキル鎖の長いアクリル酸アルキルエステルを用いることも試みられているが、その反面、粘着剤層の内部凝集力の低下によって保持力の低下を招くために、粘着剤層の架橋処理が必要となってくる。代表的な架橋処理としては、ポリイソシアネートやアミン類、エポキシ系化合物などの外部架橋剤を添加する方法や、架橋性単量体を共重合する方法などが用いられている。
【０００８】
しかしながら、外部架橋剤の添加による架橋処理や架橋性単量体の共重合による方法は、反応時間の制御やポットライフの問題があり、ロット間での粘着特性のバラツキを抑えることが難しく、製造工程での厳格な管理が必要となる。
【０００９】
一方、医療衛生用の粘着剤組成物や、これを用いた粘着テープなどは、例えば救急絆創膏やドレッシング材などのように、創傷部に貼付する場合が多いので、創傷部が雑菌によって汚染されないように、通常は滅菌処理が施されている。
【００１０】
滅菌方法としては、エチレンオキサイドガスなどによる化学的手法と、電子線やγ線などの電離性放射線の照射による物理的手法が一般的に採用されている。これらの手法のうち、設備面や経済性、法的規制などの点から、次第に電離性放射線による滅菌処理が主流になりつつある。
【００１１】
電離性放射線による滅菌処理は、上記のように優れた滅菌方法であるが、粘着剤に照射した場合には、滅菌処理と共に粘着剤が架橋されることも知られており、照射後に粘着剤中のゲル分が上昇し、その結果、皮膚接着性などの粘着特性が低下することがある。従って、電離性放射線照射後の粘着特性の低下を考慮して、予め粘着剤の粘着特性を調整しておくことも考えられるが、このような方法を採用した場合、電離性放射線の照射前の粘着剤の内部凝集力が低くなるように調整するので、保存中に粘着テープにおける粘着剤層が流動して、テープ側面から粘着剤がはみ出す、所謂、糊はみ出し現象を生じる恐れがあり、また、所定形状に打ち抜いたり、切断したりする際に用いる切断刃に粘着剤が付着して切断効率が低下するという問題も生じる。
【００１２】
【発明が解決しようとする課題】
そこで、本発明者は上記従来技術の問題点を解決するために鋭意検討した結果、医療衛生用粘着剤組成物としての各要求特性を満足する組成物を得るために、特定の単量体組成をエマルジョン重合して得られる共重合体組成物が、電離性放射線を照射しても粘着剤層中のゲル分率の変化が少なく、粘着特性を維持しながら滅菌処理を行えることを見い出し、本発明を完成するに至った。
【００１３】
【課題を解決するための手段】
即ち、本発明は炭素数５〜１５のアルキル基を有するメタクリル酸アルキルエステル７０〜９９重量％と、カルボキシル基もしくはヒドロキシル基を有する共重合性単量体１〜３０重量％を必須成分として含有する単量体混合物であって、さらに該単量体混合物中に炭素数４〜１５のアルキル基を有するアクリル酸アルキルエステルを５〜２０重量％の範囲で含有する単量体混合物を、乳化剤を用いて共重合してなるエマルジョン型粘着剤組成物に、電離性放射線が照射され、ゲル分率が４０〜１００％で、かつ電離性放射線照射前後でのゲル分率の変化率が３０％以内であることを特徴とする医療衛生用粘着剤組成物。
【００１４】
さらに、本発明は上記医療衛生用粘着剤組成物を、支持基材の片面に層状に形成してなる粘着テープもしくはシートを提供するものである。
【００１５】
【発明の実施の形態】
本発明の医療衛生用粘着剤組成物は、炭素数５〜１５のアルキル基を有するメタクリル酸アルキルエステルと、カルボキシル基もしくはヒドロキシル基を有する共重合性単量体を必須成分とする単量体混合物を乳化共重合して得られるものである。同様の生成物を均一重合系である溶液重合によって作製した場合、得られる共重合体の分子量はエマルジョン系と比べて小さくなり、その結果、皮膚面への接着性は良好であるが、粘着剤組成物の内部凝集力が不足する場合がある。このような溶液重合系によって得られた組成物から粘着テープやシートを作製すると、皮膚面からの粘着テープやシートを剥離する際に糊残り現象を生じる可能性があるので、本発明の目的を達成するには乳化重合を行うことが重要なのである。
【００１６】
上記メタクリル酸アルキルエステルとしては、炭素数５〜１５のアルキル基として、例えば、ペンチル基、ヘキシル基、ノニル基、オクチル基、デシル基、ドデシル基（ラウリル基）などのアルキル基が結合したメタクリル酸にエステル結合したものであって、これらのアルキル基は直鎖状であっても、分岐鎖状であってもよい。本発明において、特に好ましいメタクリル酸アルキルエステルとしては、炭素数８〜１４のアルキル基を有するものであり、具体的には、メタクリル酸２−エチルヘキシルやメタクリル酸ｎ−オクチル、メタクリル酸ラウリル、メタクリル酸テトラデシルが挙げられる。
【００１７】
また、上記メタクリル酸アルキルエステルに共重合させる共重合性単量体としては、アクリル酸やメタクリル酸、イタコン酸、マレイン酸、無水マレイン酸、フマール酸などのカルボキシル基を有する単量体や、（メタ）アクリル酸２−ヒドロキシエチルや（メタ）アクリル酸２−ヒドロキシプロピル、トリアクリル酸ペンタエリスリトール、トリアクリル酸トリメチロールプロパン、ヘキサアクリル酸ジペンタエリスリトールなどのヒドロキシル基を有する単量体を用いる。なお、トリアクリル酸ペンタエリスリトール、トリアクリル酸トリメチロールプロパン、ヘキサアクリル酸ジペンタエリスリトールは、分子内に二個以上の不飽和二重結合を有する多官能性単量体であって、分子内架橋剤として作用して得られる共重合体への内部凝集力付与に大きく寄与するものである。
【００１８】
上記共重合性単量体は一般に水溶性を呈するものであって、得られるエマルジョン型粘着剤に皮膚面への接着性を付与すると共に、電離性放射線を照射した際の架橋点となるものである。
【００１９】
本発明では上記各単量体を乳化共重合することによって共重合体を得ることができるが、各単量体の共重合量は、メタクリル酸アルキルエステル７０〜９９重量％、好ましくは８０〜９５重量％、共重合性単量体１〜３０重量％、好ましくは２〜２５重量％の比率になるように調整する。
【００２０】
共重合性単量体の量が１重量％に満たない場合には、皮膚面に貼付したときの耐水性、耐汗性が良好であるが、粘着剤層中の内部凝集力が小さくなる傾向を示し、また、３０重量％を超えると、粘着剤層の内部凝集力は大きくなるが、皮膚面に貼付使用した場合に耐水性や耐汗性が低下するようになる。一方、メタクリル酸アルキルエステルの量が７０重量％に満たない場合には、電離性放射線照射前後のゲル分率の変化率が３０％以上となって、大きな特性変化を生じ、皮膚面に貼付中に脱落する恐れがあり、９９重量％を超える量では、皮膚面からの剥離時に痛みや糊残り現象を生じる傾向を示すのである。
【００２１】
本発明の医療衛生用粘着剤組成物は、上記各単量体の混合物を乳化剤の存在下で乳化共重合させて得られるものであるが、必要に応じて、炭素数４〜１５のアルキル基を有するアクリル酸アルキルエステルや、酢酸ビニル、アクリロニトリルなどを適宜共重合することもできる。具体的には、これらの単量体は単量体混合物中に５〜２０重量％の範囲になるように含有させることが好ましい。
【００２２】
また、本発明の医療衛生用粘着剤組成物は、本発明の目的である電離性放射線照射前後のゲル分率の変動を抑えて、皮膚接着力の低下を抑制するために、粘着剤組成物中のゲル分率を４０〜７０重量％、好ましくは４５〜６０重量％に調整する。ゲル分率が小さすぎると粘着剤組成物の粘性が高くなって粘着力が増大し、その結果、皮膚面への糊残り現象を生じたり、皮膚刺激性が高くなったりする傾向を示すと共に、電離性放射線照射後にゲル分率の大幅な上昇を生じ、ゲル分率が大きすぎると粘着剤組成物の弾性が高まり粘着力の低下を招くようになって、その結果、皮膚面からの剥がれ（脱落現象）を生じるようになる。
【００２３】
なお、本発明におけるゲル分率とは、乾燥したサンプルをトルエン中に常温で７日間浸漬し、平均孔径０．２μｍのポリテトラフルオロエチレン製多孔質膜（日東電工社製、ＮＴＦ膜）にてトルエン不溶分を濾別、乾燥し、浸漬前の乾燥サンプル重量との比率で算出した値である。
【００２４】
本発明の医療衛生用粘着剤組成物を得るに際し、上記各単量体を混合してなる単量体混合物を、水媒体中で乳化剤を用いて乳化、ミセル形成させ、重合開始剤を配合、加温することにより、ミセル内での乳化重合反応を開始させ、エマルジョン型の粘着剤組成物を得る。
【００２５】
また、上記のように乳化重合を行うに際して、低分子量の共重合体を作製して全体の平均分子量を調整する目的で、連鎖移動剤や親水性アルコールを添加することもできる。
【００２６】
このような連鎖移動剤としては、乳化された単量体混合物中でラジカル種を捕捉して連鎖移動させるためには、疎水性の連鎖移動剤を用いる必要があり、具体的にはラウリルメルカプタンやチオグリコール酸などの硫黄系化合物を用いる。
【００２７】
また、親水性アルコールとしては、具体的にはメタノールやエタノール、イソプロピルアルコール、ｎ−プロピルアルコール、ブチルアルコールなどの炭素数が１〜４の脂肪族アルコールを用いることができる。これらも乳化重合時に水媒体中に溶解して、連鎖移動剤的に作用するものである。
【００２８】
本発明において乳化共重合の際に用いる乳化剤は、乳化重合時に水媒体中での単量体の分散安定性を良好にし、安定な乳化重合反応を維持するために重要であり、カチオン系、アニオン系、ノニオン系の乳化剤や、反応性乳化剤などを一種もしくは二種以上併用して用いることができ、これらのうち脂肪酸塩、高級アルコール硫酸エステル塩、スルホコハク酸エステル塩、ジアルキルスルホコハク酸塩などのアニオン系乳化剤を好適に用いることができる。
【００２９】
重合開始剤は乳化重合を行なう際に必要なものであり、過硫酸アンモニウム、過硫酸カリウムなどの過硫酸塩や、過酸化水素、過酸化ベンゾイルなどの過酸化物を用いる。また、必要に応じて、低い温度で重合反応を開始できるレドックス系重合開始剤として、過硫酸塩とアルカリ金属の亜硫酸塩、重亜硫酸塩などの還元剤を組み合わせて用いることもできる。
【００３０】
上記のような乳化重合における上記各成分の代表的な配合量は、単量体混合物１００重量部に対して、連鎖移動剤０．００１〜２重量部、親水性アルコール０．００１〜２重量部、乳化剤と重合開始剤は任意量である。
【００３１】
連鎖移動剤や親水性アルコールの配合量が少ないと、得られる共重合体の重量平均分子量が大きくなりすぎて、粘着特性としての粘着力が悪くなったり、重合安定性に欠けて重合中に反応系全体がゲル化してしまったり、皮膚面への接着力不足となる恐れがある。一方、配合量が多すぎると、得られる共重合体の重合平均分子量が小さくなりすぎて、粘着特性としての凝集力が悪くなったり、皮膚面へ糊残りを生じたり、皮膚刺激性が強くなる傾向を示すので、粘着特性のバランスと皮膚無刺激性を発揮しがたくなる。
【００３２】
重合方法は上記各成分を水媒体中に配合して、乳化重合できれば特に限定されず、一括仕込みで反応させる一括重合法や、種エマルジョン（シード）の存在下で乳化重合を行なうシード重合法、重合反応を段階的に行なう多段階重合法、単量体組成の組成比を連続的に変えて重合反応を行うパワーフィード重合法などから適宜選択すればよい。
【００３３】
上記のようにして得られた本発明の医療衛生用粘着剤組成物は、支持基材の片面に上記組成からなる粘着剤組成物を、層状に形成することによって、粘着テープもしくはシートとすることができる。形成する粘着剤層の厚みは、１５〜７０μｍ、好ましくは２０〜６５μｍ程度にすることによって、皮膚接着性や内部凝集性のバランスを取りやすくなり、好ましいものである。
【００３４】
本発明の粘着テープもしくはシートに用いる支持基材としては、ポリエチレンやポリプロピレン、エチレン／酢酸ビニル共重合体、ポリエステルなどの各種プラスチックフィルムや、これらのプラスチックからなる織布や不織布、編布、紙、金属箔、またはこれらの積層フィルムなどを用いることができる。
【００３５】
本発明の粘着テープもしくはシートは、医療用途、衛生材料用途に用いるものであれば、形状に限定はなく、例えば救急絆創膏や巻絆創膏、大型絆創膏、ドレッシング材などに好適に用いることができる
【００３６】
また、上記粘着テープもしくはシートは、長尺のものは支持基材の背面にシリコーン樹脂やフッ素樹脂などの剥離剤を塗布して自背面に粘着剤層が接するように巻回してロール状物としたり、剥離処理を施した剥離シートを粘着剤層面に仮着したシート状物としておくことが好ましい。
【００３７】
本発明の医療衛生用粘着組成物および粘着テープまたはシートは、上記構成からなるものであり、これを滅菌処理するに際して電離性放射線を照射した場合に、粘着剤中のゲル分の上昇は少なく、粘着特性の低下を生じにくいものである。このような滅菌処理に用いる電離性放射線としては、一般的な放射線として、γ線や電子線、Ｘ線、α線、中性子線などを用いることができ、これらのうち安全性や取扱性、生産性、法的規制などの点から、γ線や電子線を用いることが好ましい。
【００３８】
照射線量としては２０〜５０ｋＧｙ、好ましくは２５〜３５ｋＧｙがよい。なお、本発明においては電離性放射線を照射することによって、粘着剤層に滅菌処理を施すと共に、架橋処理も施されるのである。なお、本発明の粘着剤組成物では、特定の単量体組成からなるメタクリル酸エステル系の乳化共重合体を用いているので、電離性放射線を照射した場合、架橋反応が生じるが、粘着剤分子の主鎖が切断される分子鎖の崩壊現象が生じる。従って、本発明では電離性放射線を照射しても粘着剤中のゲル分率の上昇が抑制されるのである。
【００３９】
【発明の効果】
本発明の医療衛生用粘着剤組成物は、以上の構成からなるので支持基材の片面に層状に形成して粘着テープやシートとして皮膚面に貼付使用した場合に、皮膚面に対して刺激性が少なく、特に長期間の貼付に対して有用である。さらに、電子線やγ線などの電離性放射線を照射して滅菌を行った場合、照射前後の粘着剤層のゲル分率の変動が少なく、変化率３０％以内となり、粘着特性の変動が顕著に少ないものである。
【００４０】
また、粘着特性としての皮膚接着力や保持力、投錨力のバランスにも優れており、使用中の剥離脱落や剥離時の糊残り現象などもなく、ドレッシング材や絆創膏、救急絆創膏などの用途に最適な粘着テープやシートとすることができる。
【００４１】
【実施例】
以下に本発明の実施例を示し、さらに具体的に説明するが、本発明はこれらに限定されるものではなく、本発明の技術的思想を逸脱しない範囲内で種々の応用が可能である。
【００４２】
実施例１
メタクリル酸２−エチルヘキシル８００ｇ、アクリル酸２０ｇ、アクリル酸２−エチルヘキシル２００ｇからなる単量体混合物に、アニオン系乳化剤（第一工業製薬社製、商品名ハイテノールＮ−１７、有効濃度１重量％の水溶液）８００ｇを加え、不活性ガス雰囲気下で高速ホモミキサー（特殊機械社製）を用いて１５分間攪拌乳化し、攪拌を続けながら７０℃に加温した。
【００４３】
次いで、重合開始剤としての過硫酸カリウム１ｇを５０ｇの水に溶解した水溶液を添加して乳化重合反応を開始させ、約５時間反応を続けた。そののち、８５℃に昇温して２時間熟成反応を行い、重合反応を完結させて、本発明の医療衛生用粘着剤組成物を得た。
【００４４】
実施例２
単量体混合物として、メタクリル酸ラウリル８００ｇ、アクリル酸２０ｇ、アクリル酸２−エチルヘキシル２００ｇを用いた以外は、実施例１と同様な方法で本発明の医療衛生用粘着剤組成物を得た。
【００４５】
実施例３
単量体混合物として、メタクリル酸ｎ−オクチル８００ｇ、アクリル酸２０ｇ、アクリル酸２−エチルヘキシル２００ｇを用いた以外は、実施例１と同様な方法で本発明の医療衛生用粘着剤組成物を得た。
【００４６】
比較例１
単量体混合物として、アクリル酸２−エチルヘキシル９２０ｇ、アクリル酸２０ｇを用いた以外は、実施例１と同様な方法で医療衛生用粘着剤組成物を得た。
【００４７】
比較例２
単量体混合物として、アクリル酸ラウリル８００ｇ、アクリル酸２０ｇ、アクリル酸２−エチルヘキシル２００ｇを用いた以外は、実施例１と同様な方法で医療衛生用粘着剤組成物を得た。
【００４８】
比較例３
単量体混合物として、メタクリル酸ラウリル６００ｇ、アクリル酸２０ｇ、アクリル酸２−エチルヘキシル４００ｇを用いた以外は、実施例１と同様な方法で医療衛生用粘着剤組成物を得た。
【００４９】
上記各実施例および比較例にて得られた医療用粘着剤組成物を、５０μｍ厚のポリエステルフィルムの片面に、乾燥後の厚みが４０μｍとなるように塗布し、約１００℃で５分間乾燥を行い、さらに５０℃で２４時間熟成を行い、粘着テープを作製した。
【００５０】
なお、ゲル分率測定用のサンプルとして、各実施例および比較例にて得た粘着剤組成物を離型フィルム上に上記と同様の条件で塗布、乾燥して粘着剤層を形成した。
【００５１】
上記のようにして得られた各粘着テープに、下記条件で電子線を照射した。
＜照射条件＞
１台の照射用台車に、各粘着テープを１枚（７．５ｃｍ×２０ｃｍ）ずつ並べて載置し、電圧４．８ＭＶ、電流２０．０ｍＡ、台車速度１４．０ｍ／分の条件で、２５ｋＧｙの照射線量で電子線を照射した。
【００５２】
次に、電子線照射前の粘着テープおよび照射後の粘着テープについて、接着力、ゲル分率、およびゲル分率の変化率を以下の方法で測定し、その結果を表１に記載した。
【００５３】
＜接着力＞
粘着テープを２０ｍｍ幅に裁断し、２３℃、６５％Ｒ．Ｈ．の雰囲気下で、粘着剤層をベークライト板に２ｋｇ／ｃｍ2 で圧着し、圧着３０分経過後、剥離速度３００ｍｍ／分で１８０度方法に粘着テープを剥離して、その際の剥離応力を接着力とした。
【００５４】
＜ゲル分率＞
粘着剤層を形成した離型フィルム上から、所定量の粘着剤を採取、秤量し重量（Ｗ0 ）を測定した。次に、２３℃のトルエン中に７日間浸漬して可溶分を抽出し、その残渣（トルエン不溶分：ゲル分）をポリテトラフルオロエチレン多孔質膜（平均孔径０．２μｍ、日東電工社製、ＮＴＦ膜）にて濾別、１２０℃で２時間乾燥して重量（Ｗ1 ）を測定した。
上記のようにして測定したＷ1 をＷ0 で除して、初期重量に対する不溶分の重量をゲル分率（％）として算出した。
【００５５】
【表１】
表１の結果から明らかなように、実施例品では接着力およびゲル分率の値が、電子線照射前後でほとんど変化がなく、比較例品では電子線を照射すると、ゲル分率の変化率が大きいので、明らかな接着力の低下が見られた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a medical pressure-sensitive adhesive composition used for skin application in the medical hygiene field, and a pressure-sensitive adhesive tape or sheet using this composition.
[0002]
[Prior art]
The medical hygiene pressure-sensitive adhesive composition used for skin application is usually a medical or hygiene pressure-sensitive adhesive tape or sheet formed on one side of a support substrate in the form of a layer, and the skin to which this is to be applied. Used by sticking to a surface.
[0003]
The pressure-sensitive adhesive layer thus formed generally needs to be firmly bonded and fixed to the skin surface and has excellent so-called adhesive properties such as cohesive force in the layer and anchoring force with the support substrate. Must.
[0004]
In addition, since it is used for skin application, it must be non-irritating to the skin surface to which it is applied, and it must not cause physical irritation when peeled from the skin surface, causing skin irritation. The property of irritation is also required.
[0005]
Conventionally, as a pressure-sensitive adhesive composition for medical use, an acrylic pressure-sensitive adhesive composition mainly composed of alkyl acrylate and a rubber-based pressure-sensitive adhesive composition mainly composed of synthetic rubber or natural rubber are generally used. It has been. However, it is difficult to adjust the adhesive properties of rubber-based adhesives, and natural rubber has some difficulties in handling, such as the possibility of allergy due to proteins as impurities, etc., polymerization method, polymerization composition, blending, etc. Thus, a relatively large number of studies have been conducted on acrylic pressure-sensitive adhesive compositions whose adhesion characteristics can be easily adjusted.
[0006]
As described above, the acrylic pressure-sensitive adhesive composition is relatively easy to adjust the pressure-sensitive adhesive properties and can provide a well-balanced pressure-sensitive adhesive. However, there is still a lot of room for improvement, and the actual situation is that various studies have been made.
[0007]
For example, in order to improve the skin adhesive strength, the amount of copolymerization of alkyl alkyl ester having about 4 to 12 carbon atoms of the alkyl group as the skin adhesion imparting component is increased, or the alkyl alkyl ester having a long alkyl chain is used. However, on the other hand, the pressure-sensitive adhesive layer needs to be cross-linked in order to cause a decrease in holding power due to a decrease in internal cohesive force of the pressure-sensitive adhesive layer. As a typical crosslinking treatment, a method of adding an external crosslinking agent such as polyisocyanate, amines, or an epoxy compound, a method of copolymerizing a crosslinking monomer, or the like is used.
[0008]
However, the method of cross-linking treatment by adding an external cross-linking agent or copolymerization of cross-linkable monomers has problems of control of reaction time and pot life, and it is difficult to suppress variations in adhesion characteristics between lots. Strict management in the process is required.
[0009]
On the other hand, adhesive compositions for medical hygiene and adhesive tapes using the same are often affixed to wounds, such as emergency bandages and dressings, so that the wounds are not contaminated by various bacteria. In addition, it is usually sterilized.
[0010]
As a sterilization method, a chemical method using ethylene oxide gas or the like and a physical method using irradiation with ionizing radiation such as an electron beam or γ-ray are generally employed. Among these methods, sterilization with ionizing radiation is gradually becoming mainstream from the viewpoints of equipment, economy, legal regulations, and the like.
[0011]
Sterilization treatment with ionizing radiation is an excellent sterilization method as described above, but it is also known that when an adhesive is irradiated, the adhesive is cross-linked with the sterilization treatment. As a result, the gel content may increase, and as a result, adhesive properties such as skin adhesion may decrease. Therefore, it is conceivable to adjust the adhesive property of the adhesive in advance in consideration of the decrease in the adhesive property after irradiation with ionizing radiation. Since the internal cohesive force of the adhesive is adjusted to be low, the adhesive layer in the adhesive tape flows during storage, and the adhesive protrudes from the side surface of the tape, so-called glue sticking out phenomenon may occur. There also arises a problem that the adhesive is attached to the cutting blade used for punching or cutting into a predetermined shape and the cutting efficiency is lowered.
[0012]
[Problems to be solved by the invention]
Therefore, as a result of intensive studies to solve the problems of the prior art, the present inventor has obtained a specific monomer composition in order to obtain a composition satisfying each required characteristic as an adhesive composition for medical hygiene. It was found that the copolymer composition obtained by emulsion polymerization of the gel has little change in the gel fraction in the pressure-sensitive adhesive layer even when irradiated with ionizing radiation and can be sterilized while maintaining the adhesive properties. The invention has been completed.
[0013]
[Means for Solving the Problems]
That is, the present invention contains 70 to 99% by weight of a methacrylic acid alkyl ester having an alkyl group having 5 to 15 carbon atoms and 1 to 30% by weight of a copolymerizable monomer having a carboxyl group or a hydroxyl group as essential components. A monomer mixture, which further contains an alkyl acrylate ester having an alkyl group having 4 to 15 carbon atoms in the monomer mixture in the range of 5 to 20% by weight, using an emulsifier The emulsion-type pressure-sensitive adhesive composition obtained by copolymerization is irradiated with ionizing radiation, the gel fraction is 40 to 100%, and the change rate of the gel fraction before and after irradiation with ionizing radiation is within 30%. A pressure-sensitive adhesive composition for medical hygiene, comprising:
[0014]
Furthermore, this invention provides the adhesive tape or sheet | seat formed by forming the said adhesive composition for medical hygiene in a layer form on the single side | surface of a support base material.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The pressure-sensitive adhesive composition for medical hygiene of the present invention is a monomer mixture containing, as essential components, an alkyl methacrylate having 5 to 15 carbon atoms and a copolymerizable monomer having a carboxyl group or a hydroxyl group. Is obtained by emulsion copolymerization. When a similar product is produced by solution polymerization which is a homogeneous polymerization system, the molecular weight of the resulting copolymer is smaller than that of the emulsion system, and as a result, the adhesiveness to the skin surface is good. The internal cohesive strength of the composition may be insufficient. If an adhesive tape or sheet is produced from a composition obtained by such a solution polymerization system, an adhesive residue may occur when the adhesive tape or sheet is peeled from the skin surface. It is important to perform emulsion polymerization to achieve.
[0016]
Examples of the methacrylic acid alkyl ester include methacrylic acid bonded with an alkyl group such as a pentyl group, hexyl group, nonyl group, octyl group, decyl group, dodecyl group (lauryl group) as an alkyl group having 5 to 15 carbon atoms. These alkyl groups may be linear or branched. In the present invention, particularly preferred methacrylic acid alkyl esters are those having an alkyl group having 8 to 14 carbon atoms, specifically, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, methacrylic acid. Tetradecyl is mentioned.
[0017]
Examples of the copolymerizable monomer copolymerized with the alkyl methacrylate include monomers having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, and fumaric acid, A monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, or dipentaerythritol hexaacrylate is used. Note that pentaerythritol triacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate are polyfunctional monomers having two or more unsaturated double bonds in the molecule, It greatly contributes to imparting internal cohesive force to the copolymer obtained by acting as an agent.
[0018]
The copolymerizable monomer is generally water-soluble and provides the resulting emulsion-type pressure-sensitive adhesive with adhesiveness to the skin surface, as well as a crosslinking point when irradiated with ionizing radiation. is there.
[0019]
In the present invention, a copolymer can be obtained by emulsion copolymerization of each of the above monomers. The copolymerization amount of each monomer is 70 to 99% by weight, preferably 80 to 95% by weight, of methacrylic acid alkyl ester. It is adjusted so that the ratio is 1 to 30% by weight, preferably 2 to 25% by weight, and preferably 2 to 25% by weight.
[0020]
When the amount of the copolymerizable monomer is less than 1% by weight, the water resistance and sweat resistance when applied to the skin surface are good, but the internal cohesive force in the adhesive layer tends to be small When the content exceeds 30% by weight, the internal cohesive force of the pressure-sensitive adhesive layer increases, but the water resistance and sweat resistance decrease when applied to the skin surface. On the other hand, when the amount of methacrylic acid alkyl ester is less than 70% by weight, the change rate of the gel fraction before and after ionizing radiation irradiation is 30% or more, resulting in a large characteristic change and being applied to the skin surface. If the amount exceeds 99% by weight, pain or adhesive residue tends to occur at the time of peeling from the skin surface.
[0021]
The pressure-sensitive adhesive composition for medical hygiene of the present invention is obtained by emulsion copolymerization of a mixture of the above monomers in the presence of an emulsifier, and if necessary, an alkyl group having 4 to 15 carbon atoms. It is also possible to appropriately copolymerize acrylic acid alkyl ester having vinyl acetate, vinyl acetate, acrylonitrile and the like. Specifically, these monomers are preferably contained in the monomer mixture so as to be in the range of 5 to 20% by weight.
[0022]
In addition, the pressure-sensitive adhesive composition for medical hygiene of the present invention is a pressure-sensitive adhesive composition in order to suppress the change in the gel fraction before and after ionizing radiation irradiation, which is the object of the present invention, and to suppress the decrease in skin adhesive force. The gel fraction is adjusted to 40 to 70% by weight, preferably 45 to 60% by weight. If the gel fraction is too small, the viscosity of the pressure-sensitive adhesive composition is increased and the adhesive force is increased. As a result, there is a tendency for adhesive residue to occur on the skin surface, and the skin irritation tends to increase. After irradiation with ionizing radiation, the gel fraction is significantly increased. When the gel fraction is too large, the elasticity of the pressure-sensitive adhesive composition is increased, resulting in a decrease in the adhesive strength. As a result, peeling from the skin surface ( Dropout phenomenon).
[0023]
In the present invention, the gel fraction means that a dried sample is immersed in toluene at room temperature for 7 days, and is a polytetrafluoroethylene porous membrane (NTF membrane manufactured by Nitto Denko Corporation) having an average pore size of 0.2 μm. This is a value calculated by separating the toluene insolubles by filtration, drying, and the ratio to the dry sample weight before immersion.
[0024]
When obtaining the medical hygiene pressure-sensitive adhesive composition of the present invention, a monomer mixture obtained by mixing each of the above monomers is emulsified in an aqueous medium using an emulsifier, micelle formation, and a polymerization initiator is blended. By heating, an emulsion polymerization reaction in the micelle is started, and an emulsion-type pressure-sensitive adhesive composition is obtained.
[0025]
In addition, when carrying out emulsion polymerization as described above, a chain transfer agent or a hydrophilic alcohol can be added for the purpose of preparing a low molecular weight copolymer and adjusting the overall average molecular weight.
[0026]
As such a chain transfer agent, it is necessary to use a hydrophobic chain transfer agent in order to capture and chain transfer radical species in the emulsified monomer mixture, specifically, lauryl mercaptan or Sulfur compounds such as thioglycolic acid are used.
[0027]
As the hydrophilic alcohol, specifically, an aliphatic alcohol having 1 to 4 carbon atoms such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, or butyl alcohol can be used. These also dissolve in an aqueous medium at the time of emulsion polymerization and act as a chain transfer agent.
[0028]
The emulsifier used for the emulsion copolymerization in the present invention is important for improving the dispersion stability of the monomer in the aqueous medium during the emulsion polymerization and maintaining a stable emulsion polymerization reaction. And nonionic emulsifiers and reactive emulsifiers can be used alone or in combination of two or more of them. Among these, anions such as fatty acid salts, higher alcohol sulfates, sulfosuccinates, dialkylsulfosuccinates, etc. A system emulsifier can be suitably used.
[0029]
The polymerization initiator is necessary for emulsion polymerization, and a persulfate such as ammonium persulfate or potassium persulfate, or a peroxide such as hydrogen peroxide or benzoyl peroxide is used. Further, if necessary, as a redox polymerization initiator capable of starting a polymerization reaction at a low temperature, a reducing agent such as a persulfate and an alkali metal sulfite or bisulfite may be used in combination.
[0030]
The typical blending amount of each component in the emulsion polymerization as described above is 0.001 to 2 parts by weight of a chain transfer agent and 0.001 to 2 parts by weight of a hydrophilic alcohol with respect to 100 parts by weight of the monomer mixture. The emulsifier and the polymerization initiator are in arbitrary amounts.
[0031]
If the amount of the chain transfer agent or hydrophilic alcohol is too small, the weight average molecular weight of the resulting copolymer becomes too large, resulting in poor adhesion as an adhesive property or lack of polymerization stability and reaction during polymerization. There is a risk that the entire system will gel and the adhesion to the skin surface will be insufficient. On the other hand, if the blending amount is too large, the polymerization average molecular weight of the resulting copolymer will be too small, the cohesive force as adhesive properties will deteriorate, the adhesive will remain on the skin surface, and the skin irritation will be stronger Since it shows a tendency, it is difficult to exert a balance of adhesive properties and skin irritation.
[0032]
The polymerization method is not particularly limited as long as emulsion polymerization can be carried out by blending each of the above components in an aqueous medium, a batch polymerization method in which reaction is performed by batch charging, a seed polymerization method in which emulsion polymerization is performed in the presence of a seed emulsion (seed), What is necessary is just to select suitably from the multistage polymerization method which performs a polymerization reaction in steps, the power feed polymerization method which performs a polymerization reaction by changing the composition ratio of a monomer composition continuously.
[0033]
The pressure-sensitive adhesive composition for medical hygiene of the present invention obtained as described above is formed into a pressure-sensitive adhesive tape or sheet by forming the pressure-sensitive adhesive composition having the above composition on one side of a support base material in a layered manner. Can do. By forming the pressure-sensitive adhesive layer to have a thickness of 15 to 70 μm, preferably about 20 to 65 μm, it is easy to balance skin adhesiveness and internal cohesiveness, which is preferable.
[0034]
As the support substrate used for the pressure-sensitive adhesive tape or sheet of the present invention, various plastic films such as polyethylene, polypropylene, ethylene / vinyl acetate copolymer, polyester, woven fabrics and nonwoven fabrics made of these plastics, knitted fabrics, paper, A metal foil or a laminated film of these can be used.
[0035]
The pressure-sensitive adhesive tape or sheet of the present invention is not limited in shape as long as it is used for medical applications and hygiene materials, and can be suitably used for, for example, emergency bandages, wound bandages, large bandages, dressing materials, etc. ]
Also, if the adhesive tape or sheet is long, apply a release agent such as silicone resin or fluororesin to the back of the support substrate and roll it so that the adhesive layer is in contact with the back. Or a release sheet that has been subjected to a release treatment is preferably prepared as a sheet-like product temporarily attached to the pressure-sensitive adhesive layer surface.
[0037]
The medical hygiene pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape or sheet of the present invention are composed of the above-described structure, and when irradiated with ionizing radiation when sterilizing the composition, there is little increase in the gel content in the pressure-sensitive adhesive. It is difficult to cause a decrease in adhesive properties. As ionizing radiation used for such sterilization treatment, γ rays, electron rays, X rays, α rays, neutron rays, etc. can be used as general radiation, and among these, safety, handling, production From the viewpoints of property and legal regulations, it is preferable to use γ rays or electron beams.
[0038]
The irradiation dose is 20 to 50 kGy, preferably 25 to 35 kGy. In the present invention, the pressure-sensitive adhesive layer is sterilized and cross-linked by irradiating with ionizing radiation. In the pressure-sensitive adhesive composition of the present invention, since a methacrylic ester emulsion copolymer having a specific monomer composition is used, a crosslinking reaction occurs when irradiated with ionizing radiation. A molecular chain collapse phenomenon occurs in which the main chain of the molecule is broken. Therefore, in the present invention, even if ionizing radiation is irradiated, an increase in the gel fraction in the pressure-sensitive adhesive is suppressed.
[0039]
【The invention's effect】
The medical hygiene pressure-sensitive adhesive composition of the present invention is composed of the above-described structure, so that it is irritating to the skin surface when it is formed in a layer on one side of a support substrate and applied to the skin surface as an adhesive tape or sheet. This is particularly useful for long-term application. Furthermore, when sterilization is performed by irradiating ionizing radiation such as electron beam or γ-ray, the gel fraction of the adhesive layer before and after irradiation is small, the change rate is within 30%, and the change in adhesive property is remarkable. There are few things.
[0040]
In addition, it has an excellent balance of adhesive properties such as skin adhesive strength, retention strength, and anchoring force, and there is no peeling off during use or adhesive residue during peeling, and it can be used for dressing materials, adhesive plasters, emergency adhesive plasters, etc. Optimal adhesive tape and sheet can be obtained.
[0041]
【Example】
Examples of the present invention will be described below and will be described in more detail. However, the present invention is not limited to these examples, and various applications are possible without departing from the technical idea of the present invention.
[0042]
Example 1
To a monomer mixture consisting of 800 g of 2-ethylhexyl methacrylate, 20 g of acrylic acid, and 200 g of 2-ethylhexyl acrylate, an anionic emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., trade name Haitenol N-17, effective concentration of 1% by weight) 800 g of an aqueous solution) was added, emulsified and emulsified for 15 minutes using a high-speed homomixer (manufactured by Special Machinery Co., Ltd.) under an inert gas atmosphere, and the mixture was heated to 70 ° C. while stirring was continued.
[0043]
Subsequently, an aqueous solution in which 1 g of potassium persulfate as a polymerization initiator was dissolved in 50 g of water was added to start the emulsion polymerization reaction, and the reaction was continued for about 5 hours. Thereafter, the temperature was raised to 85 ° C. and a ripening reaction was performed for 2 hours to complete the polymerization reaction, thereby obtaining a medical hygiene pressure-sensitive adhesive composition of the present invention.
[0044]
Example 2
A medical hygiene pressure-sensitive adhesive composition of the present invention was obtained in the same manner as in Example 1 except that 800 g of lauryl methacrylate, 20 g of acrylic acid, and 200 g of 2-ethylhexyl acrylate were used as the monomer mixture.
[0045]
Example 3
A medical hygiene pressure-sensitive adhesive composition of the present invention was obtained in the same manner as in Example 1, except that 800 g of n-octyl methacrylate, 20 g of acrylic acid, and 200 g of 2-ethylhexyl acrylate were used as the monomer mixture. .
[0046]
Comparative Example 1
A medical hygiene pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that 920 g of 2-ethylhexyl acrylate and 20 g of acrylic acid were used as the monomer mixture.
[0047]
Comparative Example 2
A medical hygiene pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that 800 g of lauryl acrylate, 20 g of acrylic acid, and 200 g of 2-ethylhexyl acrylate were used as the monomer mixture.
[0048]
Comparative Example 3
A medical hygiene pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that 600 g of lauryl methacrylate, 20 g of acrylic acid, and 400 g of 2-ethylhexyl acrylate were used as the monomer mixture.
[0049]
The medical adhesive composition obtained in each of the above Examples and Comparative Examples was applied to one side of a 50 μm thick polyester film so that the thickness after drying was 40 μm, and dried at about 100 ° C. for 5 minutes. And aged for 24 hours at 50 ° C. to produce an adhesive tape.
[0050]
In addition, as a sample for measuring the gel fraction, the pressure-sensitive adhesive composition obtained in each example and comparative example was coated on a release film under the same conditions as described above, and dried to form a pressure-sensitive adhesive layer.
[0051]
Each adhesive tape obtained as described above was irradiated with an electron beam under the following conditions.
<Irradiation conditions>
Each adhesive tape is placed side by side (7.5 cm × 20 cm) on one irradiation carriage, and is 25 kGy under conditions of a voltage of 4.8 MV, a current of 20.0 mA, and a carriage speed of 14.0 m / min. The electron beam was irradiated with the irradiation dose.
[0052]
Next, with respect to the adhesive tape before electron beam irradiation and the adhesive tape after irradiation, the adhesive force, the gel fraction, and the change rate of the gel fraction were measured by the following methods, and the results are shown in Table 1.
[0053]
<Adhesive strength>
The adhesive tape was cut to a width of 20 mm, and 23 ° C., 65% R.D. H. Under pressure, the pressure-sensitive adhesive layer was pressure-bonded to the bakelite plate at 2 kg / cm 2 , and after 30 minutes of pressure-bonding, the pressure-sensitive adhesive tape was peeled off in a 180-degree manner at a peeling speed of 300 mm / min. Power.
[0054]
<Gel fraction>
A predetermined amount of the pressure-sensitive adhesive was collected from the release film on which the pressure-sensitive adhesive layer had been formed, weighed, and the weight (W 0 ) was measured. Next, the soluble component is extracted by soaking in toluene at 23 ° C. for 7 days, and the residue (toluene insoluble component: gel component) is removed from a polytetrafluoroethylene porous membrane (average pore size 0.2 μm, manufactured by Nitto Denko Corporation). , NTF membrane), and dried at 120 ° C. for 2 hours, and the weight (W 1 ) was measured.
W 1 measured as described above was divided by W 0 , and the weight of insoluble matter relative to the initial weight was calculated as the gel fraction (%).
[0055]
[Table 1]
As is clear from the results in Table 1, the adhesive strength and gel fraction values of the example products are almost unchanged before and after the electron beam irradiation, and the comparative sample products are irradiated with the electron beam. As a result, the adhesive strength was clearly reduced.
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001117003A JP4727839B2 (en) | 2001-04-16 | 2001-04-16 | Medical hygiene pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet using the composition |
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| JP2001117003A JP4727839B2 (en) | 2001-04-16 | 2001-04-16 | Medical hygiene pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet using the composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327219B (en) * | 2014-08-27 | 2017-02-22 | 武汉持欣科技有限公司 | Aqueous emulsion for basic binder of adhesive for hard-bonding materials and preparation method thereof |
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| CA2937330A1 (en) * | 2014-01-22 | 2015-07-30 | Adhesives Research, Inc. | Gamma resistant adhesives |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5777617A (en) * | 1980-10-20 | 1982-05-15 | Nichiban Co Ltd | Plaster for cardiac disease |
| JPS58164506A (en) * | 1982-03-24 | 1983-09-29 | Sekisui Chem Co Ltd | Adhesive tape or sheet for medical use |
| JPH03112557A (en) * | 1989-09-27 | 1991-05-14 | Sekisui Chem Co Ltd | Application agent |
| JPH03146579A (en) * | 1989-11-02 | 1991-06-21 | Sekisui Chem Co Ltd | Medical tacky base |
| JPH11226109A (en) * | 1998-02-16 | 1999-08-24 | Nitto Denko Corp | Medical pasting material |
-
2001
- 2001-04-16 JP JP2001117003A patent/JP4727839B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5777617A (en) * | 1980-10-20 | 1982-05-15 | Nichiban Co Ltd | Plaster for cardiac disease |
| JPS58164506A (en) * | 1982-03-24 | 1983-09-29 | Sekisui Chem Co Ltd | Adhesive tape or sheet for medical use |
| JPH03112557A (en) * | 1989-09-27 | 1991-05-14 | Sekisui Chem Co Ltd | Application agent |
| JPH03146579A (en) * | 1989-11-02 | 1991-06-21 | Sekisui Chem Co Ltd | Medical tacky base |
| JPH11226109A (en) * | 1998-02-16 | 1999-08-24 | Nitto Denko Corp | Medical pasting material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327219B (en) * | 2014-08-27 | 2017-02-22 | 武汉持欣科技有限公司 | Aqueous emulsion for basic binder of adhesive for hard-bonding materials and preparation method thereof |
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| JP2002306589A (en) | 2002-10-22 |
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