JP2006063123A - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP2006063123A JP2006063123A JP2004244758A JP2004244758A JP2006063123A JP 2006063123 A JP2006063123 A JP 2006063123A JP 2004244758 A JP2004244758 A JP 2004244758A JP 2004244758 A JP2004244758 A JP 2004244758A JP 2006063123 A JP2006063123 A JP 2006063123A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- component
- pressure
- polymer
- sensitive adhesive
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 239000000853 adhesive Substances 0.000 title claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 24
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 45
- 229920000098 polyolefin Polymers 0.000 claims abstract description 28
- 229920000573 polyethylene Polymers 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 38
- 239000004711 α-olefin Substances 0.000 claims description 14
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 8
- 239000008194 pharmaceutical composition Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 13
- 238000011109 contamination Methods 0.000 abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 17
- 150000001336 alkenes Chemical class 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 15
- -1 propylene, ethylene Chemical group 0.000 description 14
- 238000004898 kneading Methods 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- 229940106006 1-eicosene Drugs 0.000 description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N tridecaene Natural products CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 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
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
【課題】 低温環境下での粘着力が高く、被着体への汚染性が少ない粘着剤用組成物を提供する。
【解決手段】 非晶性オレフィン系重合体（成分（Ａ））９５〜９９．９重量％と、エチレン系重合体（成分（Ｂ））０．１〜５重量％とを含有し、前記エチレン系重合体（成分（Ｂ））が、示差走査熱量測定によって、−１００〜２００℃に観測される最大の結晶融解ピークの温度が１２０℃以下のエチレン系重合体である粘着用組成物（但し、粘着用組成物の全量を１００重量％とする）。
【選択図】 なしPROBLEM TO BE SOLVED: To provide a composition for a pressure-sensitive adhesive having high adhesive strength in a low temperature environment and little contamination to an adherend.
An amorphous olefin polymer (component (A)) 95 to 99.9% by weight and an ethylene polymer (component (B)) 0.1 to 5% by weight, the ethylene A pressure-sensitive adhesive composition (provided that the polymer (component (B)) is an ethylene polymer having a maximum crystal melting peak temperature of -100 to 200 ° C. observed by differential scanning calorimetry at −100 to 200 ° C.) The total amount of the pressure-sensitive adhesive composition is 100% by weight).
[Selection figure] None
Description
本発明は粘着剤組成物に関するものである。詳しくは、低温環境下での粘着力が高く、被着体への汚染性が少ない粘着剤用組成物に関するものである。 The present invention relates to an adhesive composition. Specifically, the present invention relates to a pressure-sensitive adhesive composition having high adhesive strength in a low-temperature environment and low contamination to an adherend.
従来から、粘着剤には、特定の結晶性ポリオレフィン系樹脂や特定のオレフィン系共重合体が用いられていた。
例えば、特開２００３−２２６８５３号公報には、有機溶媒を用いないで粘着もしくは接着し、接合体の置かれる環境温度に係らず低温環境下や高温環境下でも極端な経時変化することなく、好適な粘着性を維持する粘着剤として、結晶性ポリオレフィン樹脂を鞘とし、特定のオレフィン系共重合体を芯とする形状を有する多層ペレットからなる粘着剤が記載されている。
Conventionally, a specific crystalline polyolefin resin or a specific olefin copolymer has been used for the pressure-sensitive adhesive.
For example, Japanese Patent Application Laid-Open No. 2003-226853 is suitable for adhesion or adhesion without using an organic solvent, without causing a change over time even in a low temperature environment or a high temperature environment regardless of the environmental temperature where the joined body is placed. As a pressure-sensitive adhesive that maintains a high level of pressure-sensitive adhesiveness, a pressure-sensitive adhesive made of a multilayer pellet having a shape with a crystalline polyolefin resin as a sheath and a specific olefin copolymer as a core is described.
上記の特開２００３−２２６８５３号公報に記載の粘着剤においても、使用環境温度や用途によっては粘着力が必ずしも十分とは言えず、さらなる改良が求められていた。
かかる状況の下、本発明の目的は、低温環境下での粘着力が高く、被着体への汚染性が少ない粘着剤用組成物を提供することにある。
Even in the pressure-sensitive adhesive described in JP-A-2003-226853, the pressure-sensitive adhesive force is not always sufficient depending on the use environment temperature and application, and further improvement has been demanded.
Under such circumstances, an object of the present invention is to provide a pressure-sensitive adhesive composition having high adhesive strength in a low-temperature environment and low contamination to an adherend.
すなわち本発明は、
非晶性オレフィン系重合体（成分（Ａ））９５〜９９．９重量％と、エチレン系重合体（成分（Ｂ））０．１〜５重量％とを含有し、前記エチレン系重合体（成分（Ｂ））が、示差走査熱量測定によって、−１００〜２００℃に観測される最大の結晶融解ピークの温度が１２０℃以下のエチレン系重合体である粘着用組成物に係るものである（但し、粘着用組成物の全量を１００重量％とする）。
That is, the present invention
Amorphous olefin polymer (component (A)) 95 to 99.9 wt% and ethylene polymer (component (B)) 0.1 to 5 wt%, the ethylene polymer ( Component (B)) relates to a pressure-sensitive adhesive composition which is an ethylene polymer having a maximum crystal melting peak temperature of −100 to 200 ° C. observed by differential scanning calorimetry at −100 to 200 ° C. ( However, the total amount of the pressure-sensitive adhesive composition is 100% by weight).
本発明によれば、低温環境下での粘着力が高く、被着体への汚染性が少ない粘着剤用組成物を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the composition for adhesives which has the high adhesive force in a low-temperature environment, and has little pollution property to a to-be-adhered body can be obtained.
非晶性オレフィン系重合体（成分（Ａ））は、エチレンおよび炭素原子数３〜２０のα−オレフィンからなる群から選ばれた少なくとも二種のオレフィンを共重合して得られる非晶性オレフィン系重合体である。 The amorphous olefin polymer (component (A)) is an amorphous olefin obtained by copolymerizing at least two olefins selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms. Based polymer.
前記の炭素原子数３〜２０のα−オレフィンとしては、鎖状オレフィンが挙げられ、鎖状オレフィンとしては、直鎖状オレフィンや分岐状オレフィンが挙げられる。
直鎖状オレフィンとしては、例えば、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−へプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−ノナデセン、１−エイコセン等が挙げられ、分岐状オレフィンとしては、例えば、３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、２−エチル−１−ヘキセン、２，２，４−トリメチル−１−ペンテン等が挙げられる。
Examples of the α-olefin having 3 to 20 carbon atoms include chain olefins, and examples of the chain olefin include linear olefins and branched olefins.
Examples of the linear olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- Examples include tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like. Examples of branched olefins include 3-methyl-1-butene, Examples include 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene and the like.
非晶性オレフィン系重合体（成分（Ａ））としては、例えば、エチレン−プロピレン共重合体、エチレン−１−ブテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−１−オクテン共重合体、エチレン−４−メチル−１−ペンテン共重合体、エチレン−プロピレン−１−ブテン共重合体、エチレン−プロピレン−１−ヘキセン共重合体、エチレン−１−ブテン−１−ヘキセン共重合体、プロピレン−１−ブテン共重合体、プロピレン−１−ヘキセン共重合体、プロピレン−１−オクテン共重合体、プロピレン−４−メチル−１−ペンテン共重合体、プロピレン−１−ブテン−１−ヘキセン共重合体等が挙げられる。 As the amorphous olefin polymer (component (A)), for example, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer Polymer, ethylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-1-butene-1-hexene copolymer, Propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene-1-hexene copolymer A polymer etc. are mentioned.
非晶性オレフィン系重合体（成分（Ａ））として、好ましくは、プロピレンとエチレンおよび炭素原子数４〜２０のα−オレフィンからなる群から選ばれた少なくとも一種のオレフィンを共重合して得られる非晶性オレフィン系重合体である。例えば、プロピレン−１−ブテン共重合体、プロピレン−１−ヘキセン共重合体、プロピレン−１−オクテン共重合体、プロピレン−４−メチル−１−ペンテン共重合体、プロピレン−１−ブテン−１−ヘキセン共重合体等が挙げられ、より好ましくは、プロピレン−１−ブテン共重合体、プロピレン−エチレン−１−ブテン共重合体である。 The amorphous olefin polymer (component (A)) is preferably obtained by copolymerizing at least one olefin selected from the group consisting of propylene, ethylene and an α-olefin having 4 to 20 carbon atoms. It is an amorphous olefin polymer. For example, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene-1- A hexene copolymer etc. are mentioned, More preferably, they are a propylene-1-butene copolymer and a propylene-ethylene-1-butene copolymer.
非晶性オレフィン系重合体（成分（Ａ））は、エチレンおよび炭素原子数３〜２０のα−オレフィン以外の単量体から誘導される構造単位を含有していてもよく、エチレンおよび炭素原子数３〜２０のα−オレフィン以外の単量体としては、環状オレフィン、ビニル芳香族化合物、ポリエン化合物等が挙げられる。 The amorphous olefin polymer (component (A)) may contain a structural unit derived from a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the monomer other than the α-olefin having 3 to 20 include cyclic olefin, vinyl aromatic compound, polyene compound and the like.
非晶性オレフィン系重合体（成分（Ａ））として、好ましい非晶性オレフィン系重合体であるプロピレンとエチレンおよび炭素原子数４〜２０のα−オレフィンからなる群から選ばれた少なくとも一種のオレフィンを共重合して得られる非晶性オレフィン系重合体に含有されるプロピレンから誘導される構造単位の含有量は、粘着剤用組成物の粘着力を高めるという観点から、好ましくは５０モル％以上であり、より好ましくは７０モル％以上であり、さらに好ましくは８０モル％以上である（但し、非晶性オレフィン系重合体（成分（Ａ））に含有される単量体から誘導される構造単位の合計を１００モル％とする）。 As the amorphous olefin polymer (component (A)), at least one olefin selected from the group consisting of propylene, ethylene, and α-olefin having 4 to 20 carbon atoms, which is a preferable amorphous olefin polymer. The content of the structural unit derived from propylene contained in the amorphous olefin polymer obtained by copolymerizing is preferably 50 mol% or more from the viewpoint of increasing the adhesive strength of the pressure-sensitive adhesive composition. More preferably, it is 70 mol% or more, more preferably 80 mol% or more (provided that the structure is derived from the monomer contained in the amorphous olefin polymer (component (A)). The total unit is 100 mol%).
非晶性オレフィン系重合体（成分（Ａ））として、好ましくは、粘着剤用組成物の粘着力を高めるという観点から、示差走査熱量測定（以下、ＤＳＣと称する）によって、−１００〜２００℃に観測される結晶の融解熱量が１Ｊ／ｇ以上である融解ピーク、および、結晶化熱量が１Ｊ／ｇ以上である結晶化ピークのいずれもが観測されない重合体である。 As an amorphous olefin polymer (component (A)), preferably, from the viewpoint of increasing the adhesive strength of the pressure-sensitive adhesive composition, it is −100 to 200 ° C. by differential scanning calorimetry (hereinafter referred to as DSC). In this polymer, neither a melting peak with a crystal heat of fusion of 1 J / g or more nor a crystallization peak with a heat of crystallization of 1 J / g or more is observed.
非晶性オレフィン系重合体（成分（Ａ））の１３５℃のテトラリン中で測定される極限粘度［η］として、好ましくは、被着体への糊残りを少なくし、被着体への汚染性を少なくするという観点や、溶融混練時の加工性を良好にするという観点から、０．５〜１０ｄｌ／ｇであり、より好ましくは１．５〜５ｄｌ／ｇである。 As the intrinsic viscosity [η] measured in tetralin at 135 ° C. of the amorphous olefin polymer (component (A)), it is preferable to reduce the adhesive residue on the adherend and to contaminate the adherend. From the viewpoint of reducing the property and improving the workability during melt kneading, it is 0.5 to 10 dl / g, and more preferably 1.5 to 5 dl / g.
非晶性オレフィン系重合体（成分（Ａ））の分子量分布（Ｍｗ／Ｍｎ）は、被着体への糊残りを少なくするという観点から、好ましくは４以下であり、より好ましくは３以下である。ここで、非晶性ポリオレフィン系重合体の分子量分布（Ｍｗ／Ｍｎ）は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）によって測定される重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）から求められる値である。 The molecular weight distribution (Mw / Mn) of the amorphous olefin polymer (component (A)) is preferably 4 or less, more preferably 3 or less, from the viewpoint of reducing adhesive residue on the adherend. is there. Here, the molecular weight distribution (Mw / Mn) of the amorphous polyolefin polymer is a value obtained from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). It is.
非晶性オレフィン系重合体（成分（Ａ））の製造方法としては、公知のチーグラー・ナッタ型触媒や公知のシングルサイト触媒を用いて製造する方法が挙げられる。耐傷付き性や耐熱性をより高めるという観点から、好ましくは、公知のシングルサイト触媒を用いる製造方法である。 Examples of the method for producing the amorphous olefin polymer (component (A)) include a method using a known Ziegler-Natta type catalyst or a known single site catalyst. From the viewpoint of further improving scratch resistance and heat resistance, a production method using a known single-site catalyst is preferred.
シングルサイト触媒としては、メタロセン系触媒や非メタロセン系の錯体触媒が挙げられる。メタロセン系触媒としては、例えば、特開昭５８−１９３０９号公報、特開昭６０−３５００５号公報、特開昭６０−３５００６号公報、特開昭６０−３５００７号公報、特開昭６０−３５００８号公報、特開昭６１−１３０３１４号公報、特開平３−１６３０８８号公報、特開平４−２６８３０７号公報、特開平９−１２７９０号公報、特開平９−８７３１３号公報、特開平１１−８０２３３号公報、特表平１０−５０８０５５号公報等に記載のメタロセン系触媒が挙げられる。 Examples of the single site catalyst include metallocene catalysts and nonmetallocene complex catalysts. Examples of the metallocene catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008. JP, JP 61-130314, JP 3-163088, JP 4-268307, JP 9-12790, JP 9-87313, JP 11-80233. And metallocene catalysts described in JP-A-10-508055 and the like.
また、非メタロセン系の錯体触媒としては、例えば、特開平１０−３１６７１０号公報、特開平１１−１００３９４号公報、特開平１１−８０２２８号公報、特開平１１−８０２２７号公報、特表平１０−５１３４８９号公報、特開平１０−３３８７０６号公報、特開表１１−７１４２０号公報等に記載の非メタロセン系の錯体触媒が挙げられる。 Examples of the nonmetallocene complex catalyst include, for example, JP-A-10-316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, and JP-T-10-. Non-metallocene complex catalysts described in JP-A-513489, JP-A-10-338706, JP-A-11-71420 and the like can be mentioned.
シングルサイト触媒の中でも、好ましくは、入手が容易であるという観点から、メタロセン系触媒が好ましく、より好ましくは、少なくとも１個のシクロペンタジエン形アニオン骨格を有し、Ｃ1対掌構造を有する周期表第３族〜第１２族の遷移金属錯体を含むメタロセン系触媒である。
また、メタロセン触媒を用いた製造方法の例として、欧州特許出願公開第１２１１２８７号明細書に記載の方法が挙げられる。
Among the single site catalysts, a metallocene catalyst is preferable from the viewpoint of easy availability, and more preferably a periodic table having at least one cyclopentadiene-type anion skeleton and having a C 1 enantiomeric structure. It is a metallocene catalyst containing a Group 3 to Group 12 transition metal complex.
In addition, as an example of a production method using a metallocene catalyst, there is a method described in European Patent Application No. 1211287.
エチレン系重合体（成分（Ｂ））は、示差走査熱量測定によって、−１００〜２００℃に観測される最大の結晶融解ピークの温度（以下、Ｔｍ（℃）と称する）が１２０℃以下のエチレン系重合体である。例えば、エチレン−α−オレフィン共重合体、エチレン−エチレン系不飽和エステル共重合体等が挙げられる。
エチレン−α−オレフィン共重合体に用いられるα−オレフィンとしては、鎖状オレフィンが挙げられ、鎖状オレフィンとしては、直鎖状オレフィンや分岐状オレフィンが挙げられる。
直鎖状オレフィンとしては、例えば、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−へプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−ノナデセン、１−エイコセン等が挙げられ、分岐状オレフィンとしては、例えば、３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、２−エチル−１−ヘキセン、２，２，４−トリメチル−１−ペンテン等が挙げられる。
エチレン−α−オレフィン共重合体に用いられるα−オレフィンとして、好ましくは、１−ブテン、１−ヘキセンである。
The ethylene-based polymer (component (B)) is ethylene having a maximum crystal melting peak temperature (hereinafter referred to as Tm (° C.) observed at −100 to 200 ° C. measured by differential scanning calorimetry at 120 ° C. or lower. Based polymer. Examples thereof include an ethylene-α-olefin copolymer and an ethylene-ethylenically unsaturated ester copolymer.
Examples of the α-olefin used in the ethylene-α-olefin copolymer include a chain olefin, and examples of the chain olefin include a linear olefin and a branched olefin.
Examples of the linear olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- Examples include tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like. Examples of branched olefins include 3-methyl-1-butene, Examples include 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene and the like.
The α-olefin used in the ethylene-α-olefin copolymer is preferably 1-butene or 1-hexene.
エチレン−エチレン系不飽和エステル共重合体に用いられるエチレン系不飽和エステルとしては、酢酸ビニルやα，β−不飽和カルボン酸アルキルエステルが挙げられる。
α，β−不飽和カルボン酸アルキルエステルとしては、炭素原子数が３〜８個の不飽和カルボン酸のアルキルエステルが挙げられ、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸ｔ−ブチル、アクリル酸イソブチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸イソブチル等が挙げられる。
エチレン−エチレン系不飽和エステル共重合体に用いられるエチレン系不飽和エステルとして、好ましくは、酢酸ビニル、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、メタクリル酸メチルである。
Examples of the ethylenically unsaturated ester used in the ethylene-ethylenically unsaturated ester copolymer include vinyl acetate and α, β-unsaturated carboxylic acid alkyl esters.
Examples of α, β-unsaturated carboxylic acid alkyl esters include alkyl esters of unsaturated carboxylic acids having 3 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic Isopropyl acid, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methacryl Examples include isobutyl acid.
The ethylenically unsaturated ester used for the ethylene-ethylenically unsaturated ester copolymer is preferably vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, or methyl methacrylate.
エチレン系重合体（成分（Ｂ））として用いられるエチレン−α−オレフィン共重合体またはエチレン−エチレン系不飽和エステル共重合体には、市販のものを用いても良い。
市販のエチレン−α−オレフィン共重体としては、例えば、住友化学工業（株）製エチレン−１−ヘキセン共重合体（製品名：エクセレンＦＸ、グレード名：ＣＸ４００２、Ｔｍ＝６８℃）や、住友化学工業（株）製エチレン−１−ブテン共重合体（製品名：エクセレンＦＸ、グレード名：ＣＸ３５０２、Ｔｍ＝７０℃）が挙げられる。
また、市販のエチレン−エチレン系不飽和エステル共重合体としては、例えば、住友化学工業（株）製エチレン−メタクリル酸メチル共重合体（製品名：アクリフト、グレード名：ＷＨ３０２、Ｔｍ＝９４℃、またはグレード名：ＷＨ３０３、Ｔｍ＝８９℃）が挙げられる。
A commercially available product may be used as the ethylene-α-olefin copolymer or ethylene-ethylenically unsaturated ester copolymer used as the ethylene polymer (component (B)).
Examples of commercially available ethylene-α-olefin copolymers include ethylene-1-hexene copolymer (product name: Excellen FX, grade name: CX4002, Tm = 68 ° C.) manufactured by Sumitomo Chemical Co., Ltd., Sumitomo Chemical Co., Ltd. An ethylene-1-butene copolymer (product name: Excellen FX, grade name: CX3502, Tm = 70 ° C.) manufactured by Kogyo K.K.
Moreover, as a commercially available ethylene-ethylenically unsaturated ester copolymer, for example, an ethylene-methyl methacrylate copolymer manufactured by Sumitomo Chemical Co., Ltd. (product name: ACRlift, grade name: WH302, Tm = 94 ° C., Or grade name: WH303, Tm = 89 ° C.).
エチレン系重合体（成分（Ｂ））の示差走査熱量測定によって、−１００〜２００℃に観測される最大の結晶融解ピークの温度（Ｔｍ（℃））は１２０℃以下であり、好ましくは２０℃〜１００℃である。Ｔｍが１２０℃を超えた場合、結晶性が高くなり、粘着剤組成物の低温環境下での粘着力が低下することがある。 According to differential scanning calorimetry of the ethylene polymer (component (B)), the maximum crystal melting peak temperature (Tm (° C.)) observed at −100 to 200 ° C. is 120 ° C. or less, preferably 20 ° C. ~ 100 ° C. When Tm exceeds 120 ° C., the crystallinity becomes high, and the adhesive strength of the adhesive composition in a low temperature environment may be reduced.
エチレン系重合体（成分（Ｂ））のメルトフローレート（以下、ＭＦＲ（ｇ／１０分）と称する）は、被着体への糊残りを少なくし、被着体への汚染性を少なくするという観点や、溶融混練時の加工性を良好にするという観点から、通常０．１〜５０ｇ／１０分であり、好ましくは０．５〜３０ｇ／１０分である。
なお、エチレン系重合体（成分（Ｂ））のＭＦＲは、ＪＩＳ Ｋ６７６０−１９８１に従い、温度１９０℃、荷重２１．１８Ｎで測定されるものである。
The melt flow rate of the ethylene polymer (component (B)) (hereinafter referred to as MFR (g / 10 minutes)) reduces the amount of adhesive residue on the adherend and reduces the contamination on the adherend. From the viewpoint of improving the workability during melt-kneading, it is usually 0.1 to 50 g / 10 minutes, preferably 0.5 to 30 g / 10 minutes.
The MFR of the ethylene polymer (component (B)) is measured at a temperature of 190 ° C. and a load of 21.18 N according to JIS K6760-1981.
本発明の粘着剤用組成物は、非晶性オレフィン系重合体（成分（Ａ））９５〜９９．９重量％と、エチレン系重合体（成分（Ｂ））０．１〜５重量％とを含有する粘着用組成物である（但し、粘着用組成物の全量を１００重量％とする）。成分（Ａ）および成分（Ｂ）の含有量として、好ましくは、成分（Ａ）９７〜９９．７重量％および成分（Ｂ）０．３〜３重量％であり、より好ましくは成分（Ａ）９８〜９９．５重量％および成分（Ｂ）０．５〜２重量％である。
成分（Ｂ）の含有量が０．１重量％未満の場合や５重量％を超えた場合、低温環境下での良好な粘着力が得られないことがある。
The pressure-sensitive adhesive composition of the present invention comprises an amorphous olefin polymer (component (A)) 95 to 99.9% by weight, an ethylene polymer (component (B)) 0.1 to 5% by weight, (However, the total amount of the pressure-sensitive adhesive composition is 100% by weight). The content of component (A) and component (B) is preferably 97 to 99.7% by weight of component (A) and 0.3 to 3% by weight of component (B), more preferably component (A). 98 to 99.5% by weight and component (B) 0.5 to 2% by weight.
When the content of the component (B) is less than 0.1% by weight or exceeds 5% by weight, good adhesive strength in a low temperature environment may not be obtained.
本発明の粘着剤用組成物には、必要に応じて、公知の方法によって、イオウ架橋、過酸化物架橋、金属イオン架橋、シラン架橋、樹脂架橋、電子線架橋等の架橋を施しても良い。
架橋剤としては、例えば、硫黄、フェノール樹脂、金属酸化物、金属水酸化物、金属塩化物、ｐ−キノンジオキシム、ビスマレイミド系の架橋剤が例示される。
架橋速度を調節するために、架橋剤と架橋促進剤とを組合せて用いても良い。架橋促進剤としては、例えば、鉛丹、ジベンゾチアゾイルサルファイド等の酸化剤が例示される。
また、架橋剤と分散剤とを組合せて用いても良い。分散剤としては、例えば、金属酸化物やステアリン酸等が例示される。分散剤として用いられる金属酸化物としては、例えば、酸化亜鉛、酸化マグネシウム、酸化鉛、酸化カルシウム等が例示され、好ましくは、酸化亜鉛、酸化マグネシウムである。
そして、本発明の粘着剤用組成物には、架橋剤の存在下で動的架橋を施しても良い。
The pressure-sensitive adhesive composition of the present invention may be subjected to cross-linking such as sulfur cross-linking, peroxide cross-linking, metal ion cross-linking, silane cross-linking, resin cross-linking, electron beam cross-linking, etc., if necessary. .
Examples of the crosslinking agent include sulfur, phenol resin, metal oxide, metal hydroxide, metal chloride, p-quinonedioxime, and bismaleimide-based crosslinking agent.
In order to adjust the crosslinking rate, a crosslinking agent and a crosslinking accelerator may be used in combination. Examples of the crosslinking accelerator include oxidants such as red lead and dibenzothiazoyl sulfide.
Moreover, you may use combining a crosslinking agent and a dispersing agent. Examples of the dispersant include metal oxide and stearic acid. Examples of the metal oxide used as the dispersant include zinc oxide, magnesium oxide, lead oxide, and calcium oxide, and zinc oxide and magnesium oxide are preferable.
And the composition for adhesives of this invention may give dynamic bridge | crosslinking in presence of a crosslinking agent.
本発明の粘着剤用組成物の製造方法としては、例えば、各成分を、ラバーミル、ブラベンダーミキサー、バンバリーミキサー、加圧ニーダー、一軸および二軸押出機等の通常の混練り装置で混練する方法が例示される。
混練り装置としては、密閉式または開放式のいずれの形式であっても良く、好ましくは不活性ガスによって置換し得る密閉式装置である。
混練り温度は、通常１２０〜２５０℃、好ましくは１４０〜２４０℃である。混練り時間は、用いられる成分の種類や量、および、混練り装置の種類に応じて適宜決定すれば良く、加圧ニーダーやバンバリーミキサー等の混練り装置を使用する場合、通常、約３〜１０分である。
混練り工程で混練する方法としては、例えば、各成分を一括して混練する方法や、各成分の一部を混練りした後、残部を添加して混練りを継続する多段分割混練り法が例示される。
As a method for producing the composition for pressure-sensitive adhesives of the present invention, for example, each component is kneaded by a usual kneading apparatus such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a single screw or a twin screw extruder, or the like. Is exemplified.
The kneading apparatus may be either a closed type or an open type, and is preferably a closed type apparatus that can be replaced with an inert gas.
The kneading temperature is usually 120 to 250 ° C, preferably 140 to 240 ° C. The kneading time may be appropriately determined according to the type and amount of the components used and the type of the kneading apparatus. When a kneading apparatus such as a pressure kneader or a Banbury mixer is used, it is usually about 3 to 3. 10 minutes.
As a method of kneading in the kneading step, for example, a method of kneading each component at once, or a multistage division kneading method in which a part of each component is kneaded and then the remainder is added and kneading is continued. Illustrated.
本発明の粘着剤用組成物には、必要に応じて、本発明で用いられる非晶性オレフィン系重合体（成分（Ａ））およびエチレン系重合体（成分（Ｂ））以外の他の樹脂を添加しても良い。他の樹脂としては、例えば、ロジン系樹脂、ポリテルペン系樹脂、合成石油樹脂、クマロン系樹脂、フェノール系樹脂、キシレン系樹脂、スチレン系樹脂、イソプレン系樹脂等が例示される。 In the composition for pressure-sensitive adhesives of the present invention, if necessary, other resins other than the amorphous olefin polymer (component (A)) and ethylene polymer (component (B)) used in the present invention. May be added. Examples of other resins include rosin resins, polyterpene resins, synthetic petroleum resins, coumarone resins, phenol resins, xylene resins, styrene resins, and isoprene resins.
本発明の粘着剤用組成物には、必要に応じて、安定剤、添加剤、充填剤、鉱物油系軟化剤等を添加しても良い。
安定剤としては、例えば、老化防止剤、酸化防止剤、オゾン劣化防止剤、紫外線吸収剤、光安定剤等が挙げられ、添加剤としては、例えば、帯電防止剤、スリップ剤、難燃剤、着色剤、アンチブロッキング剤、滑剤、防曇剤等が挙げられ、充填剤としては、例えば、ガラス繊維、炭素繊維、金属繊維、ガラスビーズ、マイカ、炭酸カルシウム、チタン酸カリウムウィスカー、タルク、アラミド繊維、硫酸バリウム、ガラスフレーク、フッ素樹脂等が挙げられ、鉱物油系軟化剤としては、例えば、ナフテン油、パラフィン系鉱物油等が挙げられる。
You may add a stabilizer, an additive, a filler, a mineral oil type softening agent, etc. to the composition for adhesives of this invention as needed.
Examples of the stabilizer include an anti-aging agent, an antioxidant, an ozone deterioration preventing agent, an ultraviolet absorber, and a light stabilizer. Examples of the additive include an anti-static agent, a slip agent, a flame retardant, and a coloring agent. Agents, anti-blocking agents, lubricants, anti-fogging agents, etc., and fillers include, for example, glass fibers, carbon fibers, metal fibers, glass beads, mica, calcium carbonate, potassium titanate whiskers, talc, aramid fibers, Examples thereof include barium sulfate, glass flakes, and fluororesins. Examples of the mineral oil softener include naphthenic oil and paraffinic mineral oil.
本発明の粘着剤用組成物の用途としては、例えば、フィルムやシートが挙げられ、本発明の粘着剤用組成物を含有するフィルムやシートを単独で用いても良く、基材層と少なくとも一つの他の層を有する積層体に含まれる他の層として用いても良い。 Applications of the pressure-sensitive adhesive composition of the present invention include, for example, a film and a sheet, and the film or sheet containing the pressure-sensitive adhesive composition of the present invention may be used alone, and at least one of the base material layer and the base material layer. You may use as another layer contained in the laminated body which has two other layers.
積層体に含まれる基材層としては、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリメチルペンテン系樹脂、ポリスチレン系樹脂、エチレンとアクリル酸系モノマーとの共重合体樹脂、エチレン−酢酸ビニル共重合体樹脂、エチレン−メタクリル酸系モノマー共重合体樹脂、アクリル樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ナイロン系樹脂、ポリビニルアルコール系樹脂等が挙げられる。また、クラフト紙、不織布等が挙げられる。但し、基材層として用いられるポリエチレン系樹脂、ポリプロピレン系樹脂は、本発明で用いられる非晶性オレフィン系重合体（成分（Ａ））およびエチレン系重合体（成分（Ｂ））以外の樹脂である。
基材層として、好ましくは、粘着層と共押出しによって、安価に積層体を製造するという観点から、ポリエチレン系樹脂、ポリプロピレン系樹脂、またはこれらの混合物である。
また、基材層に用いられる樹脂には、必要に応じて、基材層の表面に滑り性を付与するために、離型剤等の添加剤を添加しても良い。
Examples of the base material layer included in the laminate include polyethylene resin, polypropylene resin, polymethylpentene resin, polystyrene resin, copolymer resin of ethylene and acrylic acid monomer, ethylene-vinyl acetate copolymer Examples include coalesced resins, ethylene-methacrylic acid monomer copolymer resins, acrylic resins, polyester resins, polycarbonate resins, nylon resins, polyvinyl alcohol resins, and the like. Moreover, a kraft paper, a nonwoven fabric, etc. are mentioned. However, the polyethylene resin and polypropylene resin used as the base material layer are resins other than the amorphous olefin polymer (component (A)) and ethylene polymer (component (B)) used in the present invention. is there.
The base material layer is preferably a polyethylene resin, a polypropylene resin, or a mixture thereof from the viewpoint of inexpensively producing a laminate by coextrusion with the adhesive layer.
Moreover, you may add additives, such as a mold release agent, in order to provide slipperiness to the surface of a base material layer as needed to resin used for a base material layer.
積層体の基材層は、単層であっても良く、少なくとも２層からなる多層であっても良い。
基材層の表面には、周知の表面処理法によって、表面処理が施されていても良く、表面処理法としては、例えば、コロナ放電処理、プラズマ処理、フレーム処理、電子線照射処理、紫外線照射処置等が挙げられる。
基材層は、無色透明の層であっても良く、着色された層または印刷された層であっても良い。
The substrate layer of the laminate may be a single layer or a multilayer composed of at least two layers.
The surface of the base material layer may be surface-treated by a well-known surface treatment method. Examples of the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, electron beam irradiation treatment, and ultraviolet irradiation. Treatment etc. are mentioned.
The base material layer may be a colorless and transparent layer, or may be a colored layer or a printed layer.
基材層は、必要に応じて、一軸方向または二軸方向に延伸されていても良い。一軸延伸の好ましい方法としては、通常用いられているロール延伸法が例示される。また、二軸延伸の方法としては、例えば、一軸延伸の後に二軸延伸を行う逐次延伸法や、チューブラ延伸法等の同時二軸延伸法が例示される。 The base material layer may be extended in a uniaxial direction or a biaxial direction as necessary. As a preferred method of uniaxial stretching, a commonly used roll stretching method is exemplified. Examples of the biaxial stretching method include a sequential stretching method in which biaxial stretching is performed after uniaxial stretching, and a simultaneous biaxial stretching method such as a tubular stretching method.
本発明の粘着剤用組成物を含む粘着剤層を有する積層体は、基材層の片面に粘着剤層を有する積層体であっても良く、基材層の両面に粘着剤層を有する積層体であっても良い。 The laminate having the pressure-sensitive adhesive layer containing the composition for pressure-sensitive adhesives of the present invention may be a laminate having a pressure-sensitive adhesive layer on one side of the base material layer, or a laminate having pressure-sensitive adhesive layers on both sides of the base material layer. It may be the body.
本発明の粘着剤用組成物を含む粘着剤層を有する積層体の製造方法としては、例えば、基材層と粘着剤層とを共押出する方法や押出コーティングする方法（「押出ラミネート法」ともいう）が例示される。前記の共押出する方法や押出コーティングする方法に用いられる装置としては、例えば、インフレーションフィルム製造装置やＴダイフィルム製造装置が例示される。 Examples of the method for producing a laminate having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition of the present invention include a method of co-extrusion of a base material layer and a pressure-sensitive adhesive layer, and a method of extrusion coating (also referred to as “extrusion lamination method”). Is exemplified). Examples of the apparatus used for the above-described coextrusion method and extrusion coating method include an inflation film manufacturing apparatus and a T-die film manufacturing apparatus.
本発明の粘着剤用組成物を含む粘着剤層を有する積層体の厚さは、通常０．００１〜５ｍｍであり、好ましくは０．００５〜２ｍｍである。基材層および粘着剤層のそれぞれの厚さは、被着体の種類や、粘着フィルムに要求される物性（例えば、粘着強度等）に応じて決めれば良い。 The thickness of the laminated body which has an adhesive layer containing the composition for adhesives of this invention is 0.001-5 mm normally, Preferably it is 0.005-2 mm. The thickness of each of the base material layer and the pressure-sensitive adhesive layer may be determined according to the type of adherend and physical properties required for the pressure-sensitive adhesive film (for example, pressure-sensitive adhesive strength).
本発明の粘着剤用組成物を含む粘着剤層を有する積層体を、重ね巻きされた巻物として製造する場合、巻物からの粘着フィルムの引き出し易さ、すなわち自己剥離性という観点から、巻物中に剥離紙を挟んだり、基材層の背面に剥離剤を塗布したりしても良い。
剥離剤としては、シリコーン系剥離剤、非シリコーン系剥離剤等が例示され、シリコーン系剥離剤としては、熱硬化型シリコーン系剥離剤、光硬化型シリコーン系剥離剤、シリコーンポリマーと他ポリマーとの共重合体剥離剤、シリコーンポリマーと他ポリマーとのブレンド系剥離剤が例示される。非シリコーン系剥離剤としては、長鎖アルキルポリマーや、ポリオレフィンや、フッ素化合物を主成分とする剥離剤が例示される。
When producing a laminate having a pressure-sensitive adhesive layer containing the composition for pressure-sensitive adhesives of the present invention as a rolled-up roll, from the viewpoint of ease of pulling out the pressure-sensitive adhesive film from the roll, that is, from the viewpoint of self-peeling, A release paper may be sandwiched, or a release agent may be applied to the back surface of the base material layer.
Examples of the release agent include silicone release agents and non-silicone release agents. Examples of silicone release agents include thermosetting silicone release agents, photocurable silicone release agents, silicone polymers and other polymers. Examples thereof include a copolymer release agent and a blend release agent of a silicone polymer and another polymer. Examples of the non-silicone release agent include release agents mainly composed of long-chain alkyl polymers, polyolefins, and fluorine compounds.
本発明の粘着剤用組成物を含む粘着剤層を有する積層体の用途としては、例えば、低温環境下や寒冷地で使用される金属板や樹脂板等の保護フィルム、表示用マーキングフィルム等が挙げられる。 The use of the laminate having the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition of the present invention includes, for example, protective films such as metal plates and resin plates used in low-temperature environments and cold regions, marking films for display, etc. Can be mentioned.
以下、実施例、および比較例によって本発明をさらに詳細に説明する。
本発明の物性測定は、以下の方法で行った。
（１）非晶性オレフィン系重合体の単量体組成（単量体含有量、単位：モル％）
核磁気共鳴装置（Ｂｒｕｋｅｒ社製 商品名ＡＣ−２５０）を用いて、13Ｃ−ＮＭＲスペクトルの測定結果に基づき算出した。具体的には、13Ｃ−ＮＭＲスペクトルにおいて、プロピレン単位由来のメチル炭素のスペクトル強度と１−ブテン単位由来のメチル炭素スペクトルとの強度比からプロピレン単位と１−ブテン単位の組成比を算出した。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The physical properties of the present invention were measured by the following method.
(1) Monomer composition of amorphous olefin polymer (monomer content, unit: mol%)
It calculated based on the measurement result of a < 13 > C-NMR spectrum using the nuclear magnetic resonance apparatus (Bruker brand name AC-250). Specifically, in the 13 C-NMR spectrum, the composition ratio of the propylene unit and the 1-butene unit was calculated from the intensity ratio of the methyl carbon spectrum derived from the propylene unit and the methyl carbon spectrum derived from the 1-butene unit.
（２）極限粘度（［η］、単位：ｄｌ／ｇ）
１３５℃において、ウベローデ粘度計を用いて行った。テトラリン単位体積あたりの非晶性オレフィン系重合体の濃度ｃが、０．６、１．０、１．５ｍｇ／ｍｌである非晶性オレフィン系重合体のテトラリン溶液を調整し、１３５℃における極限粘度を測定した。それぞれの濃度で３回繰り返し測定し、得られた３回の値の平均値をその濃度での比粘度（ηsp）とし、ηsp／ｃのｃをゼロ外挿した値を極限粘度［η］として求めた。
(2) Intrinsic viscosity ([η], unit: dl / g)
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. A tetralin solution of an amorphous olefin polymer having an amorphous olefin polymer concentration c per unit volume of tetralin of 0.6, 1.0, 1.5 mg / ml was prepared, and the limit at 135 ° C. The viscosity was measured. The measurement was repeated three times at each concentration, and the average value of the three values obtained was taken as the specific viscosity (η sp ) at that concentration, and the value obtained by extrapolating c of η sp / c to zero was used as the intrinsic viscosity [η ].
（３）分子量分布
ゲルパーミエイションクロマトグラフ（ＧＰＣ）法によって、下記の条件で測定を行った。
装置 ：Ｗａｔｅｒｓ社製 １５０Ｃ ＡＬＣ／ＧＰＣ
カラム ：昭和電工社製Ｓｈｏｄｅｘ Ｐａｃｋｅｄ ＣｏｌｕｍｎＡ−８０Ｍ
２本
温度 ：１４０℃
溶媒 ：ｏ−ジクロロベンゼン
溶出溶媒流速：１．０ｍｌ／ｍｉｎ
試料濃度：１ｍｇ／ｍｌ
測定注入量：４００μｌ
分子量標準物質：標準ポリスチレン
検出器 ：示差屈折
(3) Molecular weight distribution It measured by the gel permeation chromatograph (GPC) method on the following conditions.
Apparatus: 150C ALC / GPC manufactured by Waters
Column: Shodex Packed Column A-80M manufactured by Showa Denko KK
Two temperature: 140 ° C
Solvent: o-dichlorobenzene elution solvent flow rate: 1.0 ml / min
Sample concentration: 1 mg / ml
Measurement injection volume: 400 μl
Molecular weight reference material: Standard polystyrene detector: Differential refraction
（４）結晶融解ピーク（単位：℃）、結晶融解熱量（単位：Ｊ／ｇ）、結晶化ピーク（単位：℃）、結晶化熱量（単位：Ｊ／ｇ）
示差走査熱量計（セイコー電子工業社製ＤＳＣ２２０Ｃ：入力補償ＤＳＣ）を用い以下の条件で測定した。
（i）試料約５ｍｇを室温から３０℃／分の昇温速度で２００℃まで昇温し、昇温完了後、５分間保持した。
（ii）次いで、２００℃から１０℃／分の降温速度で−１００℃まで降温し、降温完了後、５分間、保持した。この（ii）で観察されるピークが結晶化ピークであり、ピーク面積が１Ｊ／ｇ以上の結晶化ピークの有無を確認した。
（iii）次いで、−１００℃から１０℃／分の昇温速度で２００℃まで昇温した。この（iii）で観察されるピークが結晶の融解ピークであり、ピーク面積が１Ｊ／ｇ以上の融解ピークの有無を確認した。
(4) Crystal melting peak (unit: ° C), crystal melting heat (unit: J / g), crystallization peak (unit: ° C), crystallization heat (unit: J / g)
It measured on condition of the following using the differential scanning calorimeter (Seiko Electronics Co., Ltd. DSC220C: input compensation DSC).
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a temperature increase rate of 30 ° C./min, and held for 5 minutes after the temperature increase was completed.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed. The peak observed in (ii) was a crystallization peak, and the presence or absence of a crystallization peak with a peak area of 1 J / g or more was confirmed.
(Iii) Next, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The peak observed in (iii) was a melting peak of crystals, and the presence or absence of a melting peak having a peak area of 1 J / g or more was confirmed.
（５）粘着力（剥離強度、単位：Ｎ／２５ｍｍ幅）
ＪＩＳ−Ｚ−０２３７に従い、粘着剤層と基材層とからなる積層体とＳＵＳ３０４鋼板の１８０度引き剥がしたときの剥離強度を、−１０℃ならびに２３℃雰囲気下において測定した。
(5) Adhesive strength (peel strength, unit: N / 25 mm width)
According to JIS-Z-0237, the peel strength when the laminate composed of the pressure-sensitive adhesive layer and the base material layer and the SUS304 steel plate were peeled 180 degrees was measured in an atmosphere of −10 ° C. and 23 ° C.
（６）被着体への汚染性
前項の剥離強度測定後、被着体表面を目視で観察し、外観の汚染による曇りの有無を評価した。
(6) Contamination to the adherend After the peel strength measurement in the previous section, the adherend surface was visually observed to evaluate the presence or absence of cloudiness due to contamination of the appearance.
実施例１
［１］非晶性ポリオレフィン系重合体の製造
攪拌機を備えた１００ＬのＳＵＳ製重合器中で、プロピレンと１−ブテンとを、分子量調節として水素を用い、以下の方法で連続的に共重合させて、本発明の非晶性ポリオレフィン系重合体にあたるプロピレン−１−ブテン共重合体を得た。
重合器の下部から、重合溶媒としてのヘキサンを１００Ｌ／時間の供給速度で、プロピレンを２４．００Ｋｇ／時間の供給速度で、１−ブテンを１．８１Ｋｇ／時間の供給速度で、それぞれ連続的に供給した。
重合器の上部から、重合器中の反応混合物が１００Ｌの量を保持するように、反応混合物を連続的に抜き出した。
重合器の下部から、重合触媒の成分として、ジメチルシリル（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタニウムジクロライドを０．００５ｇ／時間の供給速度で、トリフェニルメチルテトラキス（ペンタフルオロフェニル）ボレートを０．２９８ｇ／時間の供給速度で、トリイソブチルアルミニウムを２．３１５ｇ／時間の供給速度で、それぞれ連続的に供給した。
共重合反応は、重合器の外部に取り付けられたジャケットに冷却水を循環させることによって、４５℃で行った。
重合器の上部から連続的に抜き出された反応混合物に少量のエタノールを添加して重合反応を停止させた後、脱モノマー及び水洗浄をし、次いで、大量の水中でスチームによって溶媒を除去することによって、プロピレン−１−ブテン共重合体を得、これを８０℃で一昼夜減圧乾燥した。得られた共重合体の生成速度は７．１０Ｋｇ／時間であった。
得られたプロピレン−１−ブテン共重合体の物性評価結果を表１に示した。
Example 1
[1] Production of Amorphous Polyolefin Polymer In a 100 L SUS polymerizer equipped with a stirrer, propylene and 1-butene were continuously copolymerized by the following method using hydrogen as a molecular weight control. Thus, a propylene-1-butene copolymer corresponding to the amorphous polyolefin polymer of the present invention was obtained.
From the lower part of the polymerization vessel, hexane as a polymerization solvent was continuously fed at a feeding rate of 100 L / hour, propylene was fed at a feeding rate of 24.00 Kg / hour, and 1-butene was fed at a feeding rate of 1.81 Kg / hour. Supplied.
From the top of the polymerization vessel, the reaction mixture was continuously withdrawn so that the reaction mixture in the polymerization vessel maintained an amount of 100 L.
From the lower part of the polymerization vessel, as a component of the polymerization catalyst, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride is supplied at a rate of 0.005 g / hour, Triphenylmethyltetrakis (pentafluorophenyl) borate was continuously fed at a feed rate of 0.298 g / hr and triisobutylaluminum was fed at a feed rate of 2.315 g / hr.
The copolymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
A small amount of ethanol is added to the reaction mixture continuously withdrawn from the top of the polymerization vessel to stop the polymerization reaction, followed by demonomerization and water washing, and then the solvent is removed by steam in a large amount of water. Thus, a propylene-1-butene copolymer was obtained, and this was dried under reduced pressure at 80 ° C. overnight. The production rate of the obtained copolymer was 7.10 kg / hour.
The physical property evaluation results of the resulting propylene-1-butene copolymer are shown in Table 1.
［２］粘着剤用組成物の製造
成分（Ａ）として上記方法によって製造された非晶性プロピレン−１−ブテン共重合体９９重量％と、成分（Ｂ）としてエチレン−１−ヘキセン共重合体（住友化学工業（株）製 商品名：エクセレンＦＸ、グレード名：ＣＸ４００２、ＭＦＲ（１９０℃／２１．１８Ｎ荷重）＝８ｇ／１０分、Ｔｍ＝６８℃）１重量％とを配合し、ブラベンダー社製の商品名がプラスチコーダーＰＬＶ１５１型なる混練機を用い、スクリュー回転数１０ｒｐｍにて、２００℃で２分間混練した後、次いで、更に、１００ｒｐｍにて５分間混練し、粘着剤用組成物を得た。
[2] Production of composition for pressure-sensitive adhesive 99% by weight of an amorphous propylene-1-butene copolymer produced by the above method as component (A), and ethylene-1-hexene copolymer as component (B) (Sumitomo Chemical Co., Ltd. product name: Excellen FX, grade name: CX4002, MFR (190 ° C / 21.18N load) = 8 g / 10 min, Tm = 68 ° C.) 1% by weight, Brabender Using a kneader whose product name is PLASTICADER PLV151, manufactured by the company, kneaded at 200 ° C. for 2 minutes at a screw speed of 10 rpm, and then further kneaded at 100 rpm for 5 minutes to obtain an adhesive composition. Obtained.
［３］粘着フィルムの製造
基材層としてポリプロピレン樹脂（住友化学工業（株）製 商品名：エクセレンＥＰＸ、グレード名：ＥＰ３７２５、ＭＦＲ（２３０℃／２１．１８Ｎ荷重）＝２．５ｇ／１０分、Ｔｍ＝１４４℃）を用い、粘着層として前記［２］で製造した粘着剤組成物を用い、それぞれを厚さ１００μｍのフィルムに成形した後、両者を張り合わせ、次いで、１５０℃プレス成形で加熱融着させて積層体を得た。この積層体の物性を表２に示した。
[3] Production of adhesive film Polypropylene resin (Sumitomo Chemical Co., Ltd., trade name: Excelen EPX, grade name: EP3725, MFR (230 ° C / 21.18N load) = 2.5 g / 10 min as a base material layer, Tm = 144 ° C.), using the pressure-sensitive adhesive composition produced in [2] above as an adhesive layer, forming each into a film having a thickness of 100 μm, bonding them together, and then heat-melting by press molding at 150 ° C. A laminate was obtained by wearing. The physical properties of this laminate are shown in Table 2.
実施例２
実施例１の［２］で用いた成分（Ａ）の配合量を９９．５重量％、成分（Ｂ）の配合量を０．５重量％に変更した以外は、実施例１と同様にして積層体を得た。この積層体の物性を表２に示した。
Example 2
Except for changing the blending amount of the component (A) used in [2] of Example 1 to 99.5% by weight and the blending amount of the component (B) to 0.5% by weight, the same as in Example 1. A laminate was obtained. The physical properties of this laminate are shown in Table 2.
実施例３
実施例１の［２］で用いた成分（Ｂ）を、エチレン−１−ブテン共重合体（住友化学工業（株）製 商品名：エクセレンＦＸ、グレード名：ＣＸ３５０２、ＭＦＲ（１９０℃／２１．１８Ｎ荷重）＝４ｇ／１０分、Ｔｍ＝７０℃）に変更した以外は、実施例１と同様にして積層体を得た。この積層体の物性を表２に示した。
Example 3
The component (B) used in [2] of Example 1 was replaced with an ethylene-1-butene copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen FX, grade name: CX3502, MFR (190 ° C./21.1°C). 18N load) = 4 g / 10 min, Tm = 70 ° C.) A laminate was obtained in the same manner as in Example 1. The physical properties of this laminate are shown in Table 2.
比較例１
実施例１の［２］で用いた成分（Ａ）の配合量を８５重量％、成分（Ｂ）の配合量を１５重量％に変更した以外は、実施例１と同様にして積層体を得た。この積層体の物性を表２に示した。
Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that the amount of component (A) used in [2] of Example 1 was changed to 85% by weight and the amount of component (B) was changed to 15% by weight. It was. The physical properties of this laminate are shown in Table 2.
比較例２
実施例１の［２］で用いた成分（Ｂ）を、プロピレン−エチレンランダム共重合体（住友化学工業（株）製 商品名：住友ノーブレン、グレード名：ＦＳ２０１１ＤＧ２、ＭＦＲ（２３０℃／２１．１８Ｎ荷重）＝２．５ｇ／１０分、Ｔｍ＝１５８℃）に変更した以外は、実施例１と同様にして積層体を得た。この積層体の物性を表２に示した。
Comparative Example 2
Component (B) used in [2] of Example 1 was replaced with a propylene-ethylene random copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumitomo Nobrene, grade name: FS2011DG2, MFR (230 ° C./21.18N). A laminate was obtained in the same manner as in Example 1 except that the load was changed to 2.5 g / 10 min and Tm = 158 ° C. The physical properties of this laminate are shown in Table 2.
本発明の要件を満足する実施例１〜３に用いた粘着剤用組成物は、低温環境下（−１０℃）での粘着力が高く、被着体への汚染性が少ない粘着剤用組成物であることが分かる。
これに対して、比較例１は、本発明の要件、すなわち、エチレン系重合体（成分（Ｂ））の含有量に関する要件を満足しない粘着剤用組成物であり、−１０℃および２３℃のいいずれにおいても、剥離強度が不充分で、粘着力が低いものであることが分かる。
また、比較例２は、本発明の要件、すなわち、エチレン系重合体（成分（Ｂ））の示差走査熱量測定によって、−１００〜２００℃に観測される最大の結晶融解ピークの温度に関する要件を満足しない粘着剤用組成物であり、−１０℃での剥離強度が不充分で、低温環境下（−１０℃）での粘着力が低いものであることが分かる。
The pressure-sensitive adhesive composition used in Examples 1 to 3 that satisfies the requirements of the present invention has a high pressure-sensitive adhesive force in a low-temperature environment (−10 ° C.) and has little contamination to the adherend. It turns out that it is a thing.
In contrast, Comparative Example 1 is a pressure-sensitive adhesive composition that does not satisfy the requirements of the present invention, that is, the requirements regarding the content of the ethylene polymer (component (B)). In any case, it can be seen that the peel strength is insufficient and the adhesive strength is low.
Comparative Example 2 is a requirement of the present invention, that is, a requirement regarding the temperature of the maximum crystal melting peak observed at −100 to 200 ° C. by differential scanning calorimetry of the ethylene polymer (component (B)). It can be seen that this is an unsatisfactory composition for pressure-sensitive adhesives, has insufficient peel strength at −10 ° C., and low pressure-sensitive adhesive strength at low temperatures (−10 ° C.).
Claims (3)
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| JP2004244758A JP2006063123A (en) | 2004-08-25 | 2004-08-25 | Adhesive composition |
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| JP2004244758A JP2006063123A (en) | 2004-08-25 | 2004-08-25 | Adhesive composition |
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| WO2008093805A1 (en) * | 2007-02-02 | 2008-08-07 | Mitsui Chemicals, Inc. | Adhesive and multilayer body using the same |
| JP2009299021A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film |
| JP2009299019A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film |
| JP2009299020A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film |
| JP2009299022A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film roll |
| JP2013163774A (en) * | 2012-02-13 | 2013-08-22 | Nitto Denko Corp | Adhesive tape |
| WO2013183600A1 (en) * | 2012-06-04 | 2013-12-12 | 出光興産株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using same |
| WO2014069604A1 (en) * | 2012-11-02 | 2014-05-08 | 出光興産株式会社 | Adhesive composition and adhesive tape using same |
| JP2015004003A (en) * | 2013-06-21 | 2015-01-08 | 日東電工株式会社 | Adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008093805A1 (en) * | 2007-02-02 | 2008-08-07 | Mitsui Chemicals, Inc. | Adhesive and multilayer body using the same |
| JP5261196B2 (en) * | 2007-02-02 | 2013-08-14 | 三井化学株式会社 | Adhesive and laminate using the same |
| US8445582B2 (en) | 2007-02-02 | 2013-05-21 | Mitsui Chemicals, Inc. | Adhesive and multilayer structure having the same |
| JP2009299020A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film |
| JP2009299022A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film roll |
| JP2009299019A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film |
| JP2009299021A (en) * | 2008-04-23 | 2009-12-24 | Toyobo Co Ltd | Pressure-sensitive adhesive film |
| JP2013163774A (en) * | 2012-02-13 | 2013-08-22 | Nitto Denko Corp | Adhesive tape |
| WO2013183600A1 (en) * | 2012-06-04 | 2013-12-12 | 出光興産株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using same |
| WO2014069604A1 (en) * | 2012-11-02 | 2014-05-08 | 出光興産株式会社 | Adhesive composition and adhesive tape using same |
| JPWO2014069604A1 (en) * | 2012-11-02 | 2016-09-08 | 出光興産株式会社 | Adhesive composition and pressure-sensitive adhesive tape using the same |
| JP2015004003A (en) * | 2013-06-21 | 2015-01-08 | 日東電工株式会社 | Adhesive sheet |
| JP2022180481A (en) * | 2018-04-18 | 2022-12-06 | クラリアント・インターナシヨナル・リミテツド | Permanently tacky adhesive with improved environmental compatibility |
| US11851587B2 (en) | 2018-04-18 | 2023-12-26 | Clariant International Ltd | Permanently tacky adhesives with improved environmental compatibility |
| JP7431910B2 (en) | 2018-04-18 | 2024-02-15 | クラリアント・インターナシヨナル・リミテツド | Permanent adhesive pressure sensitive adhesive with improved environmental compatibility |
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