JP2002306589A - Medical tacky adhesive composition and tacky adhesive tape or sheet formed by using this composition - Google Patents
Medical tacky adhesive composition and tacky adhesive tape or sheet formed by using this compositionInfo
- Publication number
- JP2002306589A JP2002306589A JP2001117003A JP2001117003A JP2002306589A JP 2002306589 A JP2002306589 A JP 2002306589A JP 2001117003 A JP2001117003 A JP 2001117003A JP 2001117003 A JP2001117003 A JP 2001117003A JP 2002306589 A JP2002306589 A JP 2002306589A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive composition
- tacky adhesive
- composition
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 46
- 239000000853 adhesive Substances 0.000 title claims abstract description 31
- 239000002390 adhesive tape Substances 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 20
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 239000007933 dermal patch Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 9
- 230000001954 sterilising effect Effects 0.000 description 9
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 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
- 238000004132 cross linking Methods 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 206010040880 Skin irritation Diseases 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003505 polymerization initiator 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
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 239000003431 cross linking reagent Substances 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
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-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
- 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
- 230000032683 aging Effects 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
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 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
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000000622 irritating effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 231100000344 non-irritating Toxicity 0.000 description 2
- 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
- 230000009467 reduction Effects 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
- 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
- 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
- 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
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 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
- 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
- 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
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester 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
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 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
- 239000000123 paper Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Abstract
Description
【０００１】[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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical pressure-sensitive adhesive composition used for application to the skin in the field of medical hygiene, and a pressure-sensitive adhesive tape or sheet using this composition.
【０００２】[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。2. Description of the Related Art A medical hygiene pressure-sensitive adhesive composition used for application to the skin is usually formed by forming a pressure-sensitive adhesive layer in a layer on one side of a supporting substrate to form a medical or hygienic pressure-sensitive adhesive tape or sheet. Is used by attaching it to the skin surface to which it is to be applied.
【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。[0003] The pressure-sensitive adhesive layer thus formed generally needs to be firmly adhered and fixed to the skin surface, and has a so-called cohesive force in the layer and an anchoring force with a supporting substrate.
It must have excellent adhesive properties.
【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。Further, since it is used for application to the skin, it must be non-irritating to the skin surface to be applied, and must not exert physical pain when peeled from the skin surface to develop skin irritation. It is also required to have skin irritation properties.
【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。[0005] Conventionally, as a medical pressure-sensitive adhesive composition,
An acrylic pressure-sensitive adhesive composition containing alkyl acrylate as a main component and a rubber pressure-sensitive adhesive composition containing a synthetic rubber or a natural rubber as a main component are generally used. 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 allergies caused by proteins as impurities, and the polymerization method, polymerization composition, compounding, etc. Therefore, the study of acrylic pressure-sensitive adhesive compositions that can easily adjust pressure-sensitive adhesive properties has been conducted relatively frequently.
【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。[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. ), There is still much room for improvement, and various studies have actually been made.
【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。[0007] For example, in order to improve the skin adhesion, the amount of copolymerization of an alkyl acrylate having an alkyl group of about 4 to 12 carbon atoms as a skin adhesion-imparting component is increased, or acrylic having a long alkyl chain is used. Attempts have been made to use acid alkyl esters, but on the other hand, a crosslinking treatment of the pressure-sensitive adhesive layer is required because a reduction in the internal cohesion of the pressure-sensitive adhesive layer causes a reduction in the holding power. As a typical crosslinking treatment, a method of adding an external crosslinking agent such as a polyisocyanate, an amine, or an epoxy compound, a method of copolymerizing a crosslinking monomer, and the like are used.
【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。However, the method of crosslinking by adding an external crosslinking agent or the method of copolymerizing a crosslinkable monomer has problems of control of reaction time and pot life, and it is possible to suppress variation in adhesive properties between lots. It is difficult and requires strict management in the manufacturing process.
【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。On the other hand, a pressure-sensitive adhesive composition for medical hygiene and a pressure-sensitive adhesive tape using the same are often affixed to a wound portion, such as an emergency bandage or a dressing material. It is usually sterilized to prevent contamination.
【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。As a sterilization method, a chemical method using an ethylene oxide gas or the like and a physical method using irradiation of ionizing radiation such as an electron beam or γ-ray are generally adopted. Of these methods, sterilization treatment with ionizing radiation is becoming mainstream from the viewpoints of facilities, economy, and legal regulations.
【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。[0011] Sterilization by ionizing radiation is an excellent sterilization method as described above. However, it is also known that when the adhesive is irradiated, the adhesive is cross-linked together with the sterilization. The gel content in the adhesive rises, and as a result,
Adhesive properties such as skin adhesion may decrease. Therefore, in consideration of the decrease in the adhesive properties after ionizing radiation irradiation,
It is also conceivable to adjust the adhesive properties of the adhesive in advance, but if such a method is adopted, the internal cohesive force of the adhesive before irradiation with ionizing radiation is adjusted so as to be low, so during storage The adhesive layer in the adhesive tape flows,
The adhesive may protrude from the side of the tape, that is, the so-called glue may protrude. In addition, the adhesive is attached to a cutting blade used when punching or cutting into a predetermined shape, and the cutting efficiency is reduced. Also occurs.
【００１２】[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。The inventors of the present invention have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, obtained a composition satisfying each required property as a medical hygiene pressure-sensitive adhesive composition. For this reason, a copolymer composition obtained by emulsion polymerization of a specific monomer composition has a small change in the gel fraction in the pressure-sensitive adhesive layer even when irradiated with ionizing radiation, while maintaining pressure-sensitive adhesive properties. They have found that sterilization can be performed, and have completed the present invention.
【００１３】[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であって、
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を提
供するものである。That is, the present invention relates to a method for producing a compound having 5 carbon atoms.
A monomer mixture containing 70 to 99% by weight of a methacrylic acid alkyl ester having an alkyl group of from 15 to 15% by weight and a copolymerizable monomer having a carboxyl group or a hydroxyl group of 1 to 30% by weight is an emulsifier. An emulsion-type pressure-sensitive adhesive composition obtained by copolymerization using:
An object of the present invention is to provide a pressure-sensitive adhesive composition for medical hygiene, wherein the rate of change of the gel fraction before and after irradiation with ionizing radiation is within 30%.
【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。Further, the present invention provides a pressure-sensitive adhesive tape or sheet obtained by forming the above-mentioned pressure-sensitive adhesive composition for medical hygiene in a layer on one surface of a supporting substrate.
【００１５】[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。BEST MODE FOR CARRYING OUT THE INVENTION The adhesive composition for medical hygiene of the present invention comprises an alkyl methacrylate having an alkyl group having 5 to 15 carbon atoms and a copolymerizable monomer having a carboxyl group or a hydroxyl group. It is obtained by emulsion copolymerization of a monomer mixture as a component. When a similar product is prepared by solution polymerization, which is a homogeneous polymerization system, the molecular weight of the obtained copolymer is smaller than that of an emulsion system, and as a result, the adhesiveness to the skin surface is good, but the pressure-sensitive adhesive The internal cohesion of the composition may be insufficient. When an adhesive tape or sheet is produced from the composition obtained by such a solution polymerization system, there is a possibility that an adhesive residue phenomenon occurs when the adhesive tape or sheet is peeled from the skin surface. To achieve this, it is important to carry out emulsion polymerization.
【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。As the methacrylic acid alkyl ester, an alkyl group having 5 to 15 carbon atoms such as an alkyl group such as a pentyl group, a hexyl group, a nonyl group, an octyl group, a decyl group, a dodecyl group (lauryl group) is bonded. These alkyl groups may be linear or branched. In the present invention, particularly preferred alkyl methacrylates are those having an alkyl group having 8 to 14 carbon atoms.
Examples include ethylhexyl, n-octyl methacrylate, lauryl methacrylate, and tetradecyl methacrylate.
【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。Examples of the copolymerizable monomer to be 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. And monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate Is used. In addition,
Pentaerythritol triacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate are polyfunctional monomers having two or more unsaturated double bonds in the molecule, and are used as intramolecular crosslinking agents. It greatly contributes to imparting internal cohesion to the copolymer obtained by the action.
【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。The above-mentioned copolymerizable monomer generally exhibits water-solubility, imparts adhesiveness to the skin surface of the obtained emulsion-type pressure-sensitive adhesive, and has a crosslinking point when irradiated with ionizing radiation. It becomes.
【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７０〜９
９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。In the present invention, a copolymer can be obtained by emulsion-copolymerizing each of the above monomers. The copolymerization amount of each monomer is 70 to 9 of methacrylic acid alkyl ester.
The proportion is adjusted so as to be 9% by weight, preferably 80 to 95% by weight, 1 to 30% by weight, preferably 2 to 25% by weight of the copolymerizable monomer.
【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。When the amount of the copolymerizable monomer is less than 1% by weight, water resistance and sweat resistance when applied to the skin surface are good, but the internal cohesive force in the pressure-sensitive adhesive layer is low. When the content exceeds 30% by weight, the internal cohesive force of the pressure-sensitive adhesive layer increases, but the water resistance and the sweat resistance are reduced when the adhesive layer is applied to the skin surface. On the other hand, when the amount of the alkyl methacrylate is less than 70% by weight, the change rate of the gel fraction before and after the irradiation with the ionizing radiation is 30%.
As described above, there is a possibility that a large change in characteristics occurs, and there is a risk of falling off during application to the skin surface. If the amount is more than 99% by weight, there is a tendency to cause pain or adhesive residue when peeled from the skin surface.
【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。The pressure-sensitive adhesive composition for medical hygiene of the present invention is obtained by emulsion-copolymerizing a mixture of the above-mentioned monomers in the presence of an emulsifier, and if necessary, has 4 to 15 carbon atoms.
Alkyl acrylate having an alkyl group of
Vinyl acetate, acrylonitrile, and the like can be appropriately copolymerized. Specifically, these monomers are preferably contained in the monomer mixture in a range of 5 to 20% by weight.
【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。The pressure-sensitive adhesive composition for medical hygiene of the present invention is intended to suppress the fluctuation of the gel fraction before and after the irradiation of ionizing radiation, which is the object of the present invention, and to suppress the decrease in the skin adhesive force. The gel fraction in the composition is adjusted to 40 to 70% by weight, preferably 45 to 60% by weight. When the gel fraction is too small, the viscosity of the pressure-sensitive adhesive composition increases and the adhesive force increases, and as a result, a phenomenon of adhesive residue on the skin surface or a tendency to increase skin irritation, After the irradiation with ionizing radiation, a large increase in the gel fraction occurs, and if the gel fraction is too large, the elasticity of the pressure-sensitive adhesive composition increases, causing a decrease in the adhesive strength, and as a result, peeling from the skin surface ( Dropout phenomenon).
【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。The gel fraction in the present invention means that a dried sample is immersed in toluene at room temperature for 7 days, and a porous film made of polytetrafluoroethylene having an average pore diameter of 0.2 μm (NTF film manufactured by Nitto Denko Corporation) ) Is a value calculated by a ratio with the dry sample weight before immersion by filtering and drying the toluene-insoluble matter.
【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。In obtaining the pressure-sensitive adhesive composition for medical hygiene of the present invention, a monomer mixture obtained by mixing the above monomers is emulsified in an aqueous medium using an emulsifier to form micelles. Is mixed and heated to start an emulsion polymerization reaction in the micelles, thereby obtaining an emulsion-type pressure-sensitive adhesive composition.
【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。In conducting the emulsion polymerization as described above, a chain transfer agent or a hydrophilic alcohol may be added for the purpose of producing a low molecular weight copolymer and adjusting the overall average molecular weight.
【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。As such a chain transfer agent, it is necessary to use a hydrophobic chain transfer agent in order to capture a radical species in the emulsified monomer mixture and perform chain transfer.
Specifically, a sulfur-based compound such as lauryl mercaptan or thioglycolic acid is used.
【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。As the hydrophilic alcohol, specifically, aliphatic alcohols having 1 to 4 carbon atoms such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol and butyl alcohol can be used. These also dissolve in the aqueous medium during the emulsion polymerization and act as a chain transfer agent.
【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。The emulsifier used in 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 for maintaining a stable emulsion polymerization reaction. , Anionic or nonionic emulsifiers or reactive emulsifiers can be used alone or in combination of two or more. Among these, fatty acid salts, higher alcohol sulfates, sulfosuccinates, and dialkyl sulfosuccinates Such an anionic emulsifier can be suitably used.
【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。The polymerization initiator is necessary for performing emulsion polymerization, and uses a persulfate such as ammonium persulfate or potassium persulfate, or a peroxide such as hydrogen peroxide or benzoyl peroxide. Further, if necessary, a combination of a persulfate and a reducing agent such as a sulfite of an alkali metal or a bisulfite can be used as a redox-based polymerization initiator capable of initiating a polymerization reaction at a low temperature.
【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。Typical amounts of the above components in the above emulsion polymerization are 0.001 to 2 parts by weight of a chain transfer agent and 0.001 to 2 parts by weight of a hydrophilic alcohol per 100 parts by weight of a monomer mixture. 2 parts by weight, emulsifier and polymerization initiator are optional.
【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。If the amount of the chain transfer agent or hydrophilic alcohol is too small, the weight average molecular weight of the obtained copolymer becomes too large, so that the adhesive force as the adhesive property deteriorates.
Lack of polymerization stability may cause the entire reaction system to gel during polymerization, or may cause insufficient adhesion to the skin surface. On the other hand, if the compounding amount is too large, the polymerization average molecular weight of the obtained copolymer is too small, and the cohesive force as the adhesive property is deteriorated, or glue remains on the skin surface, and the skin irritation becomes strong Because of the tendency, it is difficult to exhibit the balance of the adhesive property and the skin non-irritating property.
【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。The polymerization method is not particularly limited as long as the above components can be blended in an aqueous medium and emulsion polymerization can be performed. A batch polymerization method in which the components are reacted in a batch charge or a seed method in which emulsion polymerization is performed in the presence of a seed emulsion (seed). It may be appropriately selected from a polymerization method, a multi-stage polymerization method in which the polymerization reaction is performed stepwise, a power feed polymerization method in which the polymerization reaction is performed by continuously changing the composition ratio of the monomer composition, and the like.
【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２０〜６
５μｍ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。The pressure-sensitive adhesive composition for medical hygiene of the present invention obtained as described above is obtained by forming a pressure-sensitive adhesive composition comprising the above-mentioned composition on one surface of a support substrate in a layered form. It can be. The thickness of the pressure-sensitive adhesive layer to be formed is 15 to 70 μm, preferably 20 to 6 μm.
By setting the thickness to about 5 μm, it is easy to balance skin adhesion and internal cohesion, which is preferable.
【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。As the supporting substrate used for the pressure-sensitive adhesive tape or sheet of the present invention, polyethylene, polypropylene,
Various plastic films such as ethylene / vinyl acetate copolymers and polyesters, woven and nonwoven fabrics, knitted fabrics, papers, metal foils, and laminated films of these plastics can be used.
【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The pressure-sensitive adhesive tape or sheet of the present invention is not limited in its shape as long as it is used for medical applications and sanitary materials, and for example, emergency bandages, rolled bandages, large bandages,
Suitable for dressing materials etc.
【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。The above-mentioned adhesive tape or sheet is
For long products, a release agent such as a silicone resin or a fluororesin is applied to the back of the support base material, and then rolled so that the pressure-sensitive adhesive layer is in contact with the back surface of the support substrate. Is preferably prepared as a sheet material temporarily attached to the surface of the pressure-sensitive adhesive layer.
【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。The pressure-sensitive adhesive composition for medical hygiene and the pressure-sensitive adhesive tape or sheet of the present invention have the above constitutions,
When this is irradiated with ionizing radiation during sterilization, the gel content in the adhesive is less increased, and the adhesive properties are less likely to be reduced. As the ionizing radiation used for such a sterilization treatment, γ-rays, electron beams, X-rays, α-rays, neutron rays, and the like can be used as general radiations. Among them, safety, handling, production, etc. It is preferable to use γ-rays or electron beams from the viewpoint of properties and legal regulations.
【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。The irradiation dose is 20 to 50 kGy, preferably 25 to 35 kGy. In the present invention, the adhesive layer is sterilized by irradiation with ionizing radiation, and is also subjected to a crosslinking treatment. In the pressure-sensitive adhesive composition of the present invention, since a methacrylic acid ester-based emulsion copolymer composed of a specific monomer composition is used, when irradiated with ionizing radiation, a crosslinking reaction occurs. Disruption of the molecular chain occurs in which the main chain of the molecule is cut. Therefore, in the present invention, the increase in the gel fraction in the pressure-sensitive adhesive is suppressed even when irradiation with ionizing radiation is performed.
【００３９】[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。Since the pressure-sensitive adhesive composition for medical hygiene of the present invention has the above constitution, it is formed into a layer on one surface of a supporting substrate, and when used as a pressure-sensitive adhesive tape or sheet, is applied to the skin surface. It is less irritating and is especially useful for long-term application. Furthermore, when sterilization is performed by irradiating ionizing radiation such as an electron beam or γ-ray, the change in the gel fraction of the pressure-sensitive adhesive layer before and after irradiation is small, the change rate is within 30%, and the change in the adhesive properties is remarkable. Less.
【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。Further, it has an excellent balance of skin adhesive strength, holding power, and anchoring power as adhesive properties, does not have peeling-off during use or adhesive residue at the time of peeling, and is suitable for dressing materials, bandages, emergency bandages, etc. Pressure-sensitive adhesive tapes and sheets that are most suitable for the above applications.
【００４１】[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。EXAMPLES Examples of the present invention will be described below in more detail, but the present invention is not limited thereto, and various applications can be made without departing from the technical concept of the present invention. It is possible.
【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。Example 1 An anionic emulsifier (trade name: Hytenol N-17, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a monomer mixture consisting of 800 g of 2-ethylhexyl methacrylate, 20 g of acrylic acid, and 200 g of 2-ethylhexyl acrylate. 800 g of an aqueous solution having an effective concentration of 1% by weight) was added, and the mixture was stirred and emulsified for 15 minutes using a high-speed homomixer (manufactured by Tokushu Kikai Co., Ltd.) under an inert gas atmosphere, and heated to 70 ° C. while stirring was continued.
【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。Next, 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 an emulsion polymerization reaction, and the reaction was continued for about 5 hours. after that,
The temperature was raised to 85 ° C., and an aging 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】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２０
０ｇ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。Example 2 As a monomer mixture, 800 g of lauryl methacrylate,
20 g of acrylic acid, 2-ethylhexyl acrylate 20
A pressure-sensitive adhesive composition for medical hygiene of the present invention was obtained in the same manner as in Example 1 except that 0 g was used.
【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８００
ｇ、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。Example 3 As a monomer mixture, n-octyl methacrylate 800 was used.
g, 20 g of acrylic acid, and 200 g of 2-ethylhexyl acrylate were used to obtain a medical hygiene pressure-sensitive adhesive composition of the present invention in the same manner as in Example 1.
【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９
２０ｇ、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。Comparative Example 1 As a monomer mixture, 2-ethylhexyl acrylate 9
A medical hygiene pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that 20 g and 20 g of acrylic acid were used.
【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２００
ｇ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。Comparative Example 2 As a monomer mixture, 800 g of lauryl acrylate, 20 g of acrylic acid, and 200 g of 2-ethylhexyl acrylate were used.
A pressure-sensitive adhesive composition for medical hygiene was obtained in the same manner as in Example 1 except that g was used.
【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４０
０ｇ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。Comparative Example 3 As a monomer mixture, 600 g of lauryl methacrylate,
20 g of acrylic acid, 2-ethylhexyl acrylate 40
A medical hygiene adhesive composition was obtained in the same manner as in Example 1 except that 0 g was used.
【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２
４時間熟成を行い、粘着テープを作製した。The adhesive composition for medical use 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 50 ° C for 2 minutes.
After aging for 4 hours, an adhesive tape was prepared.
【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。As a sample for measuring the gel fraction,
The pressure-sensitive adhesive composition obtained in each of Examples and Comparative Examples was applied to a release film under the same conditions as described above, and dried to form a pressure-sensitive adhesive layer.
【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。Each of the pressure-sensitive adhesive tapes obtained as described above was irradiated with an electron beam under the following conditions. <Irradiation conditions> One adhesive tape (7.5 cm × 20 cm) was placed side by side on one irradiation cart, and a voltage of 4.
The electron beam was irradiated at an irradiation dose of 25 kGy under the conditions of 8 MV, current of 20.0 mA, and bogie speed of 14.0 m / min.
【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。Next, the adhesive force, the gel fraction, and the rate of change of the gel fraction of the pressure-sensitive adhesive tape before and after the irradiation with the electron beam were measured by the following methods, and the results are shown in Table 1. did.
【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。<Adhesive Strength> The adhesive tape was cut into a width of 20 mm, and was cut at 23 ° C. and 65% RH. H. The pressure-sensitive adhesive layer is press-bonded to a bakelite plate at 2 kg / cm 2 in an atmosphere of 30 minutes, and after 30 minutes of pressure-bonding, the pressure-sensitive adhesive tape is peeled off at a peeling speed of 300 mm / min by 180 degrees and the peeling stress at that time is bonded. Power.
【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。<Gel Fraction> A predetermined amount of the pressure-sensitive adhesive was sampled from the release film on which the pressure-sensitive adhesive layer was formed, weighed, and its weight (W 0 ) was measured. Next, the residue was immersed in toluene at 23 ° C. for 7 days to extract soluble components, and the residue (toluene-insoluble component: gel component) was subjected to polytetrafluoroethylene porous membrane (average pore diameter 0.2 μm, manufactured by Nitto Denko Corporation). , NTF membrane), dried at 120 ° C. for 2 hours, and measured for weight (W 1 ). The W 1 measured as described above is divided by W 0, to calculate the weight of insolubles to the initial weight as the gel fraction (%).
【００５５】[0055]
【表１】 [Table 1]
【００５６】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。As is clear from the results shown in Table 1, the adhesive strength and the gel fraction of the example product hardly changed before and after the irradiation with the electron beam.
Since the rate of change of the gel fraction was large, a clear decrease in the adhesive strength was observed.
Claims (4)
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
粘着剤組成物であって、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。1. An essential component comprising 70 to 99% by weight of an alkyl methacrylate 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. An emulsion-type pressure-sensitive adhesive composition obtained by copolymerizing a monomer mixture with an emulsifier, wherein the rate of change in gel fraction before and after irradiation with ionizing radiation is within 30%. Hygiene adhesive composition.
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％の範囲で含有する請求項１記載の医療衛生用粘着
剤組成物。2. An acrylic acid alkyl ester having an alkyl group having 4 to 15 carbon atoms in a monomer mixture is used in an amount of 5 to 20.
The pressure-sensitive adhesive composition for medical use according to claim 1, which is contained in a range of weight%.
率が４０〜７０重量％である請求項１記載の医療衛生用
粘着剤組成物。3. The pressure-sensitive adhesive composition for medical hygiene according to claim 1, wherein the gel fraction in the pressure-sensitive adhesive before ionizing radiation irradiation is 40 to 70% by weight.
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。4. A pressure-sensitive adhesive tape or sheet comprising the pressure-sensitive adhesive composition for medical hygiene according to claim 1 formed in a layer on one surface of a support substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002306589A true JP2002306589A (en) | 2002-10-22 |
| JP4727839B2 JP4727839B2 (en) | 2011-07-20 |
Family
ID=18967644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001117003A Expired - Lifetime JP4727839B2 (en) | 2001-04-16 | 2001-04-16 | Medical hygiene pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet using the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4727839B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015112663A1 (en) * | 2014-01-22 | 2015-07-30 | Adhesives Research, Inc. | Gamma resistant adhesives |
Families Citing this family (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 |
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 |
|---|---|---|---|---|
| WO2015112663A1 (en) * | 2014-01-22 | 2015-07-30 | Adhesives Research, Inc. | Gamma resistant adhesives |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4727839B2 (en) | 2011-07-20 |
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