JP2021130731A - Aqueous emulsion type adhesive composition and adhesive tape - Google Patents
Aqueous emulsion type adhesive composition and adhesive tape Download PDFInfo
- Publication number
- JP2021130731A JP2021130731A JP2020024950A JP2020024950A JP2021130731A JP 2021130731 A JP2021130731 A JP 2021130731A JP 2020024950 A JP2020024950 A JP 2020024950A JP 2020024950 A JP2020024950 A JP 2020024950A JP 2021130731 A JP2021130731 A JP 2021130731A
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- JP
- Japan
- Prior art keywords
- mass
- adhesive composition
- sensitive adhesive
- pressure
- parts
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 106
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 51
- 239000000839 emulsion Substances 0.000 title abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 72
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 31
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 31
- 229920001194 natural rubber Polymers 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 30
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 23
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 21
- 239000005060 rubber Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 109
- 239000000463 material Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 7
- 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 claims description 7
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 26
- 238000002156 mixing Methods 0.000 description 17
- 239000004014 plasticizer Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- -1 sulfate ester Chemical class 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000011256 inorganic filler Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
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- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- DECACTMEFWAFRE-UHFFFAOYSA-N 6-o-benzyl 1-o-octyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCC1=CC=CC=C1 DECACTMEFWAFRE-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- WXZOXVVKILCOPG-UHFFFAOYSA-N bis(2-ethylhexyl) benzene-1,3-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC(C(=O)OCC(CC)CCCC)=C1 WXZOXVVKILCOPG-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- KLIYQWXIWMRMGR-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate Chemical compound C=CC=C.COC(=O)C(C)=C KLIYQWXIWMRMGR-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 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
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- AAGYFUHJQIVPIX-UHFFFAOYSA-N 2-methylpentan-2-yl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)CCC AAGYFUHJQIVPIX-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
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- 238000005299 abrasion Methods 0.000 description 1
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
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- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
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- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
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- 239000012933 diacyl peroxide Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- HCIBTBXNLVOFER-UHFFFAOYSA-N diphenylcyclopropenone Chemical compound O=C1C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 HCIBTBXNLVOFER-UHFFFAOYSA-N 0.000 description 1
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- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 description 1
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- 239000000944 linseed oil Substances 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
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- 239000012188 paraffin wax Substances 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- GULAEPPQYOTQDE-UHFFFAOYSA-N phthalic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)C1=CC=CC=C1C(O)=O GULAEPPQYOTQDE-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
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- 229920001083 polybutene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
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- 239000011112 polyethylene naphthalate Substances 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、水系のエマルジョン型粘着剤組成物及び粘着テープに関する。 The present invention relates to an aqueous emulsion type pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape.
従来、自動車の配線には、電線類を粘着テープ等で所定の形状に束ねたものが用いられている。このような電線類の結束用の粘着テープには、長期間電線類を結束できる高い粘着力が求められる。
粘着テープの粘着力を向上させる方法として、粘着付与樹脂を配合した粘着剤組成物を用いる方法が知られている。このような粘着剤組成物は、粘着剤と粘着付与樹脂とを、有機溶剤中で相溶化させることが多いため、揮発性有機化合物（ＶＯＣ）が多量に発生する。そのため、環境への負荷が大きいという問題がある。
Conventionally, as wiring for automobiles, electric wires bundled in a predetermined shape with adhesive tape or the like have been used. Such an adhesive tape for binding electric wires is required to have a high adhesive force capable of binding electric wires for a long period of time.
As a method for improving the adhesive strength of the adhesive tape, a method using an adhesive composition containing an adhesive resin is known. In such a pressure-sensitive adhesive composition, the pressure-sensitive adhesive and the pressure-imparting resin are often compatible with each other in an organic solvent, so that a large amount of volatile organic compounds (VOCs) are generated. Therefore, there is a problem that the load on the environment is large.
ところで、エンジン周り等、高温になりやすい環境下に配置される電線類の粘着テープには、上記の粘着力の他、高い耐熱性能も要求される。耐熱性の低い粘着テープを用いた場合、電線に巻き付けた粘着テープの端部が剥がれるという問題が生じる。粘着テープの耐熱性を向上させるために、架橋処理を施した粘着剤組成物（例えば、特許文献１等）を用いる方法が知られている。しかしながら、前記架橋処理は、一般にトルエン等の有機溶剤中で行われるため、やはりＶＯＣによる環境負荷の問題がある。
このようなＶＯＣによる問題を生じにくい粘着剤組成物として、粘着剤成分を水系バインダー中に分散させた水系エマルジョン型の粘着剤組成物も知られている。しかしながら、このような粘着剤組成物は一般に耐熱性が低く、前述の高温になりやすい環境下で使用されるワイヤーハーネス用粘着テープには、適用が難しいという問題がある。
By the way, in addition to the above-mentioned adhesive strength, high heat resistance is also required for the adhesive tape of electric wires arranged in an environment where the temperature tends to be high, such as around an engine. When an adhesive tape having low heat resistance is used, there arises a problem that the end portion of the adhesive tape wound around the electric wire is peeled off. In order to improve the heat resistance of the adhesive tape, a method using a crosslinked pressure-sensitive adhesive composition (for example, Patent Document 1 and the like) is known. However, since the cross-linking treatment is generally performed in an organic solvent such as toluene, there is still a problem of environmental load due to VOC.
As a pressure-sensitive adhesive composition that is less likely to cause such problems due to VOC, an water-based emulsion-type pressure-sensitive adhesive composition in which a pressure-sensitive adhesive component is dispersed in an water-based binder is also known. However, such an adhesive composition generally has low heat resistance, and has a problem that it is difficult to apply to the above-mentioned adhesive tape for a wire harness used in an environment where a high temperature is likely to occur.
そこで本発明は、高い粘着力と耐熱性能とを有し、環境への負荷が小さい水系のエマルジョン型粘着剤組成物及び前記水系のエマルジョン型粘着剤組成物を用いた粘着テープの提供を目的とする。 Therefore, an object of the present invention is to provide an aqueous emulsion type pressure-sensitive adhesive composition having high adhesive strength and heat resistance performance and having a small impact on the environment, and an adhesive tape using the water-based emulsion type pressure-sensitive adhesive composition. do.
上記課題に対して、本願発明者らは鋭意検討した結果、特定の粘着剤成分と、特定のゲル分率とを有する水系のエマルジョン型粘着剤組成物を用いることで、水系であっても、高い粘着力と高い耐熱性能とを発現できることを見出し、本発明を完成させるに至った。
すなわち、本発明は、以下の態様を有する。
［１］天然ゴム５〜４０質量部及び合成ゴム６０〜９５質量部を含むゴム成分１００質量部と、粘着付与樹脂７０〜１３０質量部と、界面活性剤０．１〜５質量部と、架橋剤５〜３０質量部とを含む、水系のエマルジョン型粘着剤組成物であって、前記水系のエマルジョン型粘着剤組成物のゲル分率が３０〜５０％である、水系のエマルジョン型粘着剤組成物。
［２］前記架橋剤が、硫黄系架橋剤である、［１］に記載の水系のエマルジョン型粘着剤組成物。
［３］前記天然ゴムのゲル分率が、７０〜１００％である［１］または［２］に記載の水系のエマルジョン型粘着剤組成物。
［４］前記合成ゴムが、スチレン−ブタジエンゴムを含む、［１］から［３］のいずれか一項に記載の水系のエマルジョン型粘着剤組成物。
［５］前記スチレン−ブタジエンゴムのスチレン比率が２０〜５０質量％である［４］に記載の水系のエマルジョン型粘着剤組成物。
［６］前記スチレン−ブタジエンゴムのゲル分率が０〜２０％である、［４］または［５］に記載の水系のエマルジョン型粘着剤組成物。
［７］前記粘着付与樹脂が、石油樹脂、ロジン樹脂、及びテルペン樹脂からなる群より選択される少なくとも１つの樹脂であり、数平均分子量が３００〜３０００である、［１］から［６］のいずれか一項に記載の水系のエマルジョン型粘着剤組成物。
［８］［１］から［７］のいずれか一項に記載の水系のエマルジョン型粘着剤組成物より得られる粘着剤層を、基材の少なくとも一方の面に備える、粘着テープ。
［９］前記基材が、塩化ビニル系樹脂を含む樹脂で構成されている、［８］に記載の粘着テープ。
As a result of diligent studies on the above problems, the inventors of the present application have used an aqueous emulsion-type pressure-sensitive adhesive composition having a specific pressure-sensitive adhesive component and a specific gel fraction, so that even if it is water-based, it can be used. We have found that high adhesive strength and high heat resistance can be exhibited, and have completed the present invention.
That is, the present invention has the following aspects.
[1] Crosslinking with 100 parts by mass of a rubber component containing 5 to 40 parts by mass of natural rubber and 60 to 95 parts by mass of synthetic rubber, 70 to 130 parts by mass of a tackifier resin, and 0.1 to 5 parts by mass of a surfactant. An aqueous emulsion-type pressure-sensitive adhesive composition containing 5 to 30 parts by mass of an agent, wherein the gel content of the water-based emulsion-type pressure-sensitive adhesive composition is 30 to 50%. thing.
[2] The aqueous emulsion-type pressure-sensitive adhesive composition according to [1], wherein the cross-linking agent is a sulfur-based cross-linking agent.
[3] The water-based emulsion-type pressure-sensitive adhesive composition according to [1] or [2], wherein the gel content of the natural rubber is 70 to 100%.
[4] The water-based emulsion-type pressure-sensitive adhesive composition according to any one of [1] to [3], wherein the synthetic rubber contains a styrene-butadiene rubber.
[5] The water-based emulsion-type pressure-sensitive adhesive composition according to [4], wherein the styrene ratio of the styrene-butadiene rubber is 20 to 50% by mass.
[6] The aqueous emulsion-type pressure-sensitive adhesive composition according to [4] or [5], wherein the styrene-butadiene rubber has a gel fraction of 0 to 20%.
[7] The tackifier resin is at least one resin selected from the group consisting of petroleum resin, rosin resin, and terpene resin, and has a number average molecular weight of 300 to 3000, according to [1] to [6]. The aqueous emulsion-type pressure-sensitive adhesive composition according to any one of the above.
[8] An adhesive tape provided with an adhesive layer obtained from the aqueous emulsion-type adhesive composition according to any one of [1] to [7] on at least one surface of a base material.
[9] The adhesive tape according to [8], wherein the base material is made of a resin containing a vinyl chloride resin.
本発明によれば、高い粘着力と耐熱性能とを有し、環境への負荷が小さい水系のエマルジョン型粘着剤組成物及び前記水系のエマルジョン型粘着剤組成物を用いた粘着テープを提供できる。 According to the present invention, it is possible to provide an aqueous emulsion type pressure-sensitive adhesive composition having high adhesive strength and heat resistance performance and having a small load on the environment, and an adhesive tape using the water-based emulsion type pressure-sensitive adhesive composition.
以下、本発明を詳細に説明するが、本発明は以下の態様に限定されるものではない。
［水系のエマルジョン型粘着剤組成物］
本発明の１つの態様は、天然ゴム５〜４０質量部及び合成ゴム６０〜９５質量部を含むゴム成分１００質量部と、粘着付与樹脂７０〜１３０質量部と、界面活性剤０．１〜５質量部と、架橋剤５〜３０質量部とを含む、水系のエマルジョン型粘着剤組成物であって、前記水系のエマルジョン型粘着剤組成物のゲル分率が３０〜５０％である、水系のエマルジョン型粘着剤組成物である。なお、本明細書において「水系のエマルジョン型」とは、水を含む分散媒を用いたエマルジョンのことを意味する。
Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following aspects.
[Aqueous emulsion type adhesive composition]
One aspect of the present invention is 100 parts by mass of a rubber component including 5 to 40 parts by mass of natural rubber and 60 to 95 parts by mass of synthetic rubber, 70 to 130 parts by mass of a tackifier resin, and 0.1 to 5 parts of a surfactant. An aqueous emulsion-type pressure-sensitive adhesive composition containing 5 to 30 parts by mass of a cross-linking agent, wherein the gel content of the water-based emulsion-type pressure-sensitive adhesive composition is 30 to 50%. It is an emulsion type pressure-sensitive adhesive composition. In addition, in this specification, "water-based emulsion type" means an emulsion using a dispersion medium containing water.
本発明の粘着剤組成物は、水系のエマルジョン型粘着剤組成物（以下、単に「粘着剤組成物」と記載することもある）である。本発明の粘着剤組成物は、揮発性有機化合物（ＶＯＣ）を用いない。そのため、本発明の粘着剤組成物より得られる粘着テープは、環境への負荷が小さい。
また、本発明の粘着剤組成物は、そのゲル分率が３０〜５０％の範囲に調整されている。これにより、水系のエマルジョン型粘着剤組成物でありながら、高い耐熱性を発現することができる。粘着剤組成物のゲル分率は、４０〜５０％であることがより好ましい。
粘着剤組成物のゲル分率は、トルエン不溶分測定によって求めた値のことを指す。
また、本発明の１つの態様において、粘着剤組成物の固形分は、４０〜６０％であることが好ましい。固形分が４０〜６０％であれば、塗工性が良好となる。
以下、粘着剤組成物の各成分について説明する。
なお、本明細書において、各成分の配合量は特に断りのない限り、固形分換算での値である。
The pressure-sensitive adhesive composition of the present invention is a water-based emulsion-type pressure-sensitive adhesive composition (hereinafter, may be simply referred to as “pressure-sensitive adhesive composition”). The pressure-sensitive adhesive composition of the present invention does not use a volatile organic compound (VOC). Therefore, the adhesive tape obtained from the pressure-sensitive adhesive composition of the present invention has a small impact on the environment.
Further, the pressure-sensitive adhesive composition of the present invention has a gel fraction adjusted to a range of 30 to 50%. As a result, high heat resistance can be exhibited even though it is an aqueous emulsion type pressure-sensitive adhesive composition. The gel fraction of the pressure-sensitive adhesive composition is more preferably 40 to 50%.
The gel fraction of the pressure-sensitive adhesive composition refers to a value obtained by measuring the insoluble toluene.
Further, in one aspect of the present invention, the solid content of the pressure-sensitive adhesive composition is preferably 40 to 60%. When the solid content is 40 to 60%, the coatability is good.
Hereinafter, each component of the pressure-sensitive adhesive composition will be described.
In the present specification, the blending amount of each component is a value in terms of solid content unless otherwise specified.
＜ゴム成分＞
本発明の粘着剤組成物はゴム成分を含む。ゴム成分は粘着剤成分であり、天然ゴムと合成ゴムとを含む。本発明の１つの態様において、ゴム成分は、天然ゴムと合成ゴムとからなることが好ましい。
天然ゴムとしては、本発明の効果を有する限り特に限定されないが、例えば、固形分が６０質量％の天然ゴムエマルジョン、固形分が６０質量％の架橋天然ゴムエマルジョン等を用いることができる。このような天然ゴムとしては、市販されているものを用いてもよく、例えば、（株）レヂテックス製の架橋天然ゴムエマルジョン（商品名「ＳＳ５８」）、（株）レヂテックス製の天然ゴムエマルジョン（商品名「ＨＡ ＬＡＴＥＸ」）等を用いることができる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
ゴム成分１００質量部中の天然ゴムの配合量は、５〜４０質量部であり、２０〜４０質量部がより好ましい。天然ゴムの配合量が５〜４０質量部であれば、高い保持力が得られやすくなる。
また、天然ゴムのゲル分率は、７０〜１００％であることが好ましく、７０〜９５％であることがより好ましく、８５〜９５％であることがさらに好ましい。天然ゴムのゲル分率が前記範囲内であれば、高い保持力が得られやすくなる。なお、天然ゴムのゲル分率は、後述のトルエン不溶分測定によって求めた値のことを指す。
<Rubber component>
The pressure-sensitive adhesive composition of the present invention contains a rubber component. The rubber component is an adhesive component and includes natural rubber and synthetic rubber. In one embodiment of the present invention, the rubber component is preferably composed of natural rubber and synthetic rubber.
The natural rubber is not particularly limited as long as it has the effect of the present invention, and for example, a natural rubber emulsion having a solid content of 60% by mass, a crosslinked natural rubber emulsion having a solid content of 60% by mass, and the like can be used. As such natural rubber, commercially available ones may be used, for example, a crosslinked natural rubber emulsion (trade name "SS58") manufactured by Reditex Co., Ltd., and a natural rubber emulsion manufactured by Reditex Co., Ltd. (commodity). The name "HA LATEX") and the like can be used. These may be used individually by 1 type, and may be used in combination of 2 or more type.
The blending amount of the natural rubber in 100 parts by mass of the rubber component is 5 to 40 parts by mass, more preferably 20 to 40 parts by mass. When the blending amount of the natural rubber is 5 to 40 parts by mass, a high holding power can be easily obtained.
The gel fraction of the natural rubber is preferably 70 to 100%, more preferably 70 to 95%, and even more preferably 85 to 95%. When the gel fraction of the natural rubber is within the above range, a high holding power can be easily obtained. The gel fraction of natural rubber refers to a value obtained by measuring the insoluble toluene, which will be described later.
合成ゴムとしては、例えば、ブタジエンゴム、イソプレンゴム、スチレン−ブタジエンゴム、アクリロニトリル−ブタジエンゴム、メタクリル酸メチル−ブタジエンゴム、イソブチレンゴム（ブチルゴム）、クロロプレンゴム、アクリルゴム等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。このうち、スチレン−ブタジエンゴムが、粘着力の観点から好ましい。また、スチレン比率が２０〜５０質量％のスチレン−ブタジエンゴムがより好ましい。
また、これら合成ゴムはエマルジョンであってもよい。合成ゴムのエマルジョンを用いる場合、固形分は４０〜６０％が好ましい。
ゴム成分１００質量部中の合成ゴムの配合量は、６０〜９５質量部であり、８０〜９５質量部がより好ましい。合成ゴムの配合量が６０〜９５質量部であれば、高い粘着力が得られる。
本発明の１つの態様において、合成ゴムのゲル分率は、０〜２０％が好ましく、０．５〜１０％がより好ましく、０．５〜５％がさらに好ましい。合成ゴムのゲル分率が前記範囲内であれば、架橋されやすく、高い保持力が得られやすくなる。なお、合成ゴムのゲル分率は、前述の天然ゴムのゲル分率と同様の方法で求めた値のことを指す。
本発明の１つの態様においては、前記合成ゴムとしてスチレン−ブタジエンゴムを用いることが好ましく、スチレン比率が２０〜５０質量％のスチレン−ブタジエンゴムを用いることが特に好ましい。
Examples of the synthetic rubber include butadiene rubber, isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, isobutylene rubber (butyl rubber), chloroprene rubber, acrylic rubber and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. Of these, styrene-butadiene rubber is preferable from the viewpoint of adhesive strength. Further, styrene-butadiene rubber having a styrene ratio of 20 to 50% by mass is more preferable.
Further, these synthetic rubbers may be emulsions. When a synthetic rubber emulsion is used, the solid content is preferably 40 to 60%.
The blending amount of the synthetic rubber in 100 parts by mass of the rubber component is 60 to 95 parts by mass, more preferably 80 to 95 parts by mass. When the blending amount of the synthetic rubber is 60 to 95 parts by mass, high adhesive strength can be obtained.
In one embodiment of the present invention, the gel fraction of the synthetic rubber is preferably 0 to 20%, more preferably 0.5 to 10%, still more preferably 0.5 to 5%. When the gel fraction of the synthetic rubber is within the above range, it is easy to be crosslinked and a high holding power can be easily obtained. The gel fraction of synthetic rubber refers to a value obtained by the same method as the gel fraction of natural rubber described above.
In one aspect of the present invention, it is preferable to use styrene-butadiene rubber as the synthetic rubber, and it is particularly preferable to use styrene-butadiene rubber having a styrene ratio of 20 to 50% by mass.
＜粘着付与樹脂＞
本発明の粘着剤組成物は、粘着付与樹脂を含む。粘着付与樹脂は、本発明の粘着剤組成物の粘着力を向上させる目的で配合される。
粘着付与樹脂としては、例えば、テルペン樹脂、ロジン樹脂、水添ロジン樹脂、クマロン・インデン樹脂、スチレン樹脂、脂肪族及び脂環族等の石油樹脂、水添した脂肪族及び脂環族などの石油樹脂、テルペン−フェノール樹脂、キシレン樹脂、その他の脂肪族炭化水素樹脂や芳香族炭化水素樹脂等が挙げられる。このうち、粘着剤組成物の粘着力がより向上しやすい観点から、石油樹脂、ロジン樹脂、及びテルペン樹脂からなる群より選択される少なくとも１つの樹脂であることが好ましい。
また、本発明の１つの態様において、粘着付与樹脂の数平均分子量が３００〜３０００であることが好ましい。数平均分子量が前記範囲内であれば、高い粘着力が得られやすくなる。また、数平均分子量が３００〜３０００の石油樹脂、ロジン樹脂、及びテルペン樹脂からなる群より選択される少なくとも１つの樹脂であることが特に好ましい。
<Adhesive-imparting resin>
The pressure-sensitive adhesive composition of the present invention contains a pressure-imparting resin. The tackifier resin is blended for the purpose of improving the adhesive strength of the pressure-sensitive adhesive composition of the present invention.
Examples of the tackifying resin include terpene resin, rosin resin, hydrocarbon rosin resin, kumaron inden resin, styrene resin, petroleum resins such as aliphatic and alicyclic groups, and petroleum such as hydrocarboned aliphatic and alicyclic groups. Examples thereof include resins, terpene-phenol resins, xylene resins, other aliphatic hydrocarbon resins and aromatic hydrocarbon resins. Of these, at least one resin selected from the group consisting of petroleum resin, rosin resin, and terpene resin is preferable from the viewpoint that the adhesive strength of the pressure-sensitive adhesive composition is more likely to be improved.
Further, in one aspect of the present invention, the number average molecular weight of the tackifier resin is preferably 300 to 3000. When the number average molecular weight is within the above range, high adhesive strength can be easily obtained. Further, it is particularly preferable that the resin is at least one selected from the group consisting of petroleum resins, rosin resins, and terpene resins having a number average molecular weight of 300 to 3000.
粘着剤組成物中の粘着付与剤の配合量は、ゴム成分１００質量部に対して、７０〜１３０質量部であり、１００〜１３０質量部であることがより好ましい。粘着付与剤の配合量が７０〜１３０質量部であれば、高い粘着力が得られる。 The blending amount of the tackifier in the pressure-sensitive adhesive composition is 70 to 130 parts by mass and more preferably 100 to 130 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount of the tackifier is 70 to 130 parts by mass, high adhesive strength can be obtained.
＜界面活性剤＞
本発明の粘着剤組成物は界面活性剤を含む。界面活性剤は、エマルジョンの安定化及び良好な塗工性付与の目的で配合される。
界面活性剤としては、例えば、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。但しアニオン性界面活性剤とカチオン系界面活性剤を併用することはお互いの効果を相殺するため好ましくない。本発明においては、水への分散性と乳化安定性、乾燥時の塗布不良（ハジキ等）が少ないことから、アニオン性界面活性剤であることが好ましい。アニオン性界面活性剤としては、例えば、スルホン酸系界面活性剤、硫酸エステル系界面活性剤、カルボン酸系界面活性剤等が挙げられる。このうち、乳化安定性の観点から、スルホン酸系界面活性剤がより好ましい。
粘着剤組成物中の界面活性剤の配合量は、ゴム成分１００質量部に対して、０．１〜５質量部であり、３〜５質量部がより好ましい。また、界面活性剤の配合量は、水分１００質量部に対し、０．１〜５質量部であり、１〜５質量部がより好ましい。界面活性剤の配合量がゴム成分１００質量部に対して０．１〜５質量部であれば、粘着力及び耐熱性能を損ねずに高い乳化安定性が得られる。また、水分１００質量部に対して０．１〜５質量部であれば、エマルジョンの高い貯蔵安定性と良好な塗工性が得られやすい。
<Surfactant>
The pressure-sensitive adhesive composition of the present invention contains a surfactant. Surfactants are blended for the purpose of stabilizing emulsions and imparting good coatability.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. However, it is not preferable to use an anionic surfactant and a cationic surfactant in combination because their effects cancel each other out. In the present invention, an anionic surfactant is preferable because of its dispersibility in water, emulsion stability, and less coating defects (repellency, etc.) during drying. Examples of the anionic surfactant include sulfonic acid-based surfactants, sulfate ester-based surfactants, carboxylic acid-based surfactants, and the like. Of these, a sulfonic acid-based surfactant is more preferable from the viewpoint of emulsion stability.
The blending amount of the surfactant in the pressure-sensitive adhesive composition is 0.1 to 5 parts by mass, more preferably 3 to 5 parts by mass, based on 100 parts by mass of the rubber component. The blending amount of the surfactant is 0.1 to 5 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of water. When the blending amount of the surfactant is 0.1 to 5 parts by mass with respect to 100 parts by mass of the rubber component, high emulsification stability can be obtained without impairing the adhesive strength and heat resistance performance. Further, if it is 0.1 to 5 parts by mass with respect to 100 parts by mass of water, high storage stability and good coatability of the emulsion can be easily obtained.
＜架橋剤＞
本発明の粘着剤組成物は架橋剤を含む。架橋剤を含むことで、粘着剤組成物のゲル分率を３０〜５０％の範囲に制御することができる。その結果、本発明の粘着剤組成物より得られる粘着テープの耐熱性が向上する。また、粘着力も向上する。
架橋剤としては、例えば、硫黄系化合物、有機過酸化物系化合物、イソシアネート系架橋剤、カルボジイミド系架橋剤等が挙げられる。
硫黄系化合物としては、例えば、硫黄、塩化硫黄、二塩化硫黄、高分子多硫化物、モルホリンジスルフィド（４，４’−ジチオジモルホリン）、アルキルフェノ−ルジスルフィド、テトラメチルチウラムジスルフィド、ジペンタメチレンチウラムテトラスルフィド、ジメチルジチオカルバミン酸セレン等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
有機過酸化物系化合物としては、例えば、ジアルキルパーオキサイド類（ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ブチルクミルパーオキサイド等）、ジアシルパーオキサイド類（ジベンゾイルパーオキサイド等）、ケトンパーオキサイド類（メチルエチルケトンパーオキサイド等）、アルキルパーエステル類（ｔ−ヘキシルペルオキシラウレート等）、パーオキシカーボネート類（ｔ−ブチルパーオキシイソプロピルカーボネート等）が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
イソシアネート系架橋剤としては、例えば、イソシアネート基を有する化合物であり、コアシェル構造等による親水性の外層によりイソシアネートを保護して保存安定性を高めた水分散性イソシアネートや、熱解離性を有するブロック剤でイソシアネートを保護したブロックイソシアネート等が挙げられる。水分散性イソシアネートの例には、三井化学（株）製のタケネートＷＤシリーズや、旭化成（株）製のデュラネートシリーズ、ＤＩＣ（株）製のバーノックシリーズなどが含まれる。ブロックイソシアネートの例には、Ｂａｘｅｎｄｅｎ社製のＡｑｕａ ＢＩ２００、Ａｑｕａ ＢＩ２２０などが含まれる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
カルボジイミド系架橋剤としては、カルボジイミド基を有する化合物であり、例えば、ポリカルボジイミド、ジシクロヘキシルカルポジイミド、ジイソプロピルカルポジイミド等が含まれる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
これら架橋剤のうち、保持力の観点から、硫黄系化合物（硫黄系架橋剤）が好ましく、、テトラチウラムジスルフィドがより好ましい。
粘着剤組成物中の架橋剤の配合量は、ゴム成分１００質量部に対して、５〜３０質量部であり、１５〜３０質量部がより好ましい。架橋剤の配合量が５〜３０質量部であれば、粘着剤組成物のゲル分率を３０〜５０％に調整でき、本発明の粘着剤組成物より得られる粘着テープの耐熱性能が向上する。また、粘着力も向上する。
<Crosslinking agent>
The pressure-sensitive adhesive composition of the present invention contains a cross-linking agent. By including the cross-linking agent, the gel fraction of the pressure-sensitive adhesive composition can be controlled in the range of 30 to 50%. As a result, the heat resistance of the adhesive tape obtained from the pressure-sensitive adhesive composition of the present invention is improved. In addition, the adhesive strength is also improved.
Examples of the cross-linking agent include sulfur-based compounds, organic peroxide-based compounds, isocyanate-based cross-linking agents, and carbodiimide-based cross-linking agents.
Examples of sulfur-based compounds include sulfur, sulfur chloride, sulfur dichloride, high molecular weight polysulfide, morpholini disulfide (4,4'-dithiodimorpholin), alkylphenol disulfide, tetramethylthiuram disulfide, and dipentamethylene. Examples thereof include thiuram tetrasulfide and selenium dimethyldithiocarbamate. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the organic peroxide compound include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, di-t-butyl cumyl peroxide, etc.), diacyl peroxides (dibenzoyl peroxide, etc.). ), Ketone peroxides (methyl ethyl ketone peroxide, etc.), alkyl peroxides (t-hexylperoxylaurate, etc.), peroxycarbonates (t-butylperoxyisopropyl carbonate, etc.). These may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the isocyanate-based cross-linking agent include water-dispersible isocyanates which are compounds having an isocyanate group and whose storage stability is enhanced by protecting the isocyanates with a hydrophilic outer layer having a core-shell structure or the like, or a blocking agent having thermal dissociation properties. Examples thereof include blocked isocyanate in which isocyanate is protected with. Examples of water-dispersible isocyanates include Takenate WD series manufactured by Mitsui Chemicals, Inc., Duranate series manufactured by Asahi Kasei Corporation, and Burnock series manufactured by DIC Corporation. Examples of blocked isocyanates include Baxenden's Aqua BI200, Aqua BI220 and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
The carbodiimide-based cross-linking agent is a compound having a carbodiimide group, and includes, for example, polycarbodiimide, dicyclohexylcarposiimide, diisopropylcarposiimide and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these cross-linking agents, sulfur-based compounds (sulfur-based cross-linking agents) are preferable, and tetrathiuram disulfide is more preferable, from the viewpoint of holding power.
The blending amount of the cross-linking agent in the pressure-sensitive adhesive composition is 5 to 30 parts by mass, more preferably 15 to 30 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount of the cross-linking agent is 5 to 30 parts by mass, the gel fraction of the pressure-sensitive adhesive composition can be adjusted to 30 to 50%, and the heat resistance performance of the pressure-sensitive adhesive tape obtained from the pressure-sensitive adhesive composition of the present invention is improved. .. In addition, the adhesive strength is also improved.
＜その他添加剤＞
本発明の粘着剤組成物は、本発明の効果を阻害しない範囲で、その他の添加剤を含んでいてもよい。その他の添加剤としては、例えば、増粘剤、軟化剤、表面潤滑剤、レベリング剤、酸化防止剤、腐食防止剤、光安定剤、紫外線吸収剤、耐熱安定剤、重合禁止剤、シランカップリンング剤、滑剤、無機又は有機の充填剤、金属粉、顔料等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
粘着剤組成物がその他の添加剤を含む場合、その合計量は、ゴム成分１００質量部に対して、０．２〜１０質量部であることが好ましい。
<Other additives>
The pressure-sensitive adhesive composition of the present invention may contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, thickeners, softeners, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, UV absorbers, heat stabilizers, polymerization inhibitors, silane cuprins. Examples include lubricants, lubricants, inorganic or organic fillers, metal powders, pigments and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
When the pressure-sensitive adhesive composition contains other additives, the total amount thereof is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the rubber component.
増粘剤としては、例えば、水溶性高分子増粘剤、会合型増粘剤等が挙げられる。水溶性高分子増粘剤を選択する場合、その配合量は、水分１００質量部に対して、０．１〜１０質量部が好ましい。会合型増粘剤を選択する場合、その配合量は、ゴム成分１００質量部に対して、０．２〜３質量部が好ましい。このうち、粘着剤塗工液の粘度の安定性の観点から、水溶性高分子増粘剤を含むことが好ましい。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the thickener include a water-soluble polymer thickener, an association type thickener and the like. When a water-soluble polymer thickener is selected, the blending amount thereof is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of water. When the association type thickener is selected, the blending amount thereof is preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component. Of these, from the viewpoint of the stability of the viscosity of the pressure-sensitive adhesive coating liquid, it is preferable to contain a water-soluble polymer thickener. These may be used individually by 1 type, and may be used in combination of 2 or more type.
本発明の粘着剤組成物は、その粘度が３０００〜９０００ｍＰａ・ｓ／２０℃であることが好ましい。前記範囲の粘度を有することにより、粘着テープを作成する際の塗工性が良好となりやすい。また、前記粘度は、Ｂ型粘度計によって求めた値のことを指す。
なお、本発明の粘着剤組成物は分散媒中に各成分が分散したエマルジョン型である。分散媒には水が含まれる。また、水のみを分散媒として用いることがより好ましい。
The pressure-sensitive adhesive composition of the present invention preferably has a viscosity of 3000 to 9000 mPa · s / 20 ° C. Having a viscosity in the above range tends to improve the coatability when producing an adhesive tape. Further, the viscosity refers to a value obtained by a B-type viscometer.
The pressure-sensitive adhesive composition of the present invention is an emulsion type in which each component is dispersed in a dispersion medium. The dispersion medium contains water. Further, it is more preferable to use only water as the dispersion medium.
［粘着剤組成物の製造方法］
本発明の粘着剤組成物は、前述のゴム成分、粘着付与樹脂、界面活性剤、架橋剤、及び必要に応じてその他添加剤を適宜選択して分散媒中に添加した後、混合する方法にて製造することができる。また、必要に応じて、適宜水を追加して、固形分及び粘度を調整してもよい。
[Manufacturing method of adhesive composition]
The pressure-sensitive adhesive composition of the present invention is used in a method in which the above-mentioned rubber component, pressure-sensitive resin, surfactant, cross-linking agent, and if necessary, other additives are appropriately selected and added to the dispersion medium, and then mixed. Can be manufactured. Further, if necessary, water may be added as appropriate to adjust the solid content and viscosity.
［粘着テープ］
本発明のその他の態様は、前記粘着剤組成物から得られる粘着剤層を、基材の少なくとも一方の面に備える、粘着テープである。本発明の粘着テープは、基材と、前記粘着剤組成物を前記基材の一方の面に塗工・乾燥することによって得られる粘着剤層とを備えるものである。本発明の粘着剤組成物から得られる粘着剤層を備える本発明の粘着テープは、高い粘着力及び耐熱性能を有し、環境への負荷が小さい。
以下、本発明の粘着テープについて詳細に説明する。
[Adhesive tape]
Another aspect of the present invention is an adhesive tape comprising a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition on at least one surface of a substrate. The pressure-sensitive adhesive tape of the present invention comprises a base material and a pressure-sensitive adhesive layer obtained by applying and drying the pressure-sensitive adhesive composition on one surface of the base material. The pressure-sensitive adhesive tape of the present invention provided with the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention has high adhesive strength and heat-resistant performance, and has a small burden on the environment.
Hereinafter, the adhesive tape of the present invention will be described in detail.
＜基材＞
本発明の粘着テープは、基材を備える。基材としては、各種の材料を各種用途に応じて適宜選択して用いることができる。例えば低密度ポリエチレン、直鎖状ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、超低密度ポリエチレン、ランダム共重合ポリプロピレン、ブロック共重合ポリプロピレン、ホモポリプロレン、ポリブテン、ポリメチルペンテン等のポリオレフィン、エチレン−酢酸ビニル共重合体、アイオノマー樹脂、エチレン−（メタ）アクリル酸共重合体、エチレン−（メタ）アクリル酸エステル（ランダム、交互）共重合体、エチレン−ブテン共重合体、エチレン−ヘキセン共重合体、ポリウレタン、ポリエチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル、ポリカーボネート、ポリイミド、ポリエーテルエーテルケトン、ポリイミド、ポリエーテルイミド、ポリアミド、全芳香族ポリアミド、ポリフェニルスルフィド、アラミド（紙）、ガラス、ガラスクロス、フッ素樹脂、塩化ビニル系樹脂、セルロース系樹脂、シリコーン樹脂、金属（箔）、紙等があげられる。
このうち、電線類等の結束用の粘着テープとして使用する場合、基材としては、塩化ビニル系樹脂が好ましい。
塩化ビニル系樹脂としては、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−エチレン共重合体、塩化ビニル−プロピレン共重合体等が挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらの中で、柔軟性、伸張性、及び成型加工性に優れ、かつ汎用的で安価に使用可能であることから、ポリ塩化ビニルが好ましい。
<Base material>
The adhesive tape of the present invention comprises a base material. As the base material, various materials can be appropriately selected and used according to various uses. For example, low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene and other polyolefins, ethylene-vinyl acetate. Copolymers, ionomer resins, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester (random, alternating) copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, polyurethanes , Polyester terephthalate, Polyethylene naphthalate and other polyesters, polycarbonate, polyimide, polyether ether ketone, polyimide, polyetherimide, polyamide, total aromatic polyamide, polyphenylsulfide, aramid (paper), glass, glass cloth, fluororesin, Examples thereof include vinyl chloride-based resins, cellulose-based resins, silicone resins, metals (foil), and paper.
Of these, when used as an adhesive tape for binding electric wires and the like, a vinyl chloride resin is preferable as the base material.
Examples of the vinyl chloride resin include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer and the like. One of these may be used alone, or two or more thereof may be used in combination. Among these, polyvinyl chloride is preferable because it has excellent flexibility, extensibility, and moldability, is versatile, and can be used inexpensively.
ポリ塩化ビニルの重合度は、本発明の効果を有する限り特に限定されないが、良好な加工性を得る観点から、平均重合度が５００〜４０００のものが好ましく、８００〜３０００のものがより好ましく、１０００〜２０００のものが特に好ましい。 The degree of polymerization of polyvinyl chloride is not particularly limited as long as it has the effect of the present invention, but from the viewpoint of obtaining good processability, the degree of polymerization is preferably 500 to 4000, more preferably 800 to 3000. Those of 1000 to 2000 are particularly preferable.
本発明の１つの態様において、基材は、可塑剤を含んでいてもよい。
可塑剤としては、フタル酸系可塑剤、イソフタル酸系可塑剤、テレフタル酸系可塑剤、アジピン酸系可塑剤及びそれらのポリエステル系可塑剤、リン酸系可塑剤、トリメリット酸系可塑剤、エポキシ系可塑剤等を使用することができる。
さらに具体的な例として、例えば、フタル酸ジイソニル（ＤＩＮＰ）、フタル酸ジヘプチル（ＤＨＰ）、フタル酸ジ−２−エチルヘキシル（ＤＯＰ）、フタル酸ジ−ｎ−オクチル（ｎ−ＤＯＰ）、フタル酸ジイソデシル（ＤＩＤＰ）、イソフタル酸ジ−２−エチルヘキシル（ＤＯＩＰ）、テレフタル酸ジ−２−エチルヘキシル（ＤＯＴＰ）、ベンジルブチルフタレート（ＢＢＰ）、トリメリット酸トリ−２−エチルヘキシル（ＴＯＴＭ）、アジピン酸ジ−２−エチルヘキシル（ＤＯＡ）、トリクレジルホスフェート（ＴＣＰ）、ベンジルオクチルアジペート（ＢＯＡ）、アジピン酸−プロピレングリコール系ポリエステル、アジピン酸−ブチレングリコール系ポリエステル、フタル酸−プロピレングリコール系ポリエステル、ジフェニルクレジルホスフェート（ＤＰＣＰ）、アジピン酸ジイソデシル、エポキシ化大豆油、エポキシ化アマニ油、塩素化パラフィン等が挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらのうち、耐熱性付与効果の高い、トリメリット酸系可塑剤が好ましく、ＴＯＴＭがより好ましい。
In one aspect of the invention, the substrate may contain a plasticizer.
Examples of plasticizers include phthalic acid-based plasticizers, isophthalic acid-based plasticizers, terephthalic acid-based plasticizers, adipic acid-based plasticizers and their polyester-based plasticizers, phosphoric acid-based plasticizers, trimellitic acid-based plasticizers, and epoxys. A plasticizer or the like can be used.
More specific examples include, for example, diisonyl phthalate (DINP), diheptyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate (n-DOP), diisodecyl phthalate. (DIDP), di-2-ethylhexyl isophthalate (DOIP), di-2-ethylhexyl terephthalate (DOTP), benzylbutylphthalate (BBP), tri-2-ethylhexyl trimeritate (TOTM), di-2 adipate -Ethylhexyl (DOA), tricresyl phosphate (TCP), benzyloctyl adipate (BOA), adipate-propylene glycol-based polyester, adipic acid-butylene glycol-based polyester, phthalate-propylene glycol-based polyester, diphenyl cresil phosphate ( DPCP), diisodecyl adipate, epoxidized soybean oil, epoxidized flaxseed oil, chlorinated paraffin and the like. One of these may be used alone, or two or more thereof may be used in combination. Of these, a trimellitic acid-based plasticizer having a high heat resistance-imparting effect is preferable, and TOTM is more preferable.
基材が可塑剤を含む場合、その配合量は、基材を構成する樹脂、例えば、塩化ビニル系樹脂１００質量部に対して２０〜１００質量部が好ましく、３０〜８０質量部がより好ましく、４０〜６０質量部がさらに好ましい。可塑剤の含有量が２０質量部以上であれば、粘着テープの伸張性が向上しやすくなり、電線や配線等を覆った後に被保護物を屈曲させやすくなる。可塑剤の含有量が１００質量部以下であれば、粘着テープの耐摩耗性が低下しにくい。また、耐熱性能が高くなりやすい。 When the base material contains a plasticizer, the blending amount thereof is preferably 20 to 100 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the resin constituting the base material, for example, a vinyl chloride resin. 40 to 60 parts by mass is more preferable. When the content of the plasticizer is 20 parts by mass or more, the extensibility of the adhesive tape is likely to be improved, and the protected object is easily bent after covering the electric wire, the wiring, or the like. When the content of the plasticizer is 100 parts by mass or less, the abrasion resistance of the adhesive tape is unlikely to decrease. In addition, the heat resistance performance tends to be high.
基材には、必要に応じて本発明の効果を阻害しない範囲で、無機充填剤、改質剤、及びその他添加剤等を配合することができる。その他添加剤としては、例えば、着色剤、安定剤、酸化防止剤、紫外線吸収剤、滑剤等が挙げられる。 If necessary, an inorganic filler, a modifier, and other additives can be added to the base material as long as the effects of the present invention are not impaired. Examples of other additives include colorants, stabilizers, antioxidants, ultraviolet absorbers, lubricants and the like.
前記無機充填剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化カルシウム、水酸化カリウム、水酸化バリウム、トリフェニルホスフィート、ポリリン酸アンモニウム、ポリリン酸アミド、酸化ジルコニウム、酸化マグネシウム、酸化亜鉛、酸化チタン、酸化モリブデン、リン酸グアニジン、ハイドロタルサイト、スネークタイト、硼酸亜鉛、無水硼酸亜鉛、メタ硼酸亜鉛、メタ硼酸バリウム、酸化アンチモン、三酸化アンチモン、五酸化アンチモン、赤燐、タルク、アルミナ、シリカ、ベーマイト、ベントナイト、珪酸ソーダ、珪酸カルシウム、硫酸カルシウム、炭酸カルシウム、炭酸マグネシウム、カーボンブラック等が挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。上記の無機充填剤のうち、タルク、アルミナ、シリカ、珪酸カルシウム、硫酸カルシウム、炭酸カルシウム、炭酸マグネシウムが好ましく、より好ましくは経済性に優れた炭酸カルシウムである。
前記無機充填剤は、天然物を粉砕して得られたものでもよく、水溶液等にしたものを中和させ析出して得られたものであっても良い。また、表面処理剤等で官能基を導入したものであってもよい。表面処理剤としては、例えば、脂肪酸、ロジン酸、リグニン酸、４級アンモニウム塩等が使用できる。
Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenylphosphite, ammonium polyphosphate, polyphosphate amide, zirconium oxide, and oxidation. Magnesium, zinc oxide, titanium oxide, molybdenum oxide, guanidine phosphate, hydrotalcite, snaketite, zinc borate, zinc anhydride borate, zinc metaborate, barium metaborate, antimony oxide, antimony trioxide, antimony pentoxide, red phosphorus , Tarku, alumina, silica, boehmite, bentonite, sodium silicate, calcium silicate, calcium sulfate, calcium carbonate, magnesium carbonate, carbon black and the like. One of these may be used alone, or two or more thereof may be used in combination. Among the above-mentioned inorganic fillers, talc, alumina, silica, calcium silicate, calcium sulfate, calcium carbonate, and magnesium carbonate are preferable, and calcium carbonate having excellent economic efficiency is more preferable.
The inorganic filler may be obtained by crushing a natural product, or may be obtained by neutralizing and precipitating an aqueous solution or the like. Further, it may be one in which a functional group is introduced by a surface treatment agent or the like. As the surface treatment agent, for example, fatty acid, rosin acid, lignin acid, quaternary ammonium salt and the like can be used.
前記改質剤としては、例えば、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−エチレン共重合体、塩化ビニル−プロピレン共重合体、塩素化ポリエチレン、塩素化ポリ塩化ビニル、エチレン−酢酸ビニル共重合体、アクリロニトリル−ブタジエン−スチレン共重合体、メチルメタクリレート−ブタジエン−スチレン共重合体、アクリロニトリル−ブタジエン共重合体、メチルメタクリレート−ブチルアクリレート共重合体、熱可塑性ポリウレタン、ポリエステル系熱可塑性エラストマー等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the modifier include vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, chlorinated polyethylene, chlorinated polyvinyl chloride, and ethylene-vinyl acetate copolymer. Examples thereof include coalescence, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, methyl methacrylate-butyl acrylate copolymer, thermoplastic polyurethane, polyester-based thermoplastic elastomer and the like. .. These may be used individually by 1 type, and may be used in combination of 2 or more type.
無機充填剤、改質剤、及びその他添加剤の含有量は、特に限定されず、本発明の効果を阻害しない範囲で配合することができる。例えば、基材に用いられる塩化ビニル系樹脂１００質量部に対して、０質量部を超え５０質量部以下を配合することができる。 The contents of the inorganic filler, the modifier, and other additives are not particularly limited, and can be blended within a range that does not impair the effects of the present invention. For example, with respect to 100 parts by mass of the vinyl chloride resin used for the base material, more than 0 parts by mass and 50 parts by mass or less can be blended.
基材の成形方法としては、例えば、塩化ビニル系樹脂、及び必要に応じて、可塑剤、無機充填剤、熱安定剤、光吸収剤、顔料、その他添加剤等を混合した組成物を溶融混練したのち、所定の厚みに成形する方法が挙げられる。溶融混練方法は、本発明の効果を有する限り特に限定されないが、例えば、二軸押出機、連続式及びバッチ式のニーダー、ロール、バンバリーミキサー等の加熱装置を備えた各種混合機、混練機が使用できる。前記混錬方法によって、前記組成物が均一分散するように混合し、得られた混合物を慣用の成形方法であるカレンダー法、Ｔダイ法、インフレーション法等によりシート状基材に成形する。成形機は生産性、色変え、形状の均一性等の面からカレンダー成形機が好ましい。カレンダー成形におけるロール配列方式は、例えば、Ｌ型、逆Ｌ型、Ｚ型等の公知の方式を採用できる。また、ロール温度は通常１５０〜２００℃、好ましくは１５５〜１９０℃に設定される。 As a method for molding the base material, for example, a composition obtained by mixing a vinyl chloride resin and, if necessary, a plasticizer, an inorganic filler, a heat stabilizer, a light absorber, a pigment, and other additives is melt-kneaded. Then, a method of molding to a predetermined thickness can be mentioned. The melt-kneading method is not particularly limited as long as it has the effect of the present invention. Can be used. The composition is mixed by the kneading method so as to be uniformly dispersed, and the obtained mixture is molded into a sheet-like substrate by a conventional molding method such as a calendar method, a T-die method, or an inflation method. The molding machine is preferably a calendar molding machine from the viewpoints of productivity, color change, shape uniformity and the like. As the roll arrangement method in calendar molding, for example, known methods such as L-type, inverted L-type, and Z-type can be adopted. The roll temperature is usually set to 150 to 200 ° C, preferably 155 to 190 ° C.
基材の厚みは、使用目的や用途等に応じて様々であるが、好ましくは３０〜４００μｍであり、より好ましくは５０〜３００μｍであり、さらに好ましくは８０〜２００μｍである。 The thickness of the base material varies depending on the purpose of use, application, etc., but is preferably 30 to 400 μm, more preferably 50 to 300 μm, and even more preferably 80 to 200 μm.
＜粘着剤層＞
本発明の粘着テープは、前記粘着剤組成物より得られる粘着剤層を備える。粘着剤層は、基材の少なくとも一方の面に設けられており、基材の両面に設けられていてもよい。
粘着剤層の厚みは、粘着力、及び塗工性の観点から、１０〜５０μｍが好ましく、１５〜４０μｍがより好ましい。
<Adhesive layer>
The pressure-sensitive adhesive tape of the present invention comprises a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition. The pressure-sensitive adhesive layer is provided on at least one surface of the base material, and may be provided on both sides of the base material.
The thickness of the pressure-sensitive adhesive layer is preferably 10 to 50 μm, more preferably 15 to 40 μm, from the viewpoint of adhesive strength and coatability.
＜中間層＞
本発明の１つの態様においては、基材と粘着剤層との密着性をより向上させる目的で、基材と粘着剤層との間に中間層を設けてもよい。
前記中間層を構成する材料としては、例えば、メタクリル酸メチルグラフト天然ゴム等が挙げられる。
メタクリル酸メチルグラフト天然ゴムは、天然ゴムとメタクリル酸とがグラフト共重合した重合体である。このような重合体は、例えば、基材として塩化ビニル系樹脂を用いた場合、塩化ビニル系樹脂と前記粘着剤組成物の両方と親和性を有するため、これを用いて中間層を形成することにより、基材と粘着剤層との接着性がより向上しやすくなる。
また、中間層を構成する材料には、前記メタクリル酸メチルグラフト天然ゴムに、その他のモノマーを共重合させたものを用いてもよい。その他のモノマーとしては、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−ブチル、アクリル酸ｉ−ブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシル、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−ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−エチルヘキシル等のメタクリル酸エステル、スチレン、アクリロニトリル、メタクリル酸等が挙げられる。これらその他のモノマーは、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
<Middle class>
In one aspect of the present invention, an intermediate layer may be provided between the base material and the pressure-sensitive adhesive layer for the purpose of further improving the adhesion between the base material and the pressure-sensitive adhesive layer.
Examples of the material constituting the intermediate layer include methyl methacrylate graft natural rubber and the like.
Methyl methacrylate graft natural rubber is a polymer obtained by graft-copolymerizing natural rubber and methacrylic acid. For example, when a vinyl chloride resin is used as a base material, such a polymer has an affinity for both the vinyl chloride resin and the pressure-sensitive adhesive composition, and thus an intermediate layer is formed by using the vinyl chloride resin. As a result, the adhesiveness between the base material and the pressure-sensitive adhesive layer is more likely to be improved.
Further, as the material constituting the intermediate layer, a material obtained by copolymerizing the methyl methacrylate graft natural rubber with other monomers may be used. Examples of other monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples thereof include methacrylic acid esters such as n-butyl, i-butyl methacrylate, t-butyl methacrylate and 2-ethylhexyl methacrylate, styrene, acrylonitrile, and methacrylic acid. These other monomers may be used alone or in combination of two or more.
中間層を構成する材料には、必要に応じて他の合成ゴムを添加してもよい。合成ゴムとしては、例えば、ブタジエンゴム、イソプレンゴム、スチレン−ブタジエンゴム、アクリロニトリル−ブタジエンゴム、メタクリル酸メチル−ブタジエンゴム、イソブチレンゴム（ブチルゴム）、クロロプレンゴム、アクリルゴム、熱可塑性エラストマー（例えば、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴム、スチレン−ブタジエン−スチレンブロックコポリマー、スチレン−イソプレン−スチレンブロックコポリマー、スチレン−エチレン−スチレンコポリマー、スチレン−エチレン−ブタジエン−スチレンコポリマー、スチレン−エチレン−プロピレン−スチレンコポリマー等）、アクリルゴム、ウレタンゴム等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Other synthetic rubbers may be added to the material constituting the intermediate layer, if necessary. Examples of synthetic rubber include butadiene rubber, isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, isobutylene rubber (butyl rubber), chloroprene rubber, acrylic rubber, and thermoplastic elastomers (for example, ethylene-ethylene-. Propylene rubber, ethylene-propylene-diene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-styrene copolymer, styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, etc. ), Acrylic rubber, urethane rubber and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
中間層の厚みは、基材と粘着剤層との密着力、中間層の構造維持の観点から、０．１〜３μｍが好ましく、０．２〜２μｍがより好ましく、０．３〜１μｍが特に好ましい。 The thickness of the intermediate layer is preferably 0.1 to 3 μm, more preferably 0.2 to 2 μm, and particularly 0.3 to 1 μm from the viewpoint of the adhesion between the base material and the pressure-sensitive adhesive layer and the structure maintenance of the intermediate layer. preferable.
［粘着テープの製造方法］
本発明の粘着テープの製造方法としては、前述の粘着剤組成物の製造方法により得られる本発明の粘着剤組成物を塗工液として、基材の少なくとも一方の面に塗工し、乾燥炉により乾燥した後、ロール状に巻き取る方法によって製造することができる。また、中間層を設ける場合は、中間層を構成する材料の溶液、エマルジョン、又はディスパージョンを、基材の少なくとも一方の面に塗工して中間層を形成した後、粘着剤組成物の塗工液を前記中間層の上に塗工して乾燥する方法によって、粘着テープを製造することができる。
巻き取り時の応力緩和、中間層及び粘着剤層の密着性の向上、粘着剤層成分同士の親和性を向上させる目的で、さらに、ロール状に巻き取った粘着テープを所定時間エージングする工程、所定温度で熱処理を施す工程を備えていてもよい。なお、粘着剤組成物、及び中間層を構成する材料の塗工方法としては、例えば、正回転ロール方式、リバースロール方式、グラビアロール方式、スプレー方式、キスロール方式、バー方式、ナイフ方式、コンマ方式、リップダイ方式等が挙げられる。
エージングや熱処理は粘着テープの性能が十分に安定する時間、温度にて行うことが好ましく、特に本発明の粘着テープの場合は、粘着剤層の軟化点またはガラス転移点以上の温度で行うことが好ましい。
具体的には、粘着テープの熱処理温度としては、例えば、１００℃以上１３０℃以下が好ましい。また、エージングの時間は、１時間以上６時間以下であることが好ましい。
[Manufacturing method of adhesive tape]
As a method for producing an adhesive tape of the present invention, the pressure-sensitive adhesive composition of the present invention obtained by the above-mentioned method for producing an adhesive composition is applied as a coating liquid on at least one surface of a base material, and a drying furnace is used. It can be produced by a method of winding it into a roll after being dried by. When the intermediate layer is provided, a solution, emulsion, or dispersion of the material constituting the intermediate layer is applied to at least one surface of the base material to form the intermediate layer, and then the pressure-sensitive adhesive composition is applied. An adhesive tape can be produced by a method in which a working solution is applied onto the intermediate layer and dried.
A step of aging the adhesive tape wound in a roll shape for a predetermined time for the purpose of stress relaxation during winding, improvement of adhesion between the intermediate layer and the pressure-sensitive adhesive layer, and improvement of affinity between the pressure-sensitive adhesive layer components. It may include a step of performing heat treatment at a predetermined temperature. Examples of the coating method for the pressure-sensitive adhesive composition and the materials constituting the intermediate layer include a forward rotation roll method, a reverse roll method, a gravure roll method, a spray method, a kiss roll method, a bar method, a knife method, and a comma method. , Lip die method and the like.
Aging and heat treatment are preferably performed at a time and temperature at which the performance of the adhesive tape is sufficiently stable, and in particular, in the case of the adhesive tape of the present invention, it is performed at a temperature equal to or higher than the softening point or the glass transition point of the adhesive layer. preferable.
Specifically, the heat treatment temperature of the adhesive tape is preferably, for example, 100 ° C. or higher and 130 ° C. or lower. The aging time is preferably 1 hour or more and 6 hours or less.
＜用途＞
本発明の粘着テープは、上述の特徴的な粘着剤組成物により得られる粘着剤層を備えるため、高い粘着力と耐熱性能とを有している。また、ＶＯＣを用いてないため環境への負荷が小さい。そのため、高い粘着力と耐熱性が要求される分野、例えば、自動車の電線類等の結束用粘着テープ、特に、エンジン周り等、高温になりやすい環境に配置される電線類等の結束用粘着テープとして好適に用いることができる。なお、当然ながら本実施形態の粘着テープは、その用途が電線類等の結束用に限定されるわけではない。
<Use>
Since the adhesive tape of the present invention has an adhesive layer obtained by the above-mentioned characteristic adhesive composition, it has high adhesive strength and heat resistance. Moreover, since VOC is not used, the load on the environment is small. Therefore, in fields where high adhesive strength and heat resistance are required, for example, adhesive tapes for binding electric wires of automobiles, especially adhesive tapes for binding electric wires arranged in an environment where high temperature is likely to occur, such as around an engine. Can be suitably used as. As a matter of course, the use of the adhesive tape of the present embodiment is not limited to binding electric wires and the like.
以下、実施例を示して本発明を詳細に説明するが、本発明は以下の記載によって限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.
［実施例１］
＜粘着剤組成物の製造＞
ゴム成分として、天然ゴム（（株）レヂテックス製、商品名「ＨＡ−ＬＡＴＥＸ」。ゲル分率６８％）２０質量部と、合成ゴム（スチレン−ブタジエンゴム；日本エイアンドエル（株）製、商品名「ナルスター（登録商標） ＳＲ−１１６」。スチレン比率５５質量％、ゲル分率１５％）８０質量部とを配合し、さらに粘着付与樹脂１００質量部、界面活性剤（両親媒性界面活性剤；花王（株）製、商品名「ぺレックス（登録商標）ＯＴ−Ｐ」）３質量部、架橋剤（イソシアネート系架橋剤；旭化成（株）製、商品名「デュラネート（登録商標） ＷＢ４０−１００」）１５質量部をそれぞれ配合し、純水で粘度を調整して、水系のエマルジョン型粘着剤組成物を製造した。なお、各成分の配合量は固形分換算の値である。得られた粘着剤組成物のゲル分率は、３５％であった。なお、上記粘着付与樹脂のエマルジョンとしては、クマロン樹脂（日塗化学（株）製、商品名「ニットレジン（登録商標） クマロン Ｇ−９０」、数平均分子量２２０）７５部をメチルシクロヘキサン２５部に溶解し、これに界面活性剤（花王（株）製、商品名「エマルゲン（登録商標）９２０」）３．５部及び水４６．５部を加えてホモミキサーにて撹拌乳化し、減圧蒸留にてメチルシクロヘキサンを除去したものである。得られた粘着剤組成物の組成を表１に示す。
[Example 1]
<Manufacturing of adhesive composition>
As rubber components, 20 parts by mass of natural rubber (manufactured by Reditex Co., Ltd., trade name "HA-LATEX". Gel content 68%) and synthetic rubber (styrene-butadiene rubber; manufactured by Nippon A & L Co., Ltd., trade name " Narustar (registered trademark) SR-116 ". Styrene ratio 55% by mass, gel content 15%) 80 parts by mass, and 100 parts by mass of tackifier resin, surfactant (parent-mediated surfactant; Kao) Made by Co., Ltd., trade name "Perex (registered trademark) OT-P") 3 parts by mass, cross-linking agent (isocyanate-based cross-linking agent; manufactured by Asahi Kasei Co., Ltd., trade name "Duranate (registered trademark) WB40-100") Each of 15 parts by mass was blended, and the viscosity was adjusted with pure water to produce an aqueous emulsion type pressure-sensitive adhesive composition. The blending amount of each component is a value in terms of solid content. The gel fraction of the obtained pressure-sensitive adhesive composition was 35%. As the emulsion of the tackifier resin, 75 parts of Kumaron resin (manufactured by Nikko Kagaku Co., Ltd., trade name "Knit Resin (registered trademark) Kumaron G-90", number average molecular weight 220) is added to 25 parts of methylcyclohexane. Dissolve, add 3.5 parts of surfactant (manufactured by Kao Co., Ltd., trade name "Emargen (registered trademark) 920") and 46.5 parts of water, emulsify with stirring with a homomixer, and perform vacuum distillation. Methylcyclohexane was removed. The composition of the obtained pressure-sensitive adhesive composition is shown in Table 1.
（粘着剤組成物のゲル分率の測定方法）
得られた粘着剤組成物について、以下の方法でゲル分率を測定した。結果を表１に示す。
エタノール１００ｇに対し、得られた粘着剤組成物１ｇを加え、恒温水槽（５０℃±２℃）に共栓付三角フラスコをセットし、スターラーで回転数６００／ｍｉｎにて２時間撹拌した。撹拌後、共栓付三角フラスコを氷水で２３℃以下まで冷却し、試料を予め重量を計量しておいた２７０メッシュの金網にて全量濾過した。濾過後の不溶分を１００±２℃で１０分間加熱し、エタノール不溶分を得た。得られたエタノール不溶分の重量をＷ１（ｇ）とし、これにトルエン１００ｇをホールピペットで加え、回転子を入れた後、密栓した。恒温水槽（５０℃±２℃）に共栓付三角フラスコをセットし、スターラーで回転数６００／ｍｉｎにて２時間撹拌した。撹拌後、共栓付三角フラスコを氷水で２３℃以下まで冷却し、重量Ｗ２（ｇ）の２７０メッシュの金網にて全量濾過した。濾過後の金網を１４０℃±２℃にて１時間加熱したのち、金網重量を計量した（乾燥後の金網重量をＷ３（ｇ）とする）。上記測定にて得られたＷ１〜Ｗ３を用いて、以下の式からゲル分率を算出した。
ゲル分率（質量％）＝［（Ｗ３−Ｗ２）／Ｗ１］×１００
(Measuring method of gel fraction of adhesive composition)
The gel fraction of the obtained pressure-sensitive adhesive composition was measured by the following method. The results are shown in Table 1.
1 g of the obtained pressure-sensitive adhesive composition was added to 100 g of ethanol, an Erlenmeyer flask with a stopper was set in a constant temperature water bath (50 ° C. ± 2 ° C.), and the mixture was stirred with a stirrer at a rotation speed of 600 / min for 2 hours. After stirring, the Erlenmeyer flask with a stopper was cooled to 23 ° C. or lower with ice water, and the whole sample was filtered through a 270 mesh wire mesh previously weighed. The insoluble matter after filtration was heated at 100 ± 2 ° C. for 10 minutes to obtain an ethanol insoluble matter. The weight of the obtained insoluble ethanol was defined as W1 (g), 100 g of toluene was added thereto with a whole pipette, a rotor was inserted, and the mixture was sealed. An Erlenmeyer flask with a stopper was set in a constant temperature water tank (50 ° C. ± 2 ° C.), and the mixture was stirred with a stirrer at a rotation speed of 600 / min for 2 hours. After stirring, the Erlenmeyer flask with a stopper was cooled to 23 ° C. or lower with ice water, and the entire amount was filtered through a 270 mesh wire mesh having a weight of W2 (g). The filtered wire mesh was heated at 140 ° C. ± 2 ° C. for 1 hour, and then the weight of the wire mesh was weighed (the weight of the wire mesh after drying is W3 (g)). Using W1 to W3 obtained in the above measurement, the gel fraction was calculated from the following formula.
Gel fraction (mass%) = [(W3-W2) / W1] x 100
＜粘着テープの製造＞
（基材の作成）
塩化ビニル系樹脂としてポリ塩化ビニル（大洋塩ビ（株）製、商品名「ＴＨ−１０００」）１００質量部に対し、トリメリット酸トリス２−エチルヘキシル（ＤＩＣ（株）製、商品名「Ｗ−７００」）を５０質量部、難燃助剤として三酸化二アンチモン（鈴裕化学（株）製、商品名「ファイヤーカットＴＯＰ−５」）、さらに安定剤、滑剤をそれぞれ配合し、バンバリーミキサーで溶融混錬し、ロール温度１６５℃のカレンダー成形機にて、厚みが１２５μｍとなるように成形して基材を得た。
<Manufacturing of adhesive tape>
(Creation of base material)
As a vinyl chloride resin, tris-2-ethylhexyl trimeritate (manufactured by DIC Co., Ltd., trade name "W-700") is based on 100 parts by mass of polyvinyl chloride (manufactured by Taiyo PVC Co., Ltd., trade name "TH-1000"). ”) 50 parts by mass, diantimony trioxide (manufactured by Suzuhiro Chemical Co., Ltd., trade name“ Firecut TOP-5 ”) as a flame retardant aid, and a stabilizer and lubricant, respectively, and melted with a Banbury mixer. The mixture was kneaded and molded with a calendar molding machine having a roll temperature of 165 ° C. so as to have a thickness of 125 μm to obtain a base material.
次に、実施例１で得られた粘着剤組成物を塗工液として用い、前記基材の一方の面に塗工後、１２０℃で１分間乾燥して粘着剤層を形成した。得られた粘着テープの粘着剤層の厚みは２５μｍであった。
得られた粘着テープの粘着力及び耐熱性能を、以下の方法に従って評価した。結果を表１に示す。
Next, the pressure-sensitive adhesive composition obtained in Example 1 was used as a coating liquid, and after coating on one surface of the base material, it was dried at 120 ° C. for 1 minute to form a pressure-sensitive adhesive layer. The thickness of the pressure-sensitive adhesive layer of the obtained pressure-sensitive adhesive tape was 25 μm.
The adhesive strength and heat resistance of the obtained adhesive tape were evaluated according to the following methods. The results are shown in Table 1.
（粘着力の評価）
以下の方法に従って、自背面粘着力の評価を行った。また、得られた粘着力が１．５Ｎ／１０ｍｍ以上のものを、「〇」（粘着力が高い）、１．５Ｎ／１０ｍｍ未満のものを「×」（粘着力が低い）として評価した。
ＪＩＳ Ｚ ０２３７に従って測定した。幅１０ｍｍの粘着テープを温度２３±２℃、湿度５０±５％ＲＨに設定された評価試験室内に２４時間以上静置した。厚さ１ｍｍの金属板に長さ１５０ｍｍの粘着テープを貼り合わせ、自背面測定用のテープ基材面サンプルを作製した。更に長さ１５０ｍｍの粘着テープを用意し、その粘着面を自背面測定用のテープ基材面上に貼り合わせたのち、重さ２０００ｇのローラーを５ｍｍ／ｓの速度で１往復させて貼り合わせた。貼り合わせ２０分後に、引張試験機（（株）島津製作所製、製品名「オートグラフＡＧＸ」）を用いてテープ粘着面とテープ基材面との間の１８０度剥離強度（Ｎ／１０ｍｍ）を測定した。
(Evaluation of adhesive strength)
The adhesive strength on the back surface was evaluated according to the following method. Further, those having an adhesive strength of 1.5 N / 10 mm or more were evaluated as "◯" (high adhesive strength), and those having an adhesive strength of less than 1.5 N / 10 mm were evaluated as "x" (low adhesive strength).
Measured according to JIS Z 0237. An adhesive tape having a width of 10 mm was allowed to stand in an evaluation test room set at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH for 24 hours or more. An adhesive tape having a length of 150 mm was attached to a metal plate having a thickness of 1 mm to prepare a tape base material surface sample for self-backward measurement. Further, an adhesive tape having a length of 150 mm was prepared, and the adhesive surface was bonded onto the surface of the tape base material for self-back measurement, and then a roller weighing 2000 g was reciprocated once at a speed of 5 mm / s and bonded. .. Twenty minutes after bonding, a tensile tester (manufactured by Shimadzu Corporation, product name "Autograph AGX") was used to determine the 180-degree peel strength (N / 10 mm) between the tape adhesive surface and the tape substrate surface. It was measured.
（耐熱性能の評価）
長さ８００±２０ｍｍの、ＪＡＳＯ Ｄ ６１１に規定されたＡＶＸ電線を１０本集束して電線束を作製し、図１に示すような試験片Ａを作成した。すなわち、電線束１の中央部を含む長さ４００±１０ｍｍの範囲に、幅２０ｍｍの粘着テープ１０をハーフラップ巻き、すなわち、１周巻いた後の粘着テープ１０が、前周のテープ幅の半分（９．５ｍｍ）に覆いかぶさるような角度で、粘着テープ１０を電線束１にらせん状に約２０周巻き付けて試験片Ａを作成した。作成した試験片Ａを、図２に示すように、直径８０ｍｍのマンドレル２に１周させた状態で粘着テープ１０で固定したのちに、１２０±２℃のオーブンで１６８時間加熱し、室温２３±２℃環境にて冷却し、試験片Ａの粘着テープ１０の端部の位置ずれ、剥がれの状態を確認した。評価基準を以下の通りとし、その結果を表に記載した。
（評価基準）
◎：粘着テープ端部の位置ずれ、剥がれが全くない。
〇：粘着テープ端部の位置がずれているが、電線から剥がれてはいない。
×：粘着テープ端部が電線から剥がれ、めくれている。
(Evaluation of heat resistance performance)
Ten AVX electric wires specified in JASO D 611 having a length of 800 ± 20 mm were bundled to prepare an electric wire bundle, and a test piece A as shown in FIG. 1 was prepared. That is, the
(Evaluation criteria)
⊚: There is no misalignment or peeling of the end of the adhesive tape.
〇: The position of the end of the adhesive tape is misaligned, but it is not peeled off from the electric wire.
X: The end of the adhesive tape is peeled off from the electric wire and turned over.
（保持力の評価）
以下の方法に従って、粘着テープの保持力を評価した。保持力は、粘着テープの粘着保持性の高さの指標となるものである。なお、得られた保持力の値が、２００分以上のものを、「〇」（粘着保持性が高い）、２００分未満のものを「×」（粘着保持性が低い）として評価した。
ＪＩＳ Ｚ ０２３７に従って測定した。幅２０ｍｍの粘着テープを温度２３±２℃、湿度５０±５％ＲＨ環境下で２４時間以上静置した後で、ガラス板に長さ２５ｍｍの粘着テープを貼り付けた。その後、粘着テープの片面に重さ１００ｇの錘をチャックで挟み、１００℃雰囲気化で２０分予熱したのち、錘１００ｇの荷重をかけ、テープがガラス板から剥がれて落下するまでの経過時間（分）を測定した。
(Evaluation of holding power)
The holding power of the adhesive tape was evaluated according to the following method. The holding power is an index of the high adhesive holding property of the adhesive tape. In addition, the obtained value of the holding power of 200 minutes or more was evaluated as "◯" (high adhesive holding property), and the value of less than 200 minutes was evaluated as "x" (low adhesive holding property).
Measured according to JIS Z 0237. An adhesive tape having a width of 20 mm was allowed to stand for 24 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH, and then an adhesive tape having a length of 25 mm was attached to a glass plate. After that, a weight of 100 g is sandwiched between one side of the adhesive tape with a chuck, preheated for 20 minutes in an atmosphere of 100 ° C., and then a load of 100 g of the weight is applied, and the elapsed time (minutes) until the tape peels off from the glass plate and falls. ) Was measured.
［実施例２〜２０、比較例１〜８］
粘着剤組成物の組成を表１に示す通りとした以外は、実施例１と同様の方法で粘着剤組成物を調整した。また得られた粘着剤組成物を用いて、実施例１と同様の方法でゲル分率を測定した。また、実施例１と同様の方法で粘着テープを作成し、粘着力及び耐熱性能について評価を行った。なお、比較例８は、基材表面に粘着剤組成物を塗布させたのち、エージングを行なわずに粘着テープを作成した。結果を表１〜２に示す。
[Examples 2 to 20, Comparative Examples 1 to 8]
The pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive composition was as shown in Table 1. Further, using the obtained pressure-sensitive adhesive composition, the gel fraction was measured in the same manner as in Example 1. In addition, an adhesive tape was prepared in the same manner as in Example 1, and the adhesive strength and heat resistance were evaluated. In Comparative Example 8, after the pressure-sensitive adhesive composition was applied to the surface of the base material, a pressure-sensitive adhesive tape was prepared without aging. The results are shown in Tables 1-2.
なお、表１〜２中の各成分の詳細は以下のとおりである。
天然ゴム１：天然ゴムエマルジョン（（株）レヂテックス製、商品名「ＨＡ−ＬＡＴＥＸ」、ゲル分率６８％）。
天然ゴム２：天然ゴムエマルジョン（（株）レヂテックス製、商品名「ＳＳ−５８」、ゲル分率９５％）。
天然ゴム３：天然ゴムエマルジョン（ムサシノケミカル（株）製、商品名「ＥＣＸＥＬＴＥＸ ＨＬＸ ＬＡＴＺ」、ゲル分率７３％）。
合成ゴム１：スチレン−ブタジエンゴム（日本エイアンドエル（株）製、「ナルスター ＳＲ−１１６」、スチレン比率：５５質量％、ゲル分率１５％）。
合成ゴム２：スチレン−ブタジエンゴム（ＪＳＲ（株）製、商品名「Ｔ−０９３Ａ」、スチレン比率：４０質量％、ゲル分率０．５％）。
合成ゴム３：スチレン−ブタジエンゴム（ＪＳＲ（株）製「０５４５」を密閉容器内で１０日間加熱、スチレン比率：２５質量％、ゲル分率１０％）。
粘着付与樹脂１：クマロン樹脂のエマルジョン（日塗化学（株）製、商品名「ニットレジン クマロン Ｇ−９０」の乳化物、固形分５０％、数平均分子量２２０）。
粘着付与樹脂２：石油樹脂（脂肪族系と芳香族系の共重合体）のエマルジョン（日本ゼオン（株）製、商品名「クイントン（登録商標） Ｇ１１５」の乳化物、固形分５０％、数平均分子量１３００）。
粘着付与樹脂３：石油樹脂（脂肪族系）のエマルジョン（ＪＸＴＧエネルギー（株）製、商品名「Ｔ−ＲＥＺ ＲＡ１００」の乳化物、固形分５０％、数平均分子量１３００）。
粘着付与樹脂４：石油樹脂（芳香族系）のエマルジョン（アリゾナケミカル（株）製、商品名「Ｓｙｌｖａｒｅｓ（登録商標） ＳＡ１４０」の乳化物、固形分５０％、数平均分子量２２００）。
粘着付与樹脂５：テルペン樹脂のエマルジョン（ヤスハラケミカル（株）製、商品名「ＹＳレジン１１５０」の乳化物、固形分５０％、数平均分子量１０００）。
粘着付与樹脂６：ロジン樹脂のエマルジョン（ハリマ化成（株）製、商品名「ハリタックＰＣＪ」の乳化物、固形分５０％、数平均分子量７００）。
界面活性剤：（花王（株）製、商品名「ぺレックスＯＴ−Ｐ」）。
架橋剤１：硫黄系架橋剤（化合物名テトラメチルチウラムジスルフィド）（レヂテックス社製、商品名「ＴＴ加硫剤分散体」）。
架橋剤２：イソシアネート系架橋剤（旭化成（株）製、商品名「デュラネート ＷＢ４０−１００」）。
架橋剤３：カルボジイミド系架橋剤（日清紡ケミカル（株）製、商品名「カルボジライト（登録商標） Ｖ−０２」）。
The details of each component in Tables 1 and 2 are as follows.
Natural rubber 1: Natural rubber emulsion (manufactured by Reditex Co., Ltd., trade name "HA-LATEX", gel fraction 68%).
Natural rubber 2: Natural rubber emulsion (manufactured by Reditex Co., Ltd., trade name "SS-58", gel fraction 95%).
Natural rubber 3: Natural rubber emulsion (manufactured by Musashino Chemical Co., Ltd., trade name "ECXELTEX HLX LATZ", gel fraction 73%).
Synthetic rubber 1: Styrene-butadiene rubber (manufactured by Nippon A & L Inc., "Nalstar SR-116", styrene ratio: 55% by mass, gel fraction 15%).
Synthetic rubber 2: Styrene-butadiene rubber (manufactured by JSR Corporation, trade name "T-093A", styrene ratio: 40% by mass, gel fraction 0.5%).
Synthetic rubber 3: Styrene-butadiene rubber ("0545" manufactured by JSR Corporation is heated in a closed container for 10 days, styrene ratio: 25% by mass,
Adhesive-imparting resin 1: Emulsion of Kumaron resin (manufactured by Nikko Kagaku Co., Ltd., emulsion of trade name "Knit Resin Kumaron G-90", solid content 50%, number average molecular weight 220).
Adhesive-imparting resin 2: Emulsion of petroleum resin (aliphatic and aromatic copolymer) (manufactured by Nippon Zeon Corporation, product name "Quinton (registered trademark) G115" emulsion, solid content 50%, number Average molecular weight 1300).
Adhesive-imparting resin 3: Emulsion of petroleum resin (aliphatic) (manufactured by JXTG Energy Co., Ltd., emulsion of trade name "T-REZ RA100", solid content 50%, number average molecular weight 1300).
Adhesive-imparting resin 4: Emulsion of petroleum resin (aromatic) (manufactured by Arizona Chemical Co., Ltd., emulsion of trade name "Sylvares (registered trademark) SA140", solid content 50%, number average molecular weight 2200).
Adhesive-imparting resin 5: Emulsion of terpene resin (manufactured by Yasuhara Chemical Co., Ltd., emulsion of trade name "YS resin 1150", solid content 50%, number average molecular weight 1000).
Adhesive-imparting resin 6: Emulsion of rosin resin (manufactured by Harima Chemicals, Inc., emulsion of trade name "Haritac PCJ", solid content 50%, number average molecular weight 700).
Surfactant: (manufactured by Kao Corporation, trade name "Perex OT-P").
Cross-linking agent 1: Sulfur-based cross-linking agent (compound name tetramethylthiuram disulfide) (manufactured by Reditex, trade name "TT vulcanizing agent dispersion").
Crosslinking agent 2: Isocyanate-based crosslinking agent (manufactured by Asahi Kasei Corporation, trade name "Duranate WB40-100").
Crosslinking agent 3: Carbodiimide-based crosslinking agent (manufactured by Nisshinbo Chemical Co., Ltd., trade name "Carbodilite (registered trademark) V-02").
表１〜２に示す通り、本発明の粘着剤組成物より得られる粘着剤層を備える実施例１〜２０の粘着テープは、高い粘着力を有し、かつ耐熱性能にも優れていた。一方、本発明の粘着剤組成物以外を用いた比較例１〜８の粘着テープは、耐熱性能が低かった。以上の結果から、本発明の粘着剤組成物及び前記粘着剤組成物を用いて得られる粘着テープは、高い粘着力と耐熱性能とを有することが確認された。また、本発明の粘着剤組成物は水系の粘着剤組成物であるため、環境への負荷が小さい。 As shown in Tables 1 and 2, the adhesive tapes of Examples 1 to 20 provided with the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention had high adhesive strength and excellent heat resistance. On the other hand, the adhesive tapes of Comparative Examples 1 to 8 using other than the pressure-sensitive adhesive composition of the present invention had low heat resistance. From the above results, it was confirmed that the pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive tape obtained by using the pressure-sensitive adhesive composition have high adhesive strength and heat resistance. Further, since the pressure-sensitive adhesive composition of the present invention is a water-based pressure-sensitive adhesive composition, the burden on the environment is small.
１：電線束
２：マンドレル
１０：粘着テープ
Ａ：試験片
1: Wire bundle 2: Mandrel 10: Adhesive tape A: Test piece
Claims (9)
前記水系のエマルジョン型粘着剤組成物のゲル分率が３０〜５０％である、水系のエマルジョン型粘着剤組成物。 100 parts by mass of rubber component including 5 to 40 parts by mass of natural rubber and 60 to 95 parts by mass of synthetic rubber, 70 to 130 parts by mass of tackifier resin, 0.1 to 5 parts by mass of surfactant, and 5 to 5 parts by mass of cross-linking agent. An aqueous emulsion-type pressure-sensitive adhesive composition containing 30 parts by mass.
A water-based emulsion-type pressure-sensitive adhesive composition having a gel fraction of 30 to 50%.
The adhesive tape according to claim 8, wherein the base material is made of a resin containing a vinyl chloride resin.
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| DE102022202268A1 (en) | 2021-03-12 | 2022-09-15 | Sintokogio, Ltd. | Management device, management method, management program and recording medium |
| WO2023047386A1 (en) * | 2021-09-27 | 2023-03-30 | 3M Innovative Properties Company | Pressure-sensitive adhesive tape including sulfur and related processes |
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| JP2011084615A (en) * | 2009-10-14 | 2011-04-28 | Denki Kagaku Kogyo Kk | Emulsion self-adhesive and self-adhesive tape using the same |
| JP2018178008A (en) * | 2017-04-17 | 2018-11-15 | 矢崎総業株式会社 | Composition for adhesive, adhesive resin tape, and wire harness |
| WO2019230067A1 (en) * | 2018-05-30 | 2019-12-05 | デンカ株式会社 | Adhesive tape |
| JPWO2020026697A1 (en) * | 2018-08-03 | 2021-08-02 | デンカ株式会社 | Adhesive and adhesive tape using the adhesive |
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| JP2000053939A (en) * | 1998-08-05 | 2000-02-22 | Yokohama Rubber Co Ltd:The | Aqueous adhesive composition |
| JP2011084615A (en) * | 2009-10-14 | 2011-04-28 | Denki Kagaku Kogyo Kk | Emulsion self-adhesive and self-adhesive tape using the same |
| JP2018178008A (en) * | 2017-04-17 | 2018-11-15 | 矢崎総業株式会社 | Composition for adhesive, adhesive resin tape, and wire harness |
| WO2019230067A1 (en) * | 2018-05-30 | 2019-12-05 | デンカ株式会社 | Adhesive tape |
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| WO2023047386A1 (en) * | 2021-09-27 | 2023-03-30 | 3M Innovative Properties Company | Pressure-sensitive adhesive tape including sulfur and related processes |
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