JP2016069480A - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP2016069480A JP2016069480A JP2014199028A JP2014199028A JP2016069480A JP 2016069480 A JP2016069480 A JP 2016069480A JP 2014199028 A JP2014199028 A JP 2014199028A JP 2014199028 A JP2014199028 A JP 2014199028A JP 2016069480 A JP2016069480 A JP 2016069480A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- pressure
- sensitive adhesive
- adhesive composition
- monomer
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 55
- 239000000853 adhesive Substances 0.000 title claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 58
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 11
- 230000035699 permeability Effects 0.000 claims description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- WYMSBXTXOHUIGT-UHFFFAOYSA-N paraoxon Chemical compound CCOP(=O)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 WYMSBXTXOHUIGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 239000002994 raw material Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- -1 polyoxyethylene lauryl ether Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 206010040880 Skin irritation Diseases 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000036556 skin irritation Effects 0.000 description 4
- 231100000475 skin irritation Toxicity 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- 239000003655 absorption accelerator Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- DGPVNNMFVYYVDF-UHFFFAOYSA-N 1-prop-2-enoylpyrrolidin-2-one Chemical compound C=CC(=O)N1CCCC1=O DGPVNNMFVYYVDF-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ZTJNPDLOIVDEEL-UHFFFAOYSA-N 2-acetyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(C)=O ZTJNPDLOIVDEEL-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
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010012335 Dependence Diseases 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229960001889 buprenorphine hydrochloride Drugs 0.000 description 1
- UAIXRPCCYXNJMQ-RZIPZOSSSA-N buprenorphine hydrochlorie Chemical compound [Cl-].C([C@]12[C@H]3OC=4C(O)=CC=C(C2=4)C[C@@H]2[C@]11CC[C@]3([C@H](C1)[C@](C)(O)C(C)(C)C)OC)C[NH+]2CC1CC1 UAIXRPCCYXNJMQ-RZIPZOSSSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000000245 forearm Anatomy 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 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
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VOKSWYLNZZRQPF-GDIGMMSISA-N pentazocine Chemical compound C1C2=CC=C(O)C=C2[C@@]2(C)[C@@H](C)[C@@H]1N(CC=C(C)C)CC2 VOKSWYLNZZRQPF-GDIGMMSISA-N 0.000 description 1
- 229960005301 pentazocine Drugs 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Abstract
Description
本発明は、特に対人用に適した粘着剤組成物に関する。 The present invention relates to a pressure-sensitive adhesive composition particularly suitable for interpersonal use.
サージカルテープ、ドレッシング材、絆創膏、更には薬剤を含有する貼付剤にて使用される対人用粘着剤組成物として、各種粘着剤組成物が提案されている。 Various pressure-sensitive adhesive compositions have been proposed as a personal pressure-sensitive adhesive composition used in surgical tapes, dressing materials, adhesive plasters, and patches containing drugs.
まず、特許文献１には、（メタ）アクリル酸アルキルエステルを主成分とする単量体組成物をラジカルが発生する開始剤の存在下で溶液重合するにあたり、重合系の溶存酸素量が飽和率５％以下の状態で重合することにより得られた医療用粘着剤が提案されている。 First, in Patent Document 1, in solution polymerization of a monomer composition mainly composed of (meth) acrylic acid alkyl ester in the presence of an initiator that generates radicals, the amount of dissolved oxygen in the polymerization system is the saturation rate. A medical pressure-sensitive adhesive obtained by polymerization in a state of 5% or less has been proposed.
更に、特許文献２には、支持体層の一面に、粘着剤、薬物及び経皮吸収促進剤からなる粘着剤層が積層されてなる経皮吸収貼付剤であって、上記薬物がペンタゾシン、臭化水素酸エプタゾシン及び塩酸ブプレノルフィンよりなる群から選ばれた一種以上の鎮痛作用を有する化合物であり、上記経皮吸収促進剤がオキシエチレン鎖数６〜１２のポリオキシエチレンラウリルエ−テル、炭素数２〜８の、ヒドロキシカルボン酸及びジカルボン酸よりなる群から選ばれる一種以上である経皮吸収貼付剤が提案されている。 Further, Patent Document 2 discloses a transdermal absorption patch in which a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive, a drug, and a transdermal absorption accelerator is laminated on one surface of a support layer, wherein the drug is pentazocine, odor It is a compound having one or more analgesic action selected from the group consisting of eptazosin hydride and buprenorphine hydrochloride, wherein the percutaneous absorption accelerator is a polyoxyethylene lauryl ether having 6 to 12 oxyethylene chains, and a carbon number 2 to 8 percutaneous absorption patches that are one or more selected from the group consisting of hydroxycarboxylic acids and dicarboxylic acids have been proposed.
更に、特許文献３には、分子内にアセトアセチル基を有する（メタ）アクリル系モノマーと、アセトアセチル基を有しないその他の（メタ）アクリル系モノマー又は共重合可能なビニルモノマーの１種又は２種以上のモノマーとを共重合して得られる共重合体を、非水性溶媒中に含む医療用経皮吸収テープ製剤用非水性粘着剤が提案されている。 Furthermore, Patent Document 3 discloses that one or two of a (meth) acrylic monomer having an acetoacetyl group in the molecule and another (meth) acrylic monomer having no acetoacetyl group or a copolymerizable vinyl monomer. There has been proposed a non-aqueous pressure-sensitive adhesive for medical transdermal absorption tape preparations containing a copolymer obtained by copolymerization with a monomer or more in a non-aqueous solvent.
更に、特許文献４には、（メタ) アクリル酸アルキルエステル４０〜９９モル％とビニルピロリドン６０〜１モル％とからなる共重合体を主成分とする医療用粘着剤であって、上記粘着剤の５重量％酢酸エチル溶液の６６０ｎｍにおける吸光度が０．０３以下である医療用粘着剤が提案されている。 Further, Patent Document 4 discloses a medical pressure-sensitive adhesive mainly comprising a copolymer composed of 40 to 99 mol% of (meth) acrylic acid alkyl ester and 60 to 1 mol% of vinylpyrrolidone, the pressure-sensitive adhesive. A medical pressure-sensitive adhesive in which the absorbance at 660 nm of a 5 wt% ethyl acetate solution is 0.03 or less has been proposed.
更に、特許文献５には、粘着性基剤に薬剤を相溶状態で含有させてなる粘着性基剤層が柔軟で薬剤を透過させない支持体上に形成され、該粘着性基材が２−エチルヘキシルアクリレート（ＥＨＡ）を４５モル％以上、Ｎ−ビニル−２−ピロリドン（ＶＰ）２０〜５５モル％、エステル部分の炭素数が３〜１２でホモポリマーのＴｇが−４０℃以下の（メタ）アクリル酸エステルを３５モル％以下、そして多官能性モノマーを全モノマー重量の０．００５〜０．５重量％の割合で含有するモノマーの重合体である経皮投与型テープ状医薬品が提案されている。 Furthermore, Patent Document 5 discloses that an adhesive base layer formed by adding a drug in a compatible state to an adhesive base is formed on a support that is flexible and does not allow the drug to permeate. (Meth) having 45 mol% or more of ethylhexyl acrylate (EHA), 20 to 55 mol% of N-vinyl-2-pyrrolidone (VP), 3 to 12 carbon atoms in the ester moiety, and Tg of the homopolymer of -40 ° C or lower There has been proposed a transdermal tape-type pharmaceutical product which is a polymer of a monomer containing an acrylic ester of 35 mol% or less and a polyfunctional monomer in a proportion of 0.005 to 0.5% by weight of the total monomer weight. Yes.
更に、特許文献６には、以下の成分（ａ）〜（ｃ）、即ち、（ａ）（メタ）アクリル酸アルキルエステル、（ｂ）アセトアセチル基を含有するビニルモノマー、（ｃ）アルコキシル基含有モノマー、カルボン酸ビニルエステル類、ビニルエーテル類、窒素原子含有の複素環を有するビニルモノマー（但し、アセトアセチル基を含有するものを除く）、スチレン誘導体からなる群から選ばれる少なくとも１種の（ａ）及び（ｂ）と共重合可能なビニルモノマー、を共重合成分として有する共重合体の架橋物を含有してなる粘着剤が提案されている。 Furthermore, Patent Document 6 includes the following components (a) to (c), that is, (a) (meth) acrylic acid alkyl ester, (b) a vinyl monomer containing an acetoacetyl group, and (c) an alkoxyl group containing At least one selected from the group consisting of monomers, carboxylic acid vinyl esters, vinyl ethers, vinyl monomers having a nitrogen atom-containing heterocyclic ring (excluding those containing an acetoacetyl group), and styrene derivatives And a pressure-sensitive adhesive containing a crosslinked product of a copolymer having a vinyl monomer copolymerizable with (b) as a copolymerization component.
更に、特許文献７には、（１）架橋可能なアクリル系共重合体１００重量部、（２）前記アクリル系共重合体（１）と相溶する、分子量８００以上であり疎水性パラメーターが−２０以上４５以下である室温で液状もしくはペースト状の可塑剤２０〜２００重量部、及び（３）架橋剤０．１〜２．０重量部とからなる皮膚用粘着剤組成物が提案されている。 Further, in Patent Document 7, (1) 100 parts by weight of a crosslinkable acrylic copolymer, (2) a molecular weight of 800 or more and a hydrophobic parameter compatible with the acrylic copolymer (1) are − A skin pressure-sensitive adhesive composition comprising 20 to 200 parts by weight of a liquid or paste plasticizer at room temperature of 20 to 45 and (3) 0.1 to 2.0 parts by weight of a crosslinking agent has been proposed. .
更に、特許文献８には、フィルムの片面に、ポリエステル系ポリウレタン樹脂を含んでなるプライマー層を有するものである経皮吸収型製剤用基材シートが提案されている。 Further, Patent Document 8 proposes a substrate sheet for a percutaneous absorption type drug product having a primer layer containing a polyester polyurethane resin on one side of a film.
更に、特許文献９には、担持フィルムの一方の面にエラストマーフィルムを有し、該エラストマーフィルムの上に粘着剤層が設けられた粘着シートであって、該粘着剤層とは反対側の最外層に凹凸が形成されており、前記担持フィルムの加熱収縮率が、縦方向で３．０％以下であり、横方向で１．２％未満であることを特徴とする粘着シートが提案されている。 Further, Patent Document 9 discloses a pressure-sensitive adhesive sheet having an elastomer film on one surface of a carrier film, and having a pressure-sensitive adhesive layer provided on the elastomer film, on the opposite side of the pressure-sensitive adhesive layer. A pressure-sensitive adhesive sheet is proposed in which irregularities are formed on the outer layer, and the heat shrinkage rate of the support film is 3.0% or less in the vertical direction and less than 1.2% in the horizontal direction. Yes.
これらの内、いくつかの技術は、後架橋に係る粘着剤に関するものである。粘着剤の後架橋は、架橋剤の添加量で特性の調節が可能であるが、ポットライフの発生や官能基の導入が必須であり、熟成期間・設備も必要となる。対人用途では皮膚刺激の原因になることもあり、活性水素とも反応しやすいため、添加物の選択が必要となることもある。他方、従来の架橋剤を用いない粘着剤（非後架橋型粘着剤）は、糊残りをしないように、粘着剤自体の凝集力の向上を図っているが、凝集力が高いと皮膚への付きは悪化する。凝集力が低いと、皮膚への付きは上がるが剥離時に糊残りを起こす。皮膚への付きがよいと剥離時に痛みを伴うこともある。また、上記の内、いくつかの技術は、透湿度が低いために皮膚と粘着剤の間に水分が溜まり、皮膚刺激や粘着力低下を招くことがある。 Among these, some techniques relate to pressure-sensitive adhesives related to post-crosslinking. In the post-crosslinking of the pressure-sensitive adhesive, the characteristics can be adjusted by the addition amount of the cross-linking agent, but generation of pot life and introduction of functional groups are essential, and an aging period and equipment are also required. In personal use, it may cause skin irritation and may easily react with active hydrogen, so it may be necessary to select an additive. On the other hand, pressure-sensitive adhesives that do not use conventional crosslinking agents (non-post-crosslinking type pressure-sensitive adhesives) attempt to improve the cohesive strength of the pressure-sensitive adhesive itself so as not to leave adhesive residue. Addiction gets worse. If the cohesive strength is low, the adhesion to the skin will rise, but it will cause adhesive residue at the time of peeling. Good skin contact may be painful at the time of peeling. In addition, among the above techniques, some techniques may cause moisture irritation between the skin and the pressure-sensitive adhesive due to low moisture permeability, leading to skin irritation and reduced adhesive strength.
以上のように、対人用粘着剤組成物として最適なものが存在しないのが現状である。よって、本発明は、糊残りしないにも関わらず良好な皮膚粘着力と剥離時の痛みの小ささを両立し、更に充分な透湿度を発現する粘着剤組成物を提供することを課題とする。 As described above, there is no optimal adhesive composition for personal use at present. Therefore, an object of the present invention is to provide a pressure-sensitive adhesive composition that achieves both good skin adhesive strength and low pain at the time of peeling, and exhibits sufficient moisture permeability even though no adhesive remains. .
本発明（１）は、
以下の成分（ａ）〜（ｅ）を含有するモノマー組成物を共重合させることにより得られた共重合体を含有する粘着剤組成物である。
（ａ）（メタ）アクリル酸アルキルエステル ４０〜６８質量％
（ｂ）アルコキシ基含有（メタ）アクリル酸エステル ２５〜４５質量％
（ｃ）エチレン性不飽和二重結合を有する窒素含有モノマー ６〜１５質量％
（ｄ）エチレン性不飽和二重結合を有するカルボキシル基含有モノマー ０．５〜５質量％
（ｅ）エチレン性不飽和二重結合を複数有する多官能モノマー ０．００５〜０．１質量％
本発明（２）は、可塑剤の含有量が、前記粘着剤組成物の全質量を基準として１０質量％未満である、前記（１）の粘着剤組成物である。
本発明（３）は、固形分３０質量％のとき、粘着剤温度３０℃にてローター回転数１０ｒｐｍでの溶液粘度が３１００ｍＰａ・ｓ以上である、前記（１）又は（２）の粘着剤組成物である。
本発明（４）は、１時間貼付での皮膚粘着力が０．５Ｎ／１５ｍｍ以上である、前記（１）〜（３）のいずれか一つの粘着剤組成物である。
本発明（５）は、３０μｍの厚みにおける透湿度が１２００ｇ／ｍ２・２４ｈ以上である、前記（１）〜（４）のいずれか一つの粘着剤組成物である。
本発明（６）は、（ｃ）成分が、Ｎ−ビニル−２−ピロリドン及びＮ−イソプロピルアクリルアミドから選択される一種以上である、前記発明（１）〜（５）のいずれか一つの粘着剤組成物である。
本発明（７）は、サージカルテープ、ドレッシング材及び絆創膏から選択される貼付材用である、前記発明（１）〜（６）のいずれか一つの粘着剤組成物である。
本発明（８）は、貼付剤用である、前記発明（１）〜（６）のいずれか一つの粘着剤組成物である。
本発明（９）は、前記発明（１）〜（６）のいずれか一つの粘着剤組成物層が基材上に設けられている、サージカルテープ、ドレッシング材及び絆創膏から選択される貼付材である。
本発明（１０）は、前記発明（１）〜（６）のいずれか一つの粘着剤組成物が基材上に設けられている貼付剤である。
The present invention (1)
It is an adhesive composition containing a copolymer obtained by copolymerizing a monomer composition containing the following components (a) to (e).
(A) (meth) acrylic acid alkyl ester 40-68 mass%
(B) Alkoxy group-containing (meth) acrylic acid ester 25 to 45% by mass
(C) Nitrogen-containing monomer having an ethylenically unsaturated double bond 6 to 15% by mass
(D) Carboxyl group-containing monomer having an ethylenically unsaturated double bond 0.5 to 5% by mass
(E) Polyfunctional monomer having a plurality of ethylenically unsaturated double bonds 0.005 to 0.1% by mass
This invention (2) is an adhesive composition of said (1) whose content of a plasticizer is less than 10 mass% on the basis of the total mass of the said adhesive composition.
In the present invention (3), when the solid content is 30% by mass, the solution viscosity at a rotor temperature of 10 rpm at an adhesive temperature of 30 ° C. is 3100 mPa · s or more. It is a thing.
The present invention (4) is the pressure-sensitive adhesive composition according to any one of the above (1) to (3), wherein the skin adhesive strength when applied for 1 hour is 0.5 N / 15 mm or more.
The present invention (5) is the pressure-sensitive adhesive composition according to any one of (1) to (4), wherein the moisture permeability at a thickness of 30 μm is 1200 g / m 2 · 24 h or more.
The present invention (6) is the pressure-sensitive adhesive according to any one of the inventions (1) to (5), wherein the component (c) is one or more selected from N-vinyl-2-pyrrolidone and N-isopropylacrylamide. It is a composition.
The present invention (7) is the pressure-sensitive adhesive composition according to any one of the inventions (1) to (6), which is used for a patch selected from a surgical tape, a dressing material and a bandage.
The present invention (8) is the pressure-sensitive adhesive composition according to any one of the inventions (1) to (6), which is for a patch.
The present invention (9) is a patch selected from surgical tape, dressing material and adhesive bandage, wherein the pressure-sensitive adhesive composition layer according to any one of the inventions (1) to (6) is provided on a substrate. .
This invention (10) is a patch in which any one adhesive composition of said invention (1)-(6) is provided on the base material.
本発明によれば、糊残りしないにも関わらず良好な皮膚粘着力と剥離時の痛みの小ささを両立し、更に充分な透湿度を発現する粘着剤組成物を提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the adhesive composition which balances favorable skin adhesive force and the small pain at the time of peeling, and expresses sufficient moisture permeability, although it does not remain glue. .
以下、本発明に係る粘着剤組成物の原料、当該粘着剤組成物の製造方法、当該粘着剤組成物の物性、当該粘着剤組成物の用途について詳述する。 Hereinafter, the raw material of the pressure-sensitive adhesive composition according to the present invention, the method for producing the pressure-sensitive adhesive composition, the physical properties of the pressure-sensitive adhesive composition, and the use of the pressure-sensitive adhesive composition will be described in detail.
≪粘着剤組成物の原料≫
本発明に係る粘着剤組成物は、以下の成分（ａ）〜（ｅ）を含有するモノマー組成物を共重合させることにより得られた共重合体を含有する粘着剤組成物である。
（ａ）（メタ）アクリル酸アルキルエステル ４０〜６８質量％
（ｂ）アルコキシ基含有（メタ）アクリル酸エステル ２５〜４５質量％
（ｃ）エチレン性不飽和二重結合を有する窒素含有モノマー ６〜１５質量％
（ｄ）エチレン性不飽和二重結合を有するカルボキシル基含有モノマー ０．５〜５質量％
（ｅ）エチレン性不飽和二重結合を複数有する多官能モノマー ０．００５〜０．１質量％
≪Raw material of adhesive composition≫
The pressure-sensitive adhesive composition according to the present invention is a pressure-sensitive adhesive composition containing a copolymer obtained by copolymerizing a monomer composition containing the following components (a) to (e).
(A) (meth) acrylic acid alkyl ester 40-68 mass%
(B) Alkoxy group-containing (meth) acrylic acid ester 25 to 45% by mass
(C) Nitrogen-containing monomer having an ethylenically unsaturated double bond 6 to 15% by mass
(D) Carboxyl group-containing monomer having an ethylenically unsaturated double bond 0.5 to 5% by mass
(E) Polyfunctional monomer having a plurality of ethylenically unsaturated double bonds 0.005 to 0.1% by mass
＜モノマー原料（ａ）＞
まず、原料（ａ）である（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ)アクリロイル基以外の炭素数が２〜１４の（メタ）アクリル酸アルキルエステルを挙げることができ、（メタ）アクリル酸アルキルエステルの具体例としては、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸ｎ−オクチル、アクリル酸イソオクチル、アクリル酸イソノニル、アクリル酸デシル、アクリル酸ドデシル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ｎ−オクチル、メタクリル酸イソオクチル、メタクリル酸イソノニル、メタクリル酸デシル、メタクリル酸ドデシル等が挙げられる。これらの中でも、アクリル酸２−エチルヘキシルが好ましい。これらの（メタ）アクリル酸アルキルエステルは、それぞれ単独で、或いは２種以上を組み合わせて使用することができる。
<Monomer raw material (a)>
First, examples of the (meth) acrylic acid alkyl ester as the raw material (a) include (meth) acrylic acid alkyl esters having 2 to 14 carbon atoms other than the (meth) acryloyl group. Specific examples of the alkyl acrylate ester include n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, decyl acrylate, Examples include dodecyl acrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate, and the like. It is done. Among these, 2-ethylhexyl acrylate is preferable. These alkyl (meth) acrylates can be used alone or in combination of two or more.
＜モノマー原料（ｂ）＞
次に、原料（ｂ）であるアルコキシ基含有（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸２−プロポキシエチル、（メタ）アクリル酸３−プロポキシエチル、（メタ）アクリル酸２−ブトキシエチル等を挙げることができる。これらの中でも、（メタ）アクリル酸２−メトキシエチルが好ましい。これらのアルコキシ基含有（メタ）アクリル酸エステルは、それぞれ単独で、或いは２種以上を組み合わせて使用することができる。
<Monomer raw material (b)>
Next, as the alkoxy group-containing (meth) acrylic acid ester as the raw material (b), for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylic acid 2- Examples include propoxyethyl, 3-propoxyethyl (meth) acrylate, and 2-butoxyethyl (meth) acrylate. Among these, 2-methoxyethyl (meth) acrylate is preferable. These alkoxy group-containing (meth) acrylic acid esters can be used alone or in combination of two or more.
＜モノマー原料（ｃ）＞
次に、原料（ｃ）であるエチレン性不飽和二重結合を有する窒素含有モノマーは、エチレン性不飽和二重結合を有しており、且つ、窒素原子を分子内に有している化合物であれば特に限定されないが、その具体的なモノマーとして、アクリロイルモルホリン、Ｎ−ビニル−２−ピロリドン、シクロヘキシルマレイミド、フェニルマレイミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−アクリロイルピロリドン、Ｎ−アクリロイルピベリジン、Ｎ−アクリロイルピロリジン等が挙げられる。これらの中でも、Ｎ−ビニル−２−ピロリドン及びＮ−イソプロピルアクリルアミドが好ましい。これらのエチレン性不飽和二重結合を有する窒素含有モノマーは、それぞれ単独で、或いは２種以上を組み合わせて使用することができる。
<Monomer raw material (c)>
Next, the nitrogen-containing monomer having an ethylenically unsaturated double bond as the raw material (c) is a compound having an ethylenically unsaturated double bond and having a nitrogen atom in the molecule. The specific monomer is not particularly limited as long as the monomer includes acryloylmorpholine, N-vinyl-2-pyrrolidone, cyclohexylmaleimide, phenylmaleimide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-acryloylpyrrolidone, N-acryloylpiberidine, N-acryloylpyrrolidine and the like can be mentioned. Among these, N-vinyl-2-pyrrolidone and N-isopropylacrylamide are preferable. These nitrogen-containing monomers having an ethylenically unsaturated double bond can be used alone or in combination of two or more.
＜モノマー原料（ｄ）＞
次に、原料（ｄ）であるエチレン性不飽和二重結合を有するカルボキシル基含有モノマーとしては、エチレン性不飽和二重結合を有しており、且つ、カルボキシル基を有している化合物であれば特に限定されないが、好適には、（メタ）アクリル酸、イタコン酸、カルボキシエチルアクリレート等を挙げることができる。これらの中でも、アクリル酸、カルボキシエチルアクリレートが好ましい。これらのエチレン性不飽和二重結合を有するカルボキシル基含有モノマーは、それぞれ単独で、或いは２種以上を組み合わせて使用することができる。
<Monomer raw material (d)>
Next, the carboxyl group-containing monomer having an ethylenically unsaturated double bond as the raw material (d) may be a compound having an ethylenically unsaturated double bond and having a carboxyl group. Although not particularly limited, (meth) acrylic acid, itaconic acid, carboxyethyl acrylate, and the like can be preferably used. Among these, acrylic acid and carboxyethyl acrylate are preferable. These carboxyl group-containing monomers having an ethylenically unsaturated double bond can be used alone or in combination of two or more.
＜モノマー原料（ｅ）＞
次に、原料（ｅ）であるエチレン性不飽和二重結合を複数有する多官能モノマーとしては、例えば、分子中にビニル基、アクリロイル基、メタクリロイル基、ビニルベンジル基を分子中に複数有する成分である限り特に限定されない。ここで、一般には、含まれるエチレン性不飽和二重結合が１０個以下のものが用いられるが、これに限定するものではない。多官能モノマーは２種以上を併用することもできる。好ましく用いうる多官能モノマーの具体例としては、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、テトラエチレングリコールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、１，６−ヘキサンジオールジアクリレート、１，６−ヘキサンジオールジメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ジビニルベンゼン、アクリル酸ビニル、メタクリル酸ビニル、アジピン酸ジビニル、Ｎ，Ｎ'−メチレンビスアクリルアミド等が挙げられる。これらの内、１，６−ヘキサンジオールジアクリレート及びトリメチロールプロパントリアクリレートが特に好適である。
<Monomer raw material (e)>
Next, the polyfunctional monomer having a plurality of ethylenically unsaturated double bonds as the raw material (e) is, for example, a component having a plurality of vinyl groups, acryloyl groups, methacryloyl groups, and vinylbenzyl groups in the molecule. As long as there is no particular limitation. In general, those having 10 or less ethylenically unsaturated double bonds are used, but the present invention is not limited thereto. Two or more polyfunctional monomers can be used in combination. Specific examples of polyfunctional monomers that can be preferably used include diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, and neopentyl. Glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol hexame Acrylate, divinylbenzene, vinyl acrylate, vinyl methacrylate, divinyl adipate, N, N'-methylene bis-acrylamide. Of these, 1,6-hexanediol diacrylate and trimethylolpropane triacrylate are particularly preferred.
＜任意のモノマー成分（ｆ）＞
上記のモノマー成分（ａ）〜（ｅ）は必須であるが、これら以外のモノマー成分を一種以上用いてもよい。例えば、不飽和二重結合を有する化合物、例えば、２−アセトアセトキシエチルメタクリレートを挙げることができる。
<Any monomer component (f)>
Although said monomer component (a)-(e) is essential, you may use 1 or more types of monomer components other than these. For example, a compound having an unsaturated double bond, for example, 2-acetoacetoxyethyl methacrylate can be mentioned.
≪粘着剤組成物の製造方法≫
本発明に係る共重合体は、一般にラジカル重合により合成することができる。重合法としては、溶液重合法、乳化重合法又は塊状重合法等が挙げられるが、良好な粘着特性を得られることから溶液重合法が好ましい。ここで、重合反応は、全単量体成分質量に対して０．１〜１質量％程度の割合でラジカル重合開始剤を加え、窒素気流下、４０から９０℃程度の温度下にて、数時間から数十時間攪拌して重合させる。尚、ここで用いる重合開始剤としては、ベンゾイルパーオキサイド及びラウロイルパーオキサイド等の有機過酸化物、アゾビスイソブチロニトリル等のアゾ系開始剤等が挙げられる。
≪Method for producing pressure-sensitive adhesive composition≫
The copolymer according to the present invention can generally be synthesized by radical polymerization. Examples of the polymerization method include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and the like, but a solution polymerization method is preferable because good adhesive properties can be obtained. Here, the polymerization reaction is carried out by adding a radical polymerization initiator at a rate of about 0.1 to 1% by mass with respect to the total monomer component mass, and at a temperature of about 40 to 90 ° C. under a nitrogen stream. The polymerization is carried out with stirring for several tens of hours. Examples of the polymerization initiator used here include organic peroxides such as benzoyl peroxide and lauroyl peroxide, and azo initiators such as azobisisobutyronitrile.
この際、原料モノマー成分（ａ）〜（ｅ）の配合量は、全モノマー成分の総質量を基準として、モノマー成分（ａ）が４０〜６８質量％（好適には４５〜６０質量％）、モノマー成分（ｂ）が２５〜４５質量％（好適には２９〜４５質量％）、モノマー成分（ｃ）が６〜１５質量％（好適には７〜１２質量％）、モノマー成分（ｄ）が０．５〜５質量％（好適には２〜４質量％）、モノマー成分（ｅ）が０．００５〜０．１質量％（好適には０．０１〜０．０５質量％）、である。 Under the present circumstances, the compounding quantity of raw material monomer component (a)-(e) is 40-68 mass% (preferably 45-60 mass%) of monomer components (a) on the basis of the total mass of all the monomer components, The monomer component (b) is 25 to 45% by mass (preferably 29 to 45% by mass), the monomer component (c) is 6 to 15% by mass (preferably 7 to 12% by mass), and the monomer component (d) is 0.5 to 5% by mass (preferably 2 to 4% by mass) and the monomer component (e) is 0.005 to 0.1% by mass (preferably 0.01 to 0.05% by mass). .
ここで、本発明に係る粘着剤組成物を製造するに際しては、後架橋を行なわない（非後架橋型）ことが好適である。粘着剤の後架橋は、架橋剤の添加量で特性の調節が可能であるが、ポットライフの発生や官能基の導入が必須であり、熟成期間・設備も必要となるからである。更に、対人用途では皮膚刺激の原因になることもあり、活性水素とも反応しやすいため、添加物の選択が必要となることもあるからである。 Here, in producing the pressure-sensitive adhesive composition according to the present invention, it is preferable not to perform post-crosslinking (non-post-crosslinked type). This is because the post-crosslinking of the pressure-sensitive adhesive can adjust the characteristics by the addition amount of the crosslinking agent, but it is essential to generate pot life and introduce functional groups, and also requires an aging period and equipment. Furthermore, in personal use, it may cause skin irritation, and since it easily reacts with active hydrogen, it may be necessary to select an additive.
加えて、本発明に係る粘着剤組成物は、可塑剤の含有量が、前記粘着剤組成物の全質量を基準として１０質量％未満であることが好適である。可塑剤が１０質量％以上含有されていると粘着剤の凝集力が低下するため、糊残りの可能性が高くなる。 In addition, the pressure-sensitive adhesive composition according to the present invention preferably has a plasticizer content of less than 10% by mass based on the total mass of the pressure-sensitive adhesive composition. When the plasticizer is contained in an amount of 10% by mass or more, the cohesive force of the pressure-sensitive adhesive is reduced, so that the possibility of adhesive residue increases.
≪粘着剤組成物の物性≫
以下、本発明に係る粘着剤組成物の物性を詳述する。
≪Physical properties of adhesive composition≫
Hereinafter, physical properties of the pressure-sensitive adhesive composition according to the present invention will be described in detail.
（溶液粘度）
本発明に係る粘着剤組成物の溶液粘度は、好適には、３１００ｍＰａ・ｓ以上であり、より好適には３３００〜２００００ｍＰａ・ｓであり、更に好適には３５００〜１００００ｍＰａ・ｓである。溶液粘度が低すぎると粘着剤組成物の凝集力がなく、溶液粘度が高すぎると塗工特性上適さない。尚、測定方法は下記の通りである。
測定方法：ブルックフィールド粘度計を用いて、固形分３０％、粘着剤温度３０℃で、１０ｒｐｍの回転数にて測定する。
(Solution viscosity)
The solution viscosity of the pressure-sensitive adhesive composition according to the present invention is preferably 3100 mPa · s or more, more preferably 3300 to 20000 mPa · s, and further preferably 3500 to 10000 mPa · s. If the solution viscosity is too low, there is no cohesive force of the pressure-sensitive adhesive composition, and if the solution viscosity is too high, the coating properties are not suitable. The measuring method is as follows.
Measurement method: Using a Brookfield viscometer, measurement is performed at a rotation rate of 10 rpm at a solid content of 30% and an adhesive temperature of 30 ° C.
（皮膚粘着力）
本発明に係る粘着剤組成物の皮膚粘着力（１時間貼付での皮膚粘着力）は、好適には、０．５Ｎ／１５ｍｍ以上であり、より好適には０．５５〜２．０Ｎ／１５ｍｍであり、更に好適には０．６〜１．５Ｎ／１５ｍｍである。皮膚粘着力が低すぎると貼付中に脱落の危険性があり、皮膚粘着力が高すぎると剥離時に痛みを発現する危険性がある。尚、測定方法は下記の通りである。
測定方法：温度２３℃、相対湿度５０％の雰囲気下、粘着テープ又はシートから幅１５ｍｍ×長さ約９０ｍｍに切り出した試験片を、ヒト前腕内側（掌側）に貼り付け圧着する。６０分経過後に、剥離速度１００ｍｍ／分で試験片を９０°方向に引き剥がし、皮膚粘着力を測定する。
(Skin adhesion)
The skin adhesive strength (skin adhesive strength after 1 hour sticking) of the pressure-sensitive adhesive composition according to the present invention is preferably 0.5 N / 15 mm or more, more preferably 0.55 to 2.0 N / 15 mm. More preferably, it is 0.6 to 1.5 N / 15 mm. If the skin adhesive strength is too low, there is a risk of falling off during application, and if the skin adhesive strength is too high, there is a risk of developing pain upon peeling. The measuring method is as follows.
Measurement method: In an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, a test piece cut out from an adhesive tape or sheet into a width of 15 mm and a length of about 90 mm is attached to the inner side of the human forearm (palm side) and pressure bonded. After 60 minutes, the test piece is peeled off in the 90 ° direction at a peeling speed of 100 mm / min, and the skin adhesive force is measured.
（透湿度）
本発明に係る粘着剤組成物の透湿度（３０μｍ厚における透湿度）は、好適には、１２００ｇ／ｍ２・２４ｈ以上であり、より好適には１３００ｇ／ｍ２・２４ｈ以上である。透湿度が低すぎると、皮膚に貼付した際に発汗や不感蒸泄により、皮膚と粘着剤の間に水分が貯留しムレを引き起こし皮膚刺激や粘着力低下を引き起こす。尚、測定方法は下記の通りである。
測定方法：ＪＩＳ Ｌ １０９９ Ａ-１法（塩化カルシウム法）に準拠し、温度４０℃、相対湿度９０％の雰囲気下にて測定する。
(Moisture permeability)
The moisture permeability (moisture permeability at 30 μm thickness) of the pressure-sensitive adhesive composition according to the present invention is preferably 1200 g / m 2 · 24 h or more, and more preferably 1300 g / m 2 · 24 h or more. If the moisture permeability is too low, moisture may accumulate between the skin and the adhesive due to sweating or insensitive steaming when applied to the skin, causing stuffiness and causing skin irritation and reduced adhesive strength. The measuring method is as follows.
Measuring method: Measured in an atmosphere of a temperature of 40 ° C. and a relative humidity of 90% in accordance with JIS L 1099 A-1 method (calcium chloride method).
（痛み）
本発明に係る粘着剤組成物の剥離時の痛みは、好適には２以下、より好適には１．５以下である。痛みは大きいと苦痛であるため、小さければ小さい程望ましい。尚、測定方法は下記の通りである。
測定方法：皮膚粘着力測定時に感じる痛みを、１．なし、２．軽度、３．中等度、４．高度、５．極度、の５段階の指標を用いて評価する。被験者は２０歳代〜５０歳代の男性又は女性の合計５名で評価し、各々の被験者の評点を平均する。
(pain)
The pain at the time of peeling of the pressure-sensitive adhesive composition according to the present invention is preferably 2 or less, more preferably 1.5 or less. Since pain is painful when it is large, the smaller the pain, the better. The measuring method is as follows.
Measuring method: Pain felt when measuring skin adhesive strength. None Minor, 3. Moderate, 4. Altitude, 5. Evaluation is made using an extreme 5-level index. Subjects are evaluated by a total of five men or women in their 20s to 50s, and the scores of each subject are averaged.
（ボールタック）
本発明に係る粘着剤組成物のボールタックは、好適には、Ｎｏ．２０〜３２であり、より好適にはＮｏ．２５〜３２である。ボールタックは値が大きければ大きいほどタック性が高い。タックが低いと、初期接着力が低く、貼付直後に引っ張りやずれ方向の応力がかかると剥れたりずれたりしやすい。ヒト皮膚に貼付する場合、関節の屈折による引っ張りや、衣服等に擦られることによるずれ方向の応力がかかりやすいため、ボールタックは大きい方が望ましい。尚、測定方法は下記の通りである。
測定方法：ＪＩＳ Ｚ ０２３７のボールタック測定法に準拠し、傾斜角は３０°、温度２３℃、相対湿度５０％の雰囲気下にて測定を行う。
(Ball tack)
The ball tack of the pressure-sensitive adhesive composition according to the present invention is preferably No. 20 to 32, and more preferably No. 25-32. The larger the value of the ball tack, the higher the tackiness. If the tack is low, the initial adhesive strength is low, and if a tensile or misalignment stress is applied immediately after application, it tends to peel off or shift. When affixed to human skin, a larger ball tack is desirable because stress due to refraction of the joints or stress in the direction of displacement due to rubbing against clothes or the like is likely to be applied. The measuring method is as follows.
Measurement method: Based on the ball tack measurement method of JIS Z 0237, the measurement is performed in an atmosphere having an inclination angle of 30 °, a temperature of 23 ° C., and a relative humidity of 50%.
（保持力）
本発明に係る粘着剤組成物の保持力は、好適には、０．４〜２０ｍｍ又は２０分以上であり、より好適には０．６〜２０ｍｍ又は３０分以上であり、更に好適には１．０ｍｍ〜２０ｍｍ以上又は４０分以上である。粘着剤の柔らかさは被着体に対する濡れや凝集力に影響しており、保持力のズレが小さい、つまり粘着剤が硬すぎると被着体への付きが悪く、貼付中に浮いたり脱落したりする危険性がある。一方保持力のズレが大きい、つまり粘着剤が柔らかすぎると被着体にはよく付くが、剥離時に糊残りや痛みを伴う原因となる危険性がある。尚、測定方法は下記の通りである。
測定方法：ＪＩＳ Ｚ ０２３７の保持力測定法に準拠し、被着体はガラス、試料は幅１２ｍｍ、長さ２０ｍｍとし、温度２３℃、相対湿度５０％の雰囲気下にて、５００ｇの重りを吊るしてから６０分後のズレ又は落下するまでの時間を測定する。
(Holding power)
The holding power of the pressure-sensitive adhesive composition according to the present invention is preferably 0.4 to 20 mm or 20 minutes or more, more preferably 0.6 to 20 mm or 30 minutes or more, and further preferably 1 0.0 mm to 20 mm or more or 40 minutes or more. The softness of the adhesive affects the wetness and cohesive strength of the adherend, and the displacement of the holding force is small.In other words, if the adhesive is too hard, it will not stick to the adherend and will float or fall off during application. There is a risk that On the other hand, if the displacement of the holding force is large, that is, the adhesive is too soft, it adheres well to the adherend, but there is a risk of causing adhesive residue or pain at the time of peeling. The measuring method is as follows.
Measuring method: In accordance with the holding power measuring method of JIS Z 0237, the adherend is glass, the sample is 12 mm wide and 20 mm long, and a 500 g weight is suspended in an atmosphere of 23 ° C. and 50% relative humidity. Measure the time until the drop or drop after 60 minutes.
≪粘着剤組成物の用途≫
本発明に係る粘着剤組成物は、サージカルテープ、ドレッシング材及び絆創膏から選択される貼付材用として有用である。この場合、当該貼付材は、当該粘着剤組成物層が基材上に設けられている形態を採る。更に、本発明に係る粘着剤組成物は、貼付剤用としても有用である。ここで、当該用途で用いる場合、当該粘着剤組成物は薬剤を含有する。この場合、当該貼付剤は、当該粘着剤組成物が基材上に設けられている形態を採る。
≪Use of adhesive composition≫
The pressure-sensitive adhesive composition according to the present invention is useful for an adhesive material selected from surgical tape, dressing material and adhesive bandage. In this case, the adhesive material takes a form in which the pressure-sensitive adhesive composition layer is provided on the substrate. Furthermore, the pressure-sensitive adhesive composition according to the present invention is also useful for patches. Here, when using for the said use, the said adhesive composition contains a chemical | medical agent. In this case, the patch takes a form in which the adhesive composition is provided on a substrate.
以下、本発明を、実施例を参照しながら具体的に説明する。但し、本発明は当該実施例に何ら限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples.
≪製造方法≫
（実施例１）
攪拌機、温度計、及び冷却管を装着した１Ｌフラスコにてラジカル重合を行った。２-エチルヘキシルアクリレート５７．９６質量％、メトキシエチルアクリレート３０質量％、Ｎ-ビニル-２-ピロリドン７質量％、アクリル酸４質量％、１，６-ヘキサンジオールジメタクリレート０．０４部、２-アセトアセトキシエチルメタクリレート１質量％を仕込み、溶媒として酢酸エチルを用い、開始剤として有機過酸化物を用いた。昇温し、窒素気流中１８時間攪拌還流下にて重合を行い粘着剤組成物を得た。
得られた前記粘着剤組成物を、シリコーン表面処理したポリエステルフィルム（離型シート）上に乾燥後の厚み３０μｍとなるように塗布し、乾燥して粘着剤層を形成した。次いで、前記粘着剤層の上面に基材（９０μｍ程度の厚みのポリエステル不織布）をラミネートして粘着テープを得た。
（実施例２〜１１及び比較例１〜４）
実施例１と同様の手法にて、表１及び表２の原料及び配合量に基づき、実施例２〜１１及び比較例１〜４に係る粘着剤組成物を調製した。
≪評価≫
実施例１〜１１及び比較例１〜４に係る粘着剤組成物及び当該粘着剤組成物層を有する粘着テープに関し、溶液粘度、皮膚粘着力、痛さ、透湿度、ボールタック、保持力（５００ｇ）を測定した（粘着剤厚は０．０３ｍｍ）。結果を表１及び表２に示す。尚、本実施例に具体的に示したものの他、モノマー成分（ａ）に関しては、４５質量％以上６０質量％以下＞４０質量％以上４５質量％未満又は６０質量％超６８質量％以下＞４０質量％未満又は６８質量％超、の効果順であることが判明した。同様に、モノマー成分（ｂ）に関しては、２９質量％以上４５質量％以下＞２５質量％以上２９質量％未満＞２５質量％未満又は４５質量％超、の効果順であることが判明した。同様に、モノマー成分（ｃ）に関しては、７質量％以上１２質量％以下＞６質量％以上７質量％未満又は１２質量％超１５質量％以下＞６質量％未満又は１５質量％超、の効果順であることが判明した。同様に、モノマー成分（ｄ）に関しては、２質量％以上４質量％以下＞０．５質量％以上２質量％未満又は４質量％超５質量％以下＞０．５質量％未満又は５質量％超、の効果順であることが判明した。同様に、モノマー成分（ｅ）に関しては、０．０１質量％以上０．０５質量％以下＞０．００５質量％以上０．０１質量％未満又は０．０５質量％超０．１質量％以下＞０．００５質量％未満又は０．１質量％超、の効果順であることが判明した。
≪Manufacturing method≫
Example 1
Radical polymerization was performed in a 1 L flask equipped with a stirrer, a thermometer, and a condenser. 2-ethylhexyl acrylate 57.96% by mass, methoxyethyl acrylate 30% by mass, N-vinyl-2-pyrrolidone 7% by mass, acrylic acid 4% by mass, 1,6-hexanediol dimethacrylate 0.04 part, 2-acetate 1% by mass of acetoxyethyl methacrylate was charged, ethyl acetate was used as a solvent, and an organic peroxide was used as an initiator. The temperature was raised and polymerization was carried out under stirring and reflux in a nitrogen stream for 18 hours to obtain a pressure-sensitive adhesive composition.
The obtained pressure-sensitive adhesive composition was applied on a silicone surface-treated polyester film (release sheet) so as to have a thickness of 30 μm after drying, and dried to form a pressure-sensitive adhesive layer. Next, a base material (polyester nonwoven fabric having a thickness of about 90 μm) was laminated on the upper surface of the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive tape.
(Examples 2-11 and Comparative Examples 1-4)
In the same manner as in Example 1, based on the raw materials and blending amounts in Tables 1 and 2, pressure-sensitive adhesive compositions according to Examples 2 to 11 and Comparative Examples 1 to 4 were prepared.
≪Evaluation≫
About the adhesive composition which concerns on Examples 1-11 and Comparative Examples 1-4 and the adhesive tape which has the said adhesive composition layer, solution viscosity, skin adhesive force, pain, moisture permeability, ball tack, holding power (500g ) Was measured (adhesive thickness was 0.03 mm). The results are shown in Tables 1 and 2. In addition to what is specifically shown in this example, the monomer component (a) is 45% by mass or more and 60% by mass or less> 40% by mass or less and less than 45% by mass or more than 60% by mass and less than 68% by mass> 40. It was found that the order of effects was less than mass% or more than 68 mass%. Similarly, regarding the monomer component (b), it was found that the order of effects was 29% by mass or more and 45% by mass or less> 25% by mass or more and less than 29% by mass> 25% by mass or less than 45% by mass. Similarly, for the monomer component (c), the effect of 7% by mass or more and 12% by mass or less> 6% by mass or more and less than 7% by mass or more than 12% by mass and 15% by mass or less> 6% by mass or less than 15% by mass. It turned out to be in order. Similarly, regarding the monomer component (d), 2% by mass or more and 4% by mass or less> 0.5% by mass or less and less than 2% by mass or more than 4% by mass and 5% by mass or less> 0.5% by mass or less than 5% by mass. It turned out to be in the order of effect. Similarly, regarding the monomer component (e), 0.01% by mass or more and 0.05% by mass or less> 0.005% by mass or more and less than 0.01% by mass or more than 0.05% by mass and 0.1% by mass or less> It was found that the order of effects was less than 0.005 mass% or more than 0.1 mass%.
Claims (10)
（ａ）（メタ）アクリル酸アルキルエステル ４０〜６８質量％
（ｂ）アルコキシ基含有（メタ）アクリル酸エステル ２５〜４５質量％
（ｃ）エチレン性不飽和二重結合を有する窒素含有モノマー ６〜１５質量％
（ｄ）エチレン性不飽和二重結合を有するカルボキシル基含有モノマー ０．５〜５質量％
（ｅ）エチレン性不飽和二重結合を複数有する多官能モノマー ０．００５〜０．１質量％ The adhesive composition containing the copolymer obtained by copolymerizing the monomer composition containing the following components (a)-(e).
(A) (meth) acrylic acid alkyl ester 40-68 mass%
(B) Alkoxy group-containing (meth) acrylic acid ester 25 to 45% by mass
(C) Nitrogen-containing monomer having an ethylenically unsaturated double bond 6 to 15% by mass
(D) Carboxyl group-containing monomer having an ethylenically unsaturated double bond 0.5 to 5% by mass
(E) Polyfunctional monomer having a plurality of ethylenically unsaturated double bonds 0.005 to 0.1% by mass
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014199028A JP2016069480A (en) | 2014-09-29 | 2014-09-29 | Adhesive composition |
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| JP2014199028A JP2016069480A (en) | 2014-09-29 | 2014-09-29 | Adhesive composition |
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| JP2016069480A true JP2016069480A (en) | 2016-05-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018235217A1 (en) * | 2017-06-22 | 2018-12-27 | 株式会社寺岡製作所 | Acrylic resin composition, adhesive agent composition, base for adhesive sheet, and adhesive sheet |
| JP2019024446A (en) * | 2017-08-02 | 2019-02-21 | 株式会社トクヤマ | Pad for nipple mouth of domestic animal, and pad assembly for nipple mouth of domestic animal |
| US11958967B2 (en) | 2017-06-22 | 2024-04-16 | Teraoka Seisakusho Co., Ltd. | Acrylic resin composition, adhesive agent composition, base for adhesive sheet, and adhesive sheet |
-
2014
- 2014-09-29 JP JP2014199028A patent/JP2016069480A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018235217A1 (en) * | 2017-06-22 | 2018-12-27 | 株式会社寺岡製作所 | Acrylic resin composition, adhesive agent composition, base for adhesive sheet, and adhesive sheet |
| JPWO2018235217A1 (en) * | 2017-06-22 | 2020-04-16 | 株式会社寺岡製作所 | Acrylic resin composition, pressure sensitive adhesive composition, base material for pressure sensitive adhesive sheet and pressure sensitive adhesive sheet |
| US11958967B2 (en) | 2017-06-22 | 2024-04-16 | Teraoka Seisakusho Co., Ltd. | Acrylic resin composition, adhesive agent composition, base for adhesive sheet, and adhesive sheet |
| JP2019024446A (en) * | 2017-08-02 | 2019-02-21 | 株式会社トクヤマ | Pad for nipple mouth of domestic animal, and pad assembly for nipple mouth of domestic animal |
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