JP2010126616A - Acrylic emulsion adhesive - Google Patents
Acrylic emulsion adhesive Download PDFInfo
- Publication number
- JP2010126616A JP2010126616A JP2008302069A JP2008302069A JP2010126616A JP 2010126616 A JP2010126616 A JP 2010126616A JP 2008302069 A JP2008302069 A JP 2008302069A JP 2008302069 A JP2008302069 A JP 2008302069A JP 2010126616 A JP2010126616 A JP 2010126616A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- sensitive adhesive
- acrylate
- acid
- pressure
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000839 emulsion Substances 0.000 title claims abstract description 31
- 239000000853 adhesive Substances 0.000 title abstract description 13
- 230000001070 adhesive effect Effects 0.000 title abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 54
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 26
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000003368 amide group Chemical group 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 5
- 239000002390 adhesive tape Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- -1 2-hydroxypropyl Chemical group 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 239000004632 polycaprolactone Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 4
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MMEJYPZZFYTVLJ-WAYWQWQTSA-N (z)-2-(2-prop-2-enoyloxyethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCOC(=O)C=C MMEJYPZZFYTVLJ-WAYWQWQTSA-N 0.000 description 2
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 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
- 125000003118 aryl group Chemical group 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic 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
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-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
- 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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- ACMIJDVJWLMBCX-PXAZEXFGSA-N 4-[(3ar,6ar)-2,3,3a,4,6,6a-hexahydro-1h-pyrrolo[2,3-c]pyrrol-5-yl]-6-fluoro-n-methyl-2-(2-methylpyrimidin-5-yl)oxy-9h-pyrimido[4,5-b]indol-8-amine Chemical compound CNC1=CC(F)=CC(C2=C(N3C[C@@H]4NCC[C@@H]4C3)N=3)=C1NC2=NC=3OC1=CN=C(C)N=C1 ACMIJDVJWLMBCX-PXAZEXFGSA-N 0.000 description 1
- ULPWBLHOWJRDBH-UHFFFAOYSA-N 5-amino-2-methylidenepentanamide Chemical compound NCCCC(=C)C(N)=O ULPWBLHOWJRDBH-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-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
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、優れた保持性・固定性を有するアクリルエマルション粘着剤およびそれが適用された両面粘着テープに関する。 The present invention relates to an acrylic emulsion pressure-sensitive adhesive having excellent retention and fixing properties, and a double-sided pressure-sensitive adhesive tape to which it is applied.
従来より、自動車、家電製品などの分野において、部品の固定には接着剤が使用されてきた。最近では、高強度の両面粘着テープも開発され、接着剤に代わって固定用途に用いられている。その一例として、厚みのある発泡体を基材とすることにより、応力を分散させ、固定性を高めたテープが知られている。また、不織布等の薄い基材に溶剤系アクリル粘着剤を適用した両面粘着テープの中にも、固定性の比較的高いものが見られる。
しかしながら、アクリルエマルション粘着剤で固定性に優れるものは見出されていない。また、基材に依らず粘着剤自体の固定性の向上を謳った技術は見受けられない。そこで、本発明は、優れた保持性・固定性を有するアクリルエマルション粘着剤を提供することを目的とする。ここで、本発明は後述するようにアクリルエマルション粘着剤の合成においてイタコン酸を共重合させることを本質とするが、アクリルエマルション粘着剤の合成に際し一原料としてイタコン酸を使用すること自体は、例えば特許文献１〜４に開示されている。しかしながら、これら文献では、原料の一部として添加してもよい重合性不飽和カルボン酸として、多種挙げられている中の一つとしてイタコン酸が列記されているに過ぎず、実施例でもイタコン酸を使用したものは無い。しかも、本明細書の実施例及び比較例から明らかなように、これら文献に記載されたイタコン酸以外の重合性不飽和カルボン酸（例えばアクリル酸やマレイン酸）を用いた場合には、固定性（Ｌ型保持力）がイタコン酸を用いた場合と比較して顕著に低い。 However, no acrylic emulsion pressure-sensitive adhesive having excellent fixability has been found. In addition, no technology has been found that improves the fixability of the adhesive itself regardless of the substrate. Then, an object of this invention is to provide the acrylic emulsion adhesive which has the outstanding retainability and fixability. Here, the present invention is based on the essence of copolymerizing itaconic acid in the synthesis of an acrylic emulsion pressure-sensitive adhesive as described later, but using itaconic acid as a raw material in the synthesis of an acrylic emulsion pressure-sensitive adhesive itself is, for example, It is disclosed in Patent Documents 1 to 4. However, in these documents, itaconic acid is only listed as one of various types of polymerizable unsaturated carboxylic acids that may be added as a part of the raw material. There is no thing using. Moreover, as is clear from the examples and comparative examples of the present specification, when a polymerizable unsaturated carboxylic acid (for example, acrylic acid or maleic acid) other than itaconic acid described in these documents is used, the fixability (L-type holding power) is remarkably low compared with the case where itaconic acid is used.
本発明者は、アクリルエマルション粘着剤の合成において、イタコン酸を共重合させることにより、固定性が飛躍的に向上し、溶剤系粘着剤を遥かに上回ることを見出した。 The present inventor has found that, in the synthesis of an acrylic emulsion pressure-sensitive adhesive, the fixability is dramatically improved by copolymerizing itaconic acid, far exceeding that of a solvent-based pressure-sensitive adhesive.
即ち、本発明（１）は、（メタ）アクリル酸アルキルエステル（ａ）を主成分とし、イタコン酸（ｂ）を含むビニル系不飽和単量体混合物｛好適には、（メタ）アクリル酸アルキルエステル（ａ）を主成分とし、イタコン酸（ｂ）を０．５〜１０重量％含むビニル系不飽和単量体混合物｝を、水性媒体中において乳化重合させることを特徴とするアクリルエマルション粘着剤である。 That is, the present invention (1) is a vinyl unsaturated monomer mixture comprising a (meth) acrylic acid alkyl ester (a) as a main component and containing itaconic acid (b) {preferably an alkyl (meth) acrylate. An acrylic emulsion pressure-sensitive adhesive comprising emulsion-polymerizing a vinyl unsaturated monomer mixture containing ester (a) as a main component and 0.5 to 10% by weight of itaconic acid (b) in an aqueous medium It is.
更に、イタコン酸は水溶性が高く、単独重合性に乏しい等の理由から、水系での重合は困難であり、従来の重合条件では重合転化率が大きく低下するという課題もある。当該課題の下、本発明者は、イタコン酸と特定モノマー（親水性モノマー等）を共重合することにより、基材に依らず優れた固定性を示す両面粘着テープとして適用可能なアクリルエマルション粘着剤が提供できることを更に見出した。具体的には、下記の本発明（２）である。 Furthermore, itaconic acid is difficult to polymerize in water due to its high water solubility and poor homopolymerizability, and there is a problem that the polymerization conversion rate is greatly reduced under conventional polymerization conditions. Under this problem, the present inventor has developed an acrylic emulsion pressure-sensitive adhesive that can be applied as a double-sided pressure-sensitive adhesive tape that exhibits excellent fixability regardless of the substrate by copolymerizing itaconic acid and a specific monomer (such as a hydrophilic monomer). Has further found that can be provided. Specifically, it is the following present invention (2).
即ち、本発明（２）は、前記ビニル系不飽和単量体混合物が、分子中にカルボキシル基、ヒドロキシル基、アミノ基及びアミド基から選択される一以上の置換基を有する単量体（ｃ）並びに／又は親水性のビニル系不飽和単量体（ｄ）を一種以上更に含む、前記発明（１）のアクリルエマルション粘着剤である。 That is, in the present invention (2), the vinyl unsaturated monomer mixture has a monomer (c) having one or more substituents selected from a carboxyl group, a hydroxyl group, an amino group and an amide group in the molecule. ) And / or one or more hydrophilic vinyl unsaturated monomers (d). The acrylic emulsion pressure-sensitive adhesive according to the invention (1).
本発明（３）は、前記発明（１）又は（２）の粘着剤が適用された両面粘着テープである。 The present invention (3) is a double-sided pressure-sensitive adhesive tape to which the pressure-sensitive adhesive of the invention (1) or (2) is applied.
本発明に係る粘着剤は、（メタ）アクリル酸アルキルエステル（ａ）とイタコン酸（ｂ）から成るポリマーであり、この２成分を必須的に含有している。より好適には、特定の官能基を有するモノマー（ｃ）または親水性モノマー（ｄ）を共重合した３成分以上からなるポリマーが望ましい。さらに、共重合可能な他の不飽和結合を有するモノマー（ｅ）を１種類以上共重合させてもよい。以下、各原料成分について詳述する。 The pressure-sensitive adhesive according to the present invention is a polymer composed of (meth) acrylic acid alkyl ester (a) and itaconic acid (b), and essentially contains these two components. More preferably, a polymer composed of three or more components obtained by copolymerization of a monomer (c) having a specific functional group or a hydrophilic monomer (d) is desirable. Furthermore, you may copolymerize 1 or more types of the monomer (e) which has another unsaturated bond which can be copolymerized. Hereinafter, each raw material component will be described in detail.
《ビニル系不飽和単量体混合物中の各成分》
（メタ）アクリル酸アルキルエステル（ａ）のアルキル基は特に限定されず、直鎖、分岐、環状を問わないが、炭素数１〜１８のものが使用される。例えば、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、ｔ−ブチルアクリレート、ｎ−ヘキシルアクリレート、シクロヘキシルアクリレート、ｎ−オクチルアクリレート、イソオクチルアクリレート、２−エチルヘキシルアクリレート、イソノニルアクリレート、ラウリルアクリレート、イソミリスチルアクリレート、ステアリルアクリレート、イソステアリルアクリレート、メチルメタクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、ｔ−ブチルメタクリレート、ｎ−ヘキシルメタクリレート、シクロヘキシルメタクリレート、ｎ−オクチルメタクリレート、イソオクチルメタクリレート、２−エチルヘキシルメタクリレート、イソノニルメタクリレート、イソデシルメタクリレート、デシルメタクリレート、ラウリルメタクリレート、トリデシルメタクリレート、ステアリルメタクリレート等が挙げられる。尚、本最良形態に係る発明において、（メタ）アクリル酸エステルとは、前記成分の中から選択された一種のモノマーのみならず、数種のモノマーの組合せであってもよく、好適には共重合物のＴｇが−２０℃以下になるように組み合わせて用いられる。なお、共重合体のＴｇは各ホモポリマーのＴｇから次式で計算される。（１／Ｔｇ＝１／Ｔｇ（ａ）＋１／Ｔｇ（ｂ）＋１／Ｔｇ（ｃ）＋・・・）。
《Each component in vinyl unsaturated monomer mixture》
The alkyl group of the (meth) acrylic acid alkyl ester (a) is not particularly limited and may be linear, branched or cyclic, but those having 1 to 18 carbon atoms are used. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate , Isononyl acrylate, lauryl acrylate, isomyristyl acrylate, stearyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate , Cyclohexyl methacrylate DOO, n- octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, decyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, and the like. In the invention according to the best mode, the (meth) acrylic acid ester may be not only one kind of monomer selected from the above components but also a combination of several kinds of monomers. They are used in combination so that the Tg of the polymer is -20 ° C or lower. In addition, Tg of a copolymer is calculated by following Formula from Tg of each homopolymer. (1 / Tg = 1 / Tg (a) + 1 / Tg (b) + 1 / Tg (c) +...).
成分（ｃ）として使用される単量体は分子中にカルボキシル基、ヒドロキシル基、アミノ基及びアミド基から選択される一種以上の官能基を有する重合性ビニル系単量体である。具体的には、カルボキシル基を含む単量体としてはアクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸モノエステル、β−カルボキシエチルアクリレート、２−（メタ）アクリロイロキシエチルコハク酸、２−（メタ）アクリロイロキシエチルフタル酸、２−（メタ）アクリロイロキシエチルマレイン酸、２−（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、ω−カルボキシ−ポリカプロラクトンモノアクリレート等がある。ヒドロキシル基を含む単量体としては２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチルアクリレート、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート（商品名：ブレンマーPE、AE（日油））、ポリプロピレングリコール（メタ）アクリレート（商品名：ブレンマーPP、AP（日油））、カプロラクトン変性（メタ）アクリル酸エステル（商品名：プラクセルF（ダイセル化学工業））、Ｎ−ヒドロキシエチルアクリルアミド等がある。アミノ基を含む単量体としては、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレートおよびその四級化塩、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレートおよびその四級化塩、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミドおよびその四級化塩等がある。アミド基を有する単量体としては、（メタ）アクリルアミド、Ｎ−イソプロピルアクリルアミド、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，Ｎ−ジメチルアミノプロピルアクリルアミドおよびその四級化塩、Ｎ−ヒドロキシエチルアクリルアミド、ダイアセトンアクリルアミド、Ｎ−ビニルアセトアミド、メタクリルアミドエチルエチレンウレア、アクリルアミドｔ−ブチルスルホン酸等がある。これらの単量体は、イタコン酸の主ポリマーへの共重合を促進し系全体の重合速度の増加に寄与すると同時にポリマーの接着性を向上させる働きがあると考えられる。前記成分の中から選択された一種のモノマーのみならず、数種のモノマーの組合せであってもよい。 The monomer used as component (c) is a polymerizable vinyl monomer having one or more functional groups selected from a carboxyl group, a hydroxyl group, an amino group and an amide group in the molecule. Specifically, monomers containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid monoester, β-carboxyethyl acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2 -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, ω-carboxy-polycaprolactone monoacrylate and the like. As the monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate (trade name) : Blenmer PE, AE (Nippon Oil)), Polypropylene glycol (meth) acrylate (trade name: Blemmer PP, AP (Nippon Oil)), caprolactone-modified (meth) acrylic acid ester (trade name: Plaxel F (Daicel Chemical Industries) ), N-hydroxyethylacrylamide and the like. Examples of the monomer containing an amino group include N, N-dimethylaminoethyl (meth) acrylate and a quaternized salt thereof, N, N-diethylaminoethyl (meth) acrylate and a quaternized salt thereof, N, N-dimethyl. Aminopropylacrylamide and its quaternized salts. Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropylacrylamide and quaternized salts thereof, N -Hydroxyethyl acrylamide, diacetone acrylamide, N-vinylacetamide, methacrylamide amethylene ethylene urea, acrylamide t-butyl sulfonic acid and the like. These monomers are considered to promote the copolymerization of itaconic acid to the main polymer, contribute to an increase in the polymerization rate of the entire system, and at the same time improve the adhesion of the polymer. Not only one kind of monomer selected from the above components but also a combination of several kinds of monomers may be used.
成分（ｄ）として使用される単量体は一般に親水性モノマーと呼ばれる単量体であり、主にイタコン酸の共重合を促進する働きをするものと考えられる。具体的には、アクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸モノエステル、β−カルボキシエチルアクリレート、２−（メタ）アクリロイロキシエチルコハク酸、２−（メタ）アクリロイロキシエチルフタル酸、２−（メタ）アクリロイロキシエチルマレイン酸、２−（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、ω−カルボキシ−ポリカプロラクトンモノアクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチルアクリレート、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート（商品名：ブレンマーPE、AE（日油））、カプロラクトン変性（メタ）アクリル酸エステル（商品名：プラクセルF（ダイセル化学工業））、Ｎ−ヒドロキシエチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレートおよびその四級化塩、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレートおよびその四級化塩、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミドおよびその四級化塩、（メタ）アクリルアミド、Ｎ−イソプロピルアクリルアミド、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、ダイアセトンアクリルアミド、Ｎ−ビニルアセトアミド、メタクリルアミドエチルエチレンウレア、アクリルアミドｔ−ブチルスルホン酸、Ｎ−ビニル−２−ピロリドン、アクリロイルモルフォリン、（メタ）アクリロニトリル、アルコキシ（メタ）アクリレート、アルコキシポリエチレングリコールモノ（メタ）アクリレート、２−（メタ）アクリロイロキシエチルアシッドフォスフェート、メタクリロイルオキシエチルカルボキシベタイン等分子中に親水性を示す構造（カルボキシル基、水酸基、エーテル基、スルホン酸基、リン酸基、アミノ基、アミド基）を有する単量体が使用される。前記成分の中から選択された一種のモノマーのみならず、数種のモノマーの組合せであってもよい。 The monomer used as component (d) is a monomer generally called a hydrophilic monomer, and is considered to function mainly to promote the copolymerization of itaconic acid. Specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid monoester, β-carboxyethyl acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalate Acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, ω-carboxy-polycaprolactone monoacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 4-hydroxybutyl acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate (trade name: Blemmer PE, AE (Nippon Oil)), caprolactone modified (meth) acrylic acid ester (trade name) : Plaxel F (Da Cell Chemical Industry)), N-hydroxyethylacrylamide, N, N-dimethylaminoethyl (meth) acrylate and quaternized salts thereof, N, N-diethylaminoethyl (meth) acrylate and quaternized salts thereof, N, N -Dimethylaminopropylacrylamide and its quaternized salts, (meth) acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, diacetone acrylamide, N-vinylacetamide, methacrylamide ethylethylene urea , Acrylamide t-butylsulfonic acid, N-vinyl-2-pyrrolidone, acryloylmorpholine, (meth) acrylonitrile, alkoxy (meth) acrylate, alkoxy polyethylene glycol mono (meth) acrylate , 2- (meth) acryloyloxyethyl acid phosphate, methacryloyloxyethyl carboxybetaine, etc., structures having hydrophilicity in the molecule (carboxyl group, hydroxyl group, ether group, sulfonic acid group, phosphoric acid group, amino group, amide) A monomer having a group) is used. Not only one kind of monomer selected from the above components but also a combination of several kinds of monomers may be used.
また、上述した成分（ｃ）と成分（ｄ）は、一部重複したものも存在する。即ち、分子中にカルボキシル基、ヒドロキシル基、アミノ基及びアミド基から選択される一種以上の官能基を有する、親水性の重合性ビニル系単量体がこれに相当する。この場合は、原料中に成分（ｃ）が存在すると捉えることも、原料中に成分（ｄ）が存在すると捉えることも可能である。ここで、より好適な成分（ｃ）／成分（ｄ）は、アクリル酸、メタクリル酸、ダイアセトンアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ビニル−２−ピロリドン、ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアクリルアミド、ω―カルボキシ−ポリカプロラクトン（ｎ≒２）モノアクリレート、アクリル酸ダイマー、２−アクリロイロキシエチル−コハク酸であり、更に好適な成分（ｃ）／成分（ｄ）は、アクリル酸、メタクリル酸、ダイアセトンアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、ω―カルボキシ−ポリカプロラクトン（ｎ≒２）モノアクリレートである。 Moreover, the component (c) and the component (d) described above may partially overlap. That is, a hydrophilic polymerizable vinyl monomer having one or more functional groups selected from a carboxyl group, a hydroxyl group, an amino group and an amide group in the molecule corresponds to this. In this case, it can be understood that the component (c) is present in the raw material, or that the component (d) is present in the raw material. Here, more preferable component (c) / component (d) is acrylic acid, methacrylic acid, diacetone acrylamide, N-isopropylacrylamide, N-vinyl-2-pyrrolidone, dimethylaminoethyl methacrylate, N, N-diethyl. Acrylamide, ω-carboxy-polycaprolactone (n≈2) monoacrylate, acrylic acid dimer, 2-acryloyloxyethyl-succinic acid, and more preferable component (c) / component (d) is acrylic acid, methacrylic acid, Acid, diacetone acrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, ω-carboxy-polycaprolactone (n≈2) monoacrylate.
原料であるビニル系不飽和単量体混合物は、上記（ａ）及び（ｂ）｛更に（ｃ）及び／又は（ｄ）｝に加え、他の不飽和結合を有する単量体（ｅ）を更に共重合成分として含有していてもよい。単量体（ｅ）としては、スチレン、酢酸ビニル等のカルボン酸ビニルエステル等がある。 In addition to the above (a) and (b) {further (c) and / or (d)}, the vinyl unsaturated monomer mixture as a raw material contains a monomer (e) having another unsaturated bond. Furthermore, you may contain as a copolymerization component. Examples of the monomer (e) include carboxylic acid vinyl esters such as styrene and vinyl acetate.
《ビニル系不飽和単量体混合物中の各成分量》
本ビニル系不飽和単量体混合物は、（メタ）アクリル酸アルキルエステル（ａ）を主成分として含有し、イタコン酸（ｂ）を必須成分として含有する。ここで、「主成分」とは、当該混合物の全重量を基準として、５０重量％以上、好適には７０重量％以上含有することを意味する。また、イタコン酸（ｂ）はポリマーの保持性・固定性を向上させるために共重合されるが、その配合量は、全単量体混合物の重量を基準として、０．１〜１５重量％が好適であり、０．５〜１０重量％がより好適であり、０．５〜５重量％であれば更に好適である。特定の官能基を有するモノマー｛成分（ｃ）｝、親水性モノマー｛成分（ｄ）｝の配合量はイタコン酸の重量に対して０〜５倍であることが好適であり、２〜５倍であればより好適である。他の不飽和結合を有する単量体（ｅ）の配合量は０〜３０重量％が好適である。更に、このビニル系不飽和単量体混合物は、アクリルエマルションを製造する際、原料を分割して添加した場合には、これら分割して添加した原料を合わせたものを意味する。
《Amount of each component in vinyl unsaturated monomer mixture》
The vinyl unsaturated monomer mixture contains (meth) acrylic acid alkyl ester (a) as a main component and itaconic acid (b) as an essential component. Here, the “main component” means containing 50% by weight or more, preferably 70% by weight or more based on the total weight of the mixture. In addition, itaconic acid (b) is copolymerized in order to improve the retention and fixing properties of the polymer, and the blending amount thereof is 0.1 to 15% by weight based on the weight of the total monomer mixture. 0.5 to 10% by weight is more preferable, and 0.5 to 5% by weight is more preferable. The blending amount of the monomer {component (c)} having a specific functional group and the hydrophilic monomer {component (d)} is preferably 0 to 5 times the weight of itaconic acid, and 2 to 5 times. If so, it is more preferable. The blending amount of the monomer (e) having another unsaturated bond is preferably 0 to 30% by weight. Furthermore, this vinyl unsaturated monomer mixture means a combination of the raw materials added in divided portions when the raw materials are added in divided portions when the acrylic emulsion is produced.
《エマルション系粘着剤》
本発明に係るエマルション系粘着剤は、前述した原料を水性媒体中で乳化重合させることにより得られるアクリルエマルションを主成分とする。ここで、「主成分」とは、全粘着剤組成物の重量を基準として、好適には５０重量％、より好適には７０重量％含有することを指す。
<Emulsion adhesive>
The emulsion-based pressure-sensitive adhesive according to the present invention contains as a main component an acrylic emulsion obtained by emulsion polymerization of the above-described raw materials in an aqueous medium. Here, the “main component” means that the content is preferably 50% by weight, more preferably 70% by weight, based on the weight of the total pressure-sensitive adhesive composition.
ここで、本発明に係る粘着剤は、上記の成分の他に、粘着付与剤樹脂として、ロジン系樹脂、テルペン系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、クマロンインデン樹脂、スチレン系樹脂、フェノール系樹脂、キシレン樹脂等の樹脂を添加することができる。 Here, the pressure-sensitive adhesive according to the present invention includes a rosin resin, a terpene resin, an aliphatic petroleum resin, an alicyclic petroleum resin, and an aromatic petroleum resin as a tackifier resin in addition to the above components. A resin such as a coumarone indene resin, a styrene resin, a phenol resin, or a xylene resin can be added.
また、本発明に係る粘着剤は、架橋剤を含有していてもよい。ここで、架橋剤として、エポキシ基、イソシアネート基、ヒドラジド基、カルボジイミド基等の反応性官能基を二以上有している物質、例えば、ジグリシジルエーテル、アジピン酸ジヒドラジドを挙げることができる。 Moreover, the adhesive which concerns on this invention may contain the crosslinking agent. Here, examples of the crosslinking agent include substances having two or more reactive functional groups such as an epoxy group, an isocyanate group, a hydrazide group, and a carbodiimide group, such as diglycidyl ether and adipic acid dihydrazide.
また、充填剤として、炭酸カルシウム、亜鉛華（酸化亜鉛）、シリカ、酸化チタン等を含有していてもよい。 Moreover, you may contain calcium carbonate, zinc white (zinc oxide), silica, titanium oxide, etc. as a filler.
その他、軟化剤として、パラフィン系プロセスオイル、ナフテン系プロセスオイル、芳香族系プロセスオイル、ひまし油、綿実油、あまに油、菜種油等を添加することができる。 In addition, paraffinic process oil, naphthenic process oil, aromatic process oil, castor oil, cottonseed oil, linseed oil, rapeseed oil, and the like can be added as a softening agent.
《アクリルエマルションの物性》
次に、本発明に係るアクリルエマルションの物性を説明する。本発明に係るアクリルエマルションは、特に限定されないが、好適には、酢酸エチル不溶分（ゲル分率）が７０％以上であり、より好適には９０％以上である。ここで、ゲル分率の測定法は下記の通りである。まず、剥離紙上でエマルションを乾燥させ、粘着剤膜を作成する。得られた粘着剤膜を円筒ろ紙に入れ、酢酸エチル中に浸漬し、１週間放置する。この不溶分をゲル分とし、ゲル分の乾燥重量と浸漬前の乾燥重量の比をゲル分率として求める。
《Physical properties of acrylic emulsion》
Next, the physical properties of the acrylic emulsion according to the present invention will be described. Although the acrylic emulsion which concerns on this invention is not specifically limited, Preferably, an ethyl acetate insoluble content (gel fraction) is 70% or more, More preferably, it is 90% or more. Here, the measuring method of a gel fraction is as follows. First, the emulsion is dried on a release paper to form an adhesive film. The obtained pressure-sensitive adhesive film is placed in a cylindrical filter paper, immersed in ethyl acetate, and allowed to stand for 1 week. The insoluble content is defined as a gel content, and the ratio of the dry weight of the gel to the dry weight before immersion is determined as the gel fraction.
《アクリルエマルションの製造方法》
本発明に係るアクリルエマルションは、前述した原料を水性媒体中で乳化重合させることにより得られる。ここで、乳化重合は公知の手段によって行うことができるが、例えば水を溶媒とし、界面活性剤の一種または二種以上とモノマー成分を加えて乳化させ、加熱した後、開始剤を添加して撹拌することにより、実施することができる。
<Method for producing acrylic emulsion>
The acrylic emulsion according to the present invention is obtained by emulsion polymerization of the above-described raw materials in an aqueous medium. Here, the emulsion polymerization can be carried out by a known means. For example, water is used as a solvent, one or more surfactants and a monomer component are added to emulsify, and after heating, an initiator is added. It can be carried out by stirring.
界面活性剤は特に限定されるものではないが、アニオン系界面活性剤として、例えば、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルスルホコハク酸ナトリウムやアクアロンＫＨ−１０（第一工業製薬（株）製反応性界面活性剤、スルホン酸系）、およびノニオン系界面活性剤として、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエート、ポリオキシエチレンソルビタンモノラウレートやアクアロンＲＮ−３０（第一工業製薬（株）製反応性界面活性剤）などを使用することができる。 The surfactant is not particularly limited, but examples of the anionic surfactant include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether sulfuric acid. Sodium, polyoxyethylene alkyl phenyl ether ammonium sulfate, sodium polyoxyethylene alkyl sulfosuccinate and Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd. reactive surfactant, sulfonic acid series), and nonionic surfactants, For example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, sorbitan monolaurate, sorbitan monostearate Sorbitan trioleate, polyoxyethylene sorbitan monolaurate and Aqualon RN-30 (Dai-ichi Kogyo Seiyaku Co., Ltd. reactive surfactants) can be used like.
上記の界面活性剤と共に、必要に応じて水溶性保護コロイドを使用することができる。例えば、ポリビニルアルコール、カルボキシメチルセルロース、ゼラチンなどが挙げられる。 A water-soluble protective colloid can be used together with the above-described surfactant as required. For example, polyvinyl alcohol, carboxymethyl cellulose, gelatin and the like can be mentioned.
重合開始剤としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩系、ｔ−ブチルハイドロパーオキシド、クメンハイドロパーオキシドなどの有機過酸化物系、過酸化水素と酒石酸などのレドックス系、Ｖ−５０（和光純薬工業（株）製）などの水溶性アゾ系開始剤等が使用できる。 Polymerization initiators include persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, and redox such as hydrogen peroxide and tartaric acid. Water-soluble azo-based initiators such as V-50, manufactured by Wako Pure Chemical Industries, Ltd. can be used.
重合に際しては、共重合体の分子量を調節するため、必要に応じて連鎖移動剤を使用することができる。例えば、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ブチルメルカプタンなどが挙げられる。 In the polymerization, a chain transfer agent can be used as necessary to adjust the molecular weight of the copolymer. For example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, and the like can be given.
《アクリルエマルション粘着剤の製造方法》
本発明に係る粘着剤は、公知の手法により製造可能であり、例えば、乳化重合体に、必要に応じて、粘着付与剤樹脂、架橋剤等を添加、撹拌し製造することができる。
<< Method for producing acrylic emulsion adhesive >>
The pressure-sensitive adhesive according to the present invention can be produced by a known technique. For example, a tackifier resin, a cross-linking agent, and the like can be added to an emulsion polymer and stirred as necessary.
《アクリルエマルション粘着剤の用途》
最後に、本発明に係る粘着剤の用途を説明する。本発明の粘着剤を公知の手法により基材上に適用することにより、各種用途に適用可能な両面粘着テープを得ることができる。例えば、紙用、プラスチック用、金属用の粘着テープを挙げることができる。具体的には、紙同士、プラスチック同士、金属同士だけではなく、異種材料同士の接合にも有用である。また、フック・ハンガーの取り付け等に有効な固定性を有する粘着テープも得ることができる。基材は、特に限定されないが、不織布、プラスチック発泡シート、ポリアミド、ポリエチレンテレフタレート、ポリウレタンなどの合成樹脂からなるフィルムまたはシートが挙げられる。
《Use of acrylic emulsion adhesive》
Finally, the use of the pressure-sensitive adhesive according to the present invention will be described. By applying the pressure-sensitive adhesive of the present invention on a substrate by a known method, a double-sided pressure-sensitive adhesive tape applicable to various uses can be obtained. For example, an adhesive tape for paper, plastic, and metal can be mentioned. Specifically, it is useful not only for papers, plastics, and metals but also for joining different materials. In addition, an adhesive tape having a fixing property effective for attaching a hook or a hanger can be obtained. Although a base material is not specifically limited, The film or sheet | seat which consists of synthetic resins, such as a nonwoven fabric, a plastic foam sheet, polyamide, a polyethylene terephthalate, and a polyurethane, is mentioned.
以下、本発明について実施例を参照しながら更に具体的に説明する。尚、本発明の技術的範囲は実施例に限定されるものではない。また、特記しない限り、以下の実施例における「部」は重量部を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. The technical scope of the present invention is not limited to the examples. Unless otherwise specified, “parts” in the following examples means parts by weight.
製造例 乳化重合による共重合体の製造方法
温度計、コンデンサー、窒素導入管、撹拌機を備えた温度調節可能な反応容器に蒸留水２００部、反応型アニオン系界面活性剤（アクアロンＫＨ−１０：第一工業製薬（株）製）０．４５部、２−エチルヘキシルアクリレート（以下、「２−ＥＨＡ」とする）２２．５部、ｎ−ブチルアクリレート（以下、「ｎ−ＢＡ」とする）３．６部、メチルメタクリレート（以下、「ＭＭＡ」とする）３．０部、イタコン酸（以下、「ＩＴＡ」とする）０．９部を仕込み、窒素気流下で８０℃まで昇温した後、過硫酸カリウム０．６部を蒸留水１０部に溶解させた液を滴下し、１０分後から、２−ＥＨＡ２０２．５部、ｎ−ＢＡ３２．４部、ＭＭＡ２７．０部、ＩＴＡ８．１部からなるモノマー混合物を、反応型アニオン系界面活性剤（アクアロンＫＨ−１０：第一工業製薬（株）製）４．０５部、蒸留水９０部に乳化分散させたモノマー乳化物を、２時間で連続的に添加し、さらに８０℃で２時間反応を継続し、重合を完結させた後冷却した。アンモニア水でｐＨ７．５に調整後、金網等で濾過し、固形分５０％のアクリル共重合体エマルションを得た。尚、本実施例および比較例で用いた他の乳化重合体は、当該製造例に従い製造して用いた。
Production Example Copolymer Production Method by Emulsion Polymerization 200 parts of distilled water in a temperature-controllable reaction vessel equipped with a thermometer, a condenser, a nitrogen introduction tube and a stirrer, a reactive anionic surfactant (Aqualon KH-10: Daiichi Kogyo Seiyaku Co., Ltd.) 0.45 parts, 2-ethylhexyl acrylate (hereinafter referred to as “2-EHA”) 22.5 parts, n-butyl acrylate (hereinafter referred to as “n-BA”) 3 .6 parts, 3.0 parts of methyl methacrylate (hereinafter referred to as “MMA”) and 0.9 part of itaconic acid (hereinafter referred to as “ITA”) were charged to 80 ° C. under a nitrogen stream, A solution prepared by dissolving 0.6 part of potassium persulfate in 10 parts of distilled water was added dropwise, and 10 minutes later, 202.5 parts of 2-EHA, 32.4 parts of n-BA, 27.0 parts of MMA, 8.1 parts of ITA A monomer mixture that reacts Type anionic surfactant (AQUALON KH-10: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a monomer emulsion emulsified and dispersed in 90 parts of distilled water were continuously added in 2 hours. The reaction was continued at 80 ° C. for 2 hours to complete the polymerization and then cooled. After adjusting the pH to 7.5 with aqueous ammonia, the mixture was filtered through a wire mesh or the like to obtain an acrylic copolymer emulsion having a solid content of 50%. In addition, the other emulsion polymer used by the present Example and the comparative example was manufactured according to the said manufacture example, and was used.
重合転化率の測定方法
ポリマーの重合転化率は、反応終了したエマルジョン液の固形分濃度から、下記式により求めた。
重合転化率＝（実測固形分濃度／設定固形分濃度）×１００
ここで、実測固形分濃度は、反応終了したエマルジョン液を１２０℃で２時間乾燥させ、乾燥前後の重量比により算出した。
実測固形分濃度＝（乾燥後の重量／乾燥前の重量）×１００
Method for Measuring Polymerization Conversion The polymerization conversion rate of the polymer was determined from the solid content concentration of the emulsion liquid after the reaction by the following formula.
Polymerization conversion rate = (actually measured solid content concentration / set solid content concentration) × 100
Here, the measured solid content concentration was calculated based on the weight ratio before and after drying after drying the emulsion after the reaction at 120 ° C. for 2 hours.
Measured solid content concentration = (weight after drying / weight before drying) × 100
粘着剤の評価方法
剥離紙上に本発明に係る粘着剤を乾燥後の厚さが５０μｍになるように塗工し、乾燥した後、不織布基材の両面に貼り合せて転写して、両面粘着シートを得た。得られたシートを２５×２５ｍｍ２に裁断し、固定性を調査した。不織布基材としては、レーヨン不織布（厚さ５０μm、坪量１４g/ｍ２）を用いた。
Evaluation method of pressure-sensitive adhesive The pressure-sensitive adhesive according to the present invention is coated on a release paper so that the thickness after drying is 50 μm, dried, and then pasted onto both sides of a nonwoven fabric substrate and transferred to a double-sided pressure-sensitive adhesive sheet. Got. The obtained sheet was cut into 25 × 25 mm 2, it was investigated fixity. As the nonwoven fabric substrate, a rayon nonwoven fabric (thickness 50 μm, basis weight 14 g / m 2 ) was used.
固定性の評価方法
両面粘着テープの片面を、ステンレス製のＬ型パネルに貼付し、余った部分を切断した。試験片の上から５ｋｇの圧着ローラーを用い、圧着速度毎分約３００ｍｍで１往復圧着した。次に試験片のもう一方の面をステンレス製の試験板に貼り合せ、５ｋｇの圧着ローラーを用い、圧着速度毎分約３００ｍｍで１往復圧着した。７２時間放置した後、１ｋｇの荷重をＬ型パネルに吊り下げ、落下するまでの時間を測定した。測定は２３℃５０％ＲＨの条件下で行った。ここで、Ｌ型パネルとは、図１に示す形のもので、２５×２５ｍｍ２のステンレス板をアルミニウム製のＬ型チップに接着剤を用いて固定したものであり、ステンレス板表面より２０mm離れた位置の中央部に定荷重を負荷することを可能ならしめるべき約１ｍｍφの穴をあけたものである。固定性１０時間未満を×、１０時間以上１００時間未満を○、１００時間以上を◎と評価した。
Evaluation method of fixability One side of the double-sided pressure-sensitive adhesive tape was attached to a stainless steel L-shaped panel, and the remaining part was cut. Using a 5 kg pressure roller from the top of the test piece, one reciprocal pressure was applied at a pressure speed of about 300 mm per minute. Next, the other surface of the test piece was bonded to a stainless steel test plate and subjected to one reciprocal pressure bonding using a 5 kg pressure roller at a pressure speed of about 300 mm / min. After being left for 72 hours, a load of 1 kg was suspended on the L-shaped panel, and the time until dropping was measured. The measurement was performed under conditions of 23 ° C. and 50% RH. Here, the L-shaped panel has the shape shown in FIG. 1 and is a 25 × 25 mm 2 stainless steel plate fixed to an aluminum L-shaped chip with an adhesive, and is 20 mm away from the stainless steel plate surface. A hole of about 1 mmφ that should be able to be applied with a constant load at the center of the position. The fixability of less than 10 hours was evaluated as x, 10 hours or more but less than 100 hours was evaluated as ◯, and 100 hours or more was evaluated as ◎.
比較例１〜３、実施例１
（メタ）アクリル酸エステルとカルボキシル基含有モノマーからなる乳化重合体を用いて、重合転化率および固定性（Ｌ型保持力）の評価を行った。結果を表１及び図２に示す。イタコン酸を共重合したときに、非常に高い固定性が得られた。しかし、重合転化率の低下が見られた。
Comparative Examples 1-3, Example 1
Using an emulsion polymer composed of a (meth) acrylic acid ester and a carboxyl group-containing monomer, the polymerization conversion rate and fixability (L-type holding power) were evaluated. The results are shown in Table 1 and FIG. When itaconic acid was copolymerized, very high fixability was obtained. However, a decrease in polymerization conversion was observed.
ｎ−ＢＡ：ｎ−ブチルアクリレート
ＭＭＡ：メチルメタクリレート
ＡＡ：アクリル酸
ＭＡＡ：メタクリル酸
ＩＴＡ：イタコン酸
実施例１〜１１
（メタ）アクリル酸エステルとイタコン酸に、さらに親水性モノマーを加えて共重合することにより、重合転化率を低下させることなく、高い保持性を有する粘着剤が得られた。結果を表２に示す。
Examples 1-11
By adding a hydrophilic monomer to (meth) acrylic acid ester and itaconic acid for copolymerization, a pressure-sensitive adhesive having high retention was obtained without lowering the polymerization conversion rate. The results are shown in Table 2.
ＮＩＰＡＭ：Ｎ−イソプロピルアクリルアミド
ＮＶＰ：Ｎ−ビニル−２−ピロリドン
ＤＭ：ジメチルアミノエチルメタクリレート
ＤＥＡＡ：Ｎ，Ｎ−ジエチルアクリルアミド
アロニックスＭ−５３００：東亞合成社製、ω―カルボキシ−ポリカプロラクトン（ｎ≒２）モノアクリレート
アロニックスＭ−５６００：東亞合成社製、アクリル酸ダイマー
ＨＯＡ−ＭＳ：２−アクリロイロキシエチル−コハク酸
実施例１２〜１４、比較例４
実施例２〜１８において特に効果の高かった、親水性モノマーとしてアクリル酸を用いた場合において、イタコン酸とアクリル酸の配合比による効果の確認を行った。結果を表３に示す。イタコン酸が多い方が固定性は高く、アクリル酸が多いほど重合転化率は高くなる傾向が認められた。尚、実施例１４に係るアクリルエマルションのゲル分率は、９５．４％であった。
Examples 12-14, Comparative Example 4
In the case where acrylic acid was used as the hydrophilic monomer, which was particularly effective in Examples 2 to 18, the effect due to the mixing ratio of itaconic acid and acrylic acid was confirmed. The results are shown in Table 3. A higher amount of itaconic acid showed higher fixability, and a higher amount of acrylic acid tended to increase the polymerization conversion rate. The gel fraction of the acrylic emulsion according to Example 14 was 95.4%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014051252A1 (en) * | 2012-09-27 | 2014-04-03 | 롯데케미칼 주식회사 | Coating composition for easily adhering polyester film with excellent surface smoothness, and polyester film using same |
| WO2015046872A1 (en) * | 2013-09-26 | 2015-04-02 | 주식회사 엘지화학 | Adhesive composition for a polypropylene film and method for preparing same |
| CN114214874A (en) * | 2021-12-16 | 2022-03-22 | 山东龙德复合材料科技股份有限公司 | Air filter paper coating glue solution and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014051252A1 (en) * | 2012-09-27 | 2014-04-03 | 롯데케미칼 주식회사 | Coating composition for easily adhering polyester film with excellent surface smoothness, and polyester film using same |
| KR101428859B1 (en) * | 2012-09-27 | 2014-08-14 | 롯데케미칼 주식회사 | Coating composition for adhesive polyester film with excellent surface smoothness and polyester film using same |
| WO2015046872A1 (en) * | 2013-09-26 | 2015-04-02 | 주식회사 엘지화학 | Adhesive composition for a polypropylene film and method for preparing same |
| CN114214874A (en) * | 2021-12-16 | 2022-03-22 | 山东龙德复合材料科技股份有限公司 | Air filter paper coating glue solution and application thereof |
| CN114214874B (en) * | 2021-12-16 | 2023-03-10 | 山东龙德复合材料科技股份有限公司 | Air filter paper coating glue solution and application thereof |
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