JP2015117335A - Hot melt type adhesive film and molded body - Google Patents
Hot melt type adhesive film and molded body Download PDFInfo
- Publication number
- JP2015117335A JP2015117335A JP2013262689A JP2013262689A JP2015117335A JP 2015117335 A JP2015117335 A JP 2015117335A JP 2013262689 A JP2013262689 A JP 2013262689A JP 2013262689 A JP2013262689 A JP 2013262689A JP 2015117335 A JP2015117335 A JP 2015117335A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive film
- ethylene
- resin
- hot
- melt 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.)
- Granted
Links
- 239000002313 adhesive film Substances 0.000 title abstract description 18
- 239000012943 hotmelt Substances 0.000 title abstract description 11
- 239000004711 α-olefin Substances 0.000 claims abstract description 48
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 32
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 12
- 229920001400 block copolymer Polymers 0.000 claims abstract description 10
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- 239000004831 Hot glue Substances 0.000 claims description 48
- -1 polypropylene Polymers 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000004743 Polypropylene Substances 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
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- 239000007769 metal material Substances 0.000 claims description 3
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- 229920001225 polyester resin Polymers 0.000 claims description 3
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- 239000000463 material Substances 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 18
- 238000000465 moulding Methods 0.000 abstract description 9
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- 239000000203 mixture Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 238000004898 kneading Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000004840 adhesive resin Substances 0.000 description 16
- 229920006223 adhesive resin Polymers 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 11
- 239000000758 substrate Substances 0.000 description 7
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
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- 235000007586 terpenes Nutrition 0.000 description 6
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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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 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical class OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
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- 229920000359 diblock copolymer Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
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- 229920001778 nylon Polymers 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
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- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QBTIBZGUQWGDLP-UHFFFAOYSA-N O1OOC(C=2C(=C(C(=O)OO1)C=CC2C(C)(C)C)C(C)(C)C)=O Chemical class O1OOC(C=2C(=C(C(=O)OO1)C=CC2C(C)(C)C)C(C)(C)C)=O QBTIBZGUQWGDLP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 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
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- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- SBYMUDUGTIKLCR-VOTSOKGWSA-N [(e)-2-chloroethenyl]benzene Chemical compound Cl\C=C\C1=CC=CC=C1 SBYMUDUGTIKLCR-VOTSOKGWSA-N 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920013640 amorphous poly alpha olefin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- MLVSWIXRZNPEKF-UPHRSURJSA-N bis(oxiran-2-ylmethyl) (z)-but-2-enedioate Chemical compound C1OC1COC(=O)\C=C/C(=O)OCC1CO1 MLVSWIXRZNPEKF-UPHRSURJSA-N 0.000 description 1
- NRTSLUOVGBFANI-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 2-methylidenebutanedioate Chemical compound C1OC1COC(=O)C(=C)CC(=O)OCC1CO1 NRTSLUOVGBFANI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- GOAJGXULHASQGJ-UHFFFAOYSA-N ethene;prop-2-enenitrile Chemical group C=C.C=CC#N GOAJGXULHASQGJ-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JFHBKKGEVRVZPE-UHFFFAOYSA-N oxiran-2-ylmethyl 4-ethenylbenzoate Chemical compound C1=CC(C=C)=CC=C1C(=O)OCC1OC1 JFHBKKGEVRVZPE-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 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
- 238000012546 transfer Methods 0.000 description 1
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- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明はホットメルト接着剤に関する。さらに詳しくはポリオレフィン系樹脂、アクリル系樹脂、ポリカーボネート系樹脂などの難接着性材料との接着性に優れたホットメルト型接着フィルムに関する。 The present invention relates to a hot melt adhesive. More specifically, the present invention relates to a hot-melt adhesive film excellent in adhesiveness to difficult-to-adhere materials such as polyolefin resin, acrylic resin, and polycarbonate resin.
熱可塑性エラストマー、エンジニアリングプラスチックス等の熱可塑性樹脂は、物性、成形性および表面特性等に優れているため、塊状、シート状、フィルム状等に加工して自動車、家電、エレクトロニクス、建築、雑貨などの分野で多く使用されている。これらの成形品は、異種材料の成形品を複合化することで性能の高度化、機能の多様化を図ることが一般的に行われている。例えば、自動車内装、住宅内装、家電機器分野において、力学的な物性に富むエンジニアリングプラスチックス等の材料からなる成形品を基材とし、その外層に表面特性、耐候性、装飾性に優れるポリエステル、アクリル、金属箔等からなる表皮材や加飾シートを積層することが幅広く行われている。しかしながら、このような積層体は、異種材を複合化、つまりは接着させる必要があるがため、一般的に各層間の接着力に乏しい例が多く課題である。接着材料としては、溶剤型接着剤とホットメルト型接着フィルムなど使用される。現在、溶剤型接着剤が主流となっているが、塗布むらが出やすいこと、有機溶剤の使用により環境、衛生上の悪影響を生じるという欠点を有する。そのため、簡便かつ接着強度の優れたホットメルト接着フィルムへの置き換えが求められている。 Thermoplastic resins such as thermoplastic elastomers and engineering plastics are excellent in physical properties, moldability and surface properties, etc., so they are processed into lumps, sheets, films, etc., such as automobiles, home appliances, electronics, architecture, sundries, etc. It is used in many fields. In general, these molded products have been improved in performance and diversified in function by combining molded products of different materials. For example, in the fields of automobile interiors, house interiors, and home appliances, polyesters and acrylics that use molded products made of materials such as engineering plastics with high mechanical properties as the base material, and have excellent surface properties, weather resistance, and decorative properties on the outer layer Laminating a skin material or a decorative sheet made of metal foil or the like is widely performed. However, since it is necessary to combine different materials, that is, to bond them, such a laminated body generally has many examples in which the adhesive strength between each layer is poor. As the adhesive material, a solvent-type adhesive and a hot-melt adhesive film are used. At present, solvent-based adhesives are mainstream, but they have the disadvantages that uneven coating is likely to occur and that the use of organic solvents causes adverse environmental and hygienic effects. Therefore, replacement with a hot melt adhesive film that is simple and excellent in adhesive strength is required.
このようなホットメルト型接着フィルムとしては、エチレン系共重合体、スチレン系ブロック共重合体およびオレフィン系（共）重合体からなる群から選ばれる1種以上のベースポリマーと粘着付与樹脂、結晶性極性基含有化合物を含有するもの（特許文献１）、アモルファスポリα−オレフィン、粘着付与樹脂およびポリプロピレン系ワックスを必須成分とするもの（特許文献２）、スチレン−エチレンプロピレン−スチレンブロック共重合ゴムあるいはスチレン−ブタジエン−スチレンブロック共重合ゴムに、粘着付与樹脂成分およびプロセスオイルなどの液状可塑剤を添加してなるもの（特許文献３、４）、変性ポリオレフィンと粘着付与剤を配合してなるもの（特許文献５）、スチレン系ブロック共重合体と酸変性ワックスを配合してなるもの（特許文献６）、酸変性ポリプロピレンと酸変性スチレン系ブロック共重合体を配合してなるもの（特許文献７）、スチレン系ブロック共重合体と粘着付与剤、エチレン系重合体を配合してなるもの（特許文献８、９、１０）などが提案されているが、種々の異種材料に対する接着性に満足できるものがない。また、基材となる成形品と加飾シートをホットメルト型接着フィルムにより複合化させる際、加飾シートとホットメルト型接着フィルムとを、加飾シート表面に高温度でエンボス加工すると同時に複合化した後、次いで加飾シート／ホットメルト型接着フィルムと基材とを低温度で複合化させる場合がある。このように二段階で複合化かつ処理温度が異なるといった複雑な成形方法への対応が求められる。また、自動車内装など用途によって接着層に耐熱性が要求されることも増えつつある。 Such hot-melt adhesive films include one or more base polymers selected from the group consisting of ethylene copolymers, styrene block copolymers, and olefinic (co) polymers, tackifying resins, and crystallinity. A material containing a polar group-containing compound (Patent Document 1), an amorphous poly α-olefin, a tackifier resin and a polypropylene-based wax (Patent Document 2), a styrene-ethylenepropylene-styrene block copolymer rubber, or A styrene-butadiene-styrene block copolymer rubber added with a liquid plasticizer such as a tackifier resin component and process oil (Patent Documents 3 and 4), and a mixture of a modified polyolefin and a tackifier ( Patent Document 5), blending styrenic block copolymer and acid-modified wax (Patent Document 6), an acid-modified polypropylene and an acid-modified styrene block copolymer (Patent Document 7), a styrene block copolymer, a tackifier, and an ethylene polymer. (Patent Documents 8, 9, and 10) have been proposed, but none are satisfactory in adhesion to various different materials. In addition, when a molded article and a decorative sheet as a base material are combined with a hot melt adhesive film, the decorative sheet and the hot melt adhesive film are embossed on the decorative sheet surface at a high temperature and simultaneously combined. Then, the decorative sheet / hot melt adhesive film and the substrate may be combined at a low temperature. Thus, it is required to cope with complicated molding methods such as compounding in two steps and different processing temperatures. In addition, heat resistance is required for the adhesive layer depending on applications such as automobile interiors.
従って、本発明の課題は、耐熱性に優れ、異種材が接着可能であり、かつ、二段階で複合化かつ処理温度が異なる成形方法への対応可能なホットメルト型接着フィルムを提供することである。 Accordingly, an object of the present invention is to provide a hot-melt adhesive film that has excellent heat resistance, can be bonded to different materials, can be combined in two steps, and can be applied to molding methods having different processing temperatures. is there.
本発明者らは、上述の現状に鑑み、鋭意検討した結果、
１）（Ｄ）ベース樹脂１００重量部および（Ｃ）粘着付与剤３０〜６０重量部を含有する第一層と、
（Ｅ）前記（Ｃ）を含まない熱可塑性樹脂を含有する第二層からなるホットメルト型接着フィ
ルムであって、
前記（Ｄ）が、（Ａ）（a）エポキシ基含有ビニル単量体および（ｂ）芳香族ビニル単量体で
変性された、変性エチレンーαオレフィン共重合体６０〜９０重量部と、
（Ｂ）スチレン共役ジエン系ブロック共重合体４０〜１０重量部を含有するものである、
ホットメルト型接着フィルム。
２）（a）エポキシ基含有ビニル単量体がメタクリル酸グリシジルである、請求項１に記載のホットメルト型接着フィルム。
３）変性エチレンーαオレフィンが、密度が０．８５ｇ/ｃｍ３〜０．８７ｇ/ｃｍ３であるエチレンーαオレフィン共重合体を変性してなる、請求項１または２に記載のホットメルト型接着フィルム。
４）エチレンーαオレフィンが、エチレン含量が１０〜２０重量％のエチレンープロピレン共重合体である、請求項３に記載のホットメルト型接着フィルム。
５）必要に応じて第一層に（Ｄ）ポリプロピレン、ポリエチレン、エチレン−αオレフィン共重合体からなる群より選ばれるオレフィン系樹脂１５重量部以下を含む請求項１〜４に記載のホットメルト型接着フィルム。
６）第二層の熱可塑性樹脂がポリプロピレン、ポリエチレン、エチレンーαオレフィン共重合体からなる群より選ばれる、少なくとも一種以上を含む樹脂である、請求項１〜５に記載のホットメルト型接着フィルム。
７）第二層の熱可塑性樹脂が（a）エポキシ基含有ビニル単量体、（ｂ）芳香族ビニル単量体および（ｃ）無水マレイン酸単量で変性された樹脂である、請求項１〜６に記載のホットメルト型接着フィルム。
８）請求項１〜８いずれか一項に記載のホットメルト型接着フィルムの第一層側の面と、ポリオレフィン系樹脂、スチレン系樹脂、ポリカーボネート系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂および金属製材料からなる群より選ばれた少なくとも１種以上が接着してなる積層体。
As a result of intensive studies in view of the above-described present situation, the present inventors have
1) (D) a first layer containing 100 parts by weight of a base resin and (C) 30-60 parts by weight of a tackifier;
(E) A hot melt adhesive film comprising a second layer containing a thermoplastic resin not containing (C),
60 to 90 parts by weight of the modified ethylene-α-olefin copolymer modified with (A) (a) an epoxy group-containing vinyl monomer and (b) an aromatic vinyl monomer,
(B) It contains 40 to 10 parts by weight of a styrene conjugated diene block copolymer.
Hot melt adhesive film.
2) (a) The hot melt adhesive film according to claim 1, wherein the epoxy group-containing vinyl monomer is glycidyl methacrylate.
3) The hot melt adhesive film according to claim 1 or 2, wherein the modified ethylene-α-olefin is obtained by modifying an ethylene-α-olefin copolymer having a density of 0.85 g / cm3 to 0.87 g / cm3.
4) The hot melt adhesive film according to claim 3, wherein the ethylene-α-olefin is an ethylene-propylene copolymer having an ethylene content of 10 to 20% by weight.
5) The hot melt mold according to any one of claims 1 to 4, wherein the first layer contains 15 parts by weight or less of an olefin resin selected from the group consisting of (D) polypropylene, polyethylene, and ethylene-α olefin copolymer, as necessary. Adhesive film.
6) The hot-melt adhesive film according to any one of claims 1 to 5, wherein the thermoplastic resin of the second layer is a resin containing at least one selected from the group consisting of polypropylene, polyethylene, and ethylene-α-olefin copolymer.
7) The thermoplastic resin of the second layer is (a) an epoxy group-containing vinyl monomer, (b) an aromatic vinyl monomer, and (c) a resin modified with a single amount of maleic anhydride. The hot-melt adhesive film according to -6.
8) The surface on the first layer side of the hot-melt adhesive film according to any one of claims 1 to 8, polyolefin resin, styrene resin, polycarbonate resin, acrylic resin, polyamide resin, polyester resin A laminate formed by adhering at least one selected from the group consisting of a resin and a metal material.
本発明のホットメルト型接着フィルムは、異種の難接着基材に複合化することができ、文具、雑貨、食品などの包装材、自動車用部品、住宅資材、家電などの電気電子部品、各種産業用資材などの幅広い分野に用いられる。また、ホットメルト型接着フィルムを製造する際、接着フィルムの片方の面のみにセパレーターフィルムを貼り合せるだけで、ロール状のフィルムを製造することができ、製造コストが安価である。 The hot-melt adhesive film of the present invention can be composited on different difficult-to-adhere base materials, packaging materials for stationery, miscellaneous goods, foods, etc., electrical and electronic parts such as automobile parts, housing materials, home appliances, and various industries. Used in a wide range of fields such as industrial materials. Moreover, when manufacturing a hot-melt type adhesive film, a roll-like film can be manufactured only by bonding a separator film only to one side of the adhesive film, and the manufacturing cost is low.
以下に本発明の詳細について述べる。
（１）変性エチレン−αオレフィン共重合体
変性エチレン−αオレフィン共重合体とは、エチレン−αオレフィン共重合体に芳香族ビニル単量体とエポキシ基含有ビニル単量体をグラフト重合したものである。特に、低温加工での難接着樹脂への接着性を得るためには、変性に用いるエチレン−αオレフィン共重合体の密度が０．８５ｇ/ｃｍ３〜０．８７ｇ/ｃｍ３の、低結晶性、非晶性のエチレンーαオレフィンランダム共重合体であることが好ましい。エチレンーαオレフィンランダム共重合体を形成するα−オレフィンとしては、通常炭素数３〜２０のα−オレフィン、例えばプロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−テトラデセン、１−オクタデセンが挙げられるが、グラフト変性の際、ポリオレフィン上にラジカルが発生しやすくなる点および耐熱性の観点から、プロピレンであることが好ましい。エチレンープロピレン共重合体中のエチレンとプロピレンの含有比率としては、プロピレン含量が８０〜９０重量％、エチレン含量が１０〜２０重量％であることが好ましい。エチレン含量がこの範囲より多いと、エチレンープロピレン共重合体の密度が高く低温接着性能が低下するか、耐熱性の面で実用に耐えないといった問題が生じる。さらに、変性時にエチレン部分で架橋反応が先行し、低温接着性が低下するだけでなく、接着性フィルムとして良好な外観のものとして取得できない可能性がある。一方、エチレン含量がこの範囲より少ないと、低温接着性が低下する傾向がある。
Details of the present invention will be described below.
(1) Modified ethylene-α olefin copolymer A modified ethylene-α olefin copolymer is a polymer obtained by graft-polymerizing an aromatic vinyl monomer and an epoxy group-containing vinyl monomer to an ethylene-α olefin copolymer. is there. In particular, in order to obtain adhesion to difficult-to-bond resin at a low temperature processing, the density of the ethylene -α-olefin copolymer used for the modification of 0.85g / cm 3 ~0.87g / cm 3 , low crystalline It is preferably an amorphous ethylene-α-olefin random copolymer. The α-olefin forming the ethylene-α-olefin random copolymer is usually an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, Although 1-decene, 1-tetradecene, and 1-octadecene are mentioned, propylene is preferable from the viewpoint of heat generation and a point that radicals are easily generated on the polyolefin during graft modification. As a content ratio of ethylene and propylene in the ethylene-propylene copolymer, it is preferable that the propylene content is 80 to 90% by weight and the ethylene content is 10 to 20% by weight. When the ethylene content is higher than this range, the ethylene-propylene copolymer has a high density, resulting in a problem that the low-temperature adhesion performance is deteriorated or the heat resistance is not practical. Furthermore, there is a possibility that the cross-linking reaction is preceded at the ethylene portion at the time of modification, not only the low-temperature adhesiveness is lowered, but also cannot be obtained as an adhesive film having a good appearance. On the other hand, when the ethylene content is less than this range, the low-temperature adhesiveness tends to decrease.
変性に使用する共重合体には、上述の、変性樹脂の熱特性を損なわない範囲であれば、他のジエン、ビニルエステルなどを第３成分として共重合してもよい。また、これらの変性エチレン−αオレフィン共重合体は、２種以上を混合して用いてもよく、２種以上の共重合体を混合したものを変性して用いてもかまわない。これらは、粒子状のものであってもペレット状のものであってもよく、その大きさや形はとくに制限されるものではない。 The copolymer used for modification may be copolymerized with another diene, vinyl ester, or the like as the third component as long as the above-described thermal properties of the modified resin are not impaired. These modified ethylene-α olefin copolymers may be used as a mixture of two or more, or a mixture of two or more copolymers may be used after modification. These may be in the form of particles or pellets, and the size and shape are not particularly limited.
変性エチレン−αオレフィン共重合体の製造には、溶融混練による方法、溶液による方法、懸濁法などの一般的なラジカルグラフト法によって行うことが出来る。この中で、経済的で、簡便かつ生産性に富む点では溶融混練法が好ましい。 The modified ethylene-α-olefin copolymer can be produced by a general radical grafting method such as a melt kneading method, a solution method, or a suspension method. Of these, the melt-kneading method is preferred because it is economical, simple and highly productive.
変性に用いるモノマーとしては、極性のある被着体との接着性を向上させるため、極性基含有ビニルモノマーが一般に用いられるが、中でも（a）エポキシ基含有ビニル単量体が、得られる接着剤組成物の接着性、フィルム成形性の面で好適である。a）エポキシ基含有ビニル単量体としては、特に制限されないが、好ましくは炭素数４〜２０、より好ましくは４〜１０のエポキシ基含有ビニル単量体であり、メタクリル酸グリシジル、アクリル酸グリシジル、マレイン酸モノグリシジル、マレイン酸ジグリシジル、イタコン酸モノグリシジル、イタコン酸ジグリシジル、アリルコハク酸モノグリシジル、アリルコハク酸ジグリシジル、ｐ−スチレンカルボン酸グリシジル、アリルグリシジルエーテル、メタアリルグリシジルエーテル、スチレン−ｐ−グリシジルエーテル、ｐ−グリシジルスチレンなどのグリシジル基含有ビニル単量体、３，４−エポキシ−１−ブテン、３，４−エポキシ−３−メチル−１−ブテンなどのエポキシオレフィン、ビニルシクロヘキセンモノオキシドなどの１種または２種以上が挙げられる。これらのうち、メタクリル酸グリシジルが安価で、溶融変性で適用しやすい点で好ましく、不飽和カルボン酸モノマーと比較して押出変性時に真空脱揮することで容易に除去でき、フィッシュアイや、発泡による穴あきなどの少ない外観の良好なホットメルト型接着フィルムの製造に好適である。 As a monomer used for modification, a polar group-containing vinyl monomer is generally used in order to improve adhesion to a polar adherend. Among them, (a) an epoxy group-containing vinyl monomer is obtained. It is suitable in terms of the adhesiveness and film moldability of the composition. a) Although it does not restrict | limit especially as an epoxy-group containing vinyl monomer, Preferably it is C4-C20, More preferably, it is an epoxy-group containing vinyl monomer of 4-10, glycidyl methacrylate, glycidyl acrylate, Monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, glycidyl p-styrenecarboxylate, allyl glycidyl ether, methallyl glycidyl ether, styrene-p-glycidyl ether, Glycidyl group-containing vinyl monomers such as p-glycidylstyrene, epoxy olefins such as 3,4-epoxy-1-butene and 3,4-epoxy-3-methyl-1-butene, and one kind such as vinylcyclohexene monoxide Or 2 or more types are mentioned. Among these, glycidyl methacrylate is preferable because it is inexpensive and easy to apply by melt modification, and can be easily removed by vacuum devolatilization during extrusion modification compared to unsaturated carboxylic acid monomers. It is suitable for producing a hot-melt adhesive film having a good appearance with few holes.
変性エチレン−αオレフィン共重合体中のエポキシ基含有ビニル単量体の含有量は、ベース樹脂１００重量部に対して、０．１〜５重量％であることが好ましい。０．１重量％より少ないと接着性が不充分であり、５重量％より多いと溶融混練中にグラフト鎖が反応して一部架橋を起こし、成形性が劣ると同時にフィッシュアイ、ブツなどによる製品外観が悪化し、且つ、かつ接着性も低下する。（a）エポキシ基含有ビニル単量体の添加量は、エチレン−αオレフィン共重合体１００重量部に対して、０．５〜１０重量部であることが好ましい。添加量が少なすぎると接着性が充分に改善されない傾向があり、添加量が多すぎるとグラフトに寄与しないフリーポリマーの副生が増大する傾向や、好適な形状や外観を有するフィルム状接着樹脂組成物として取得できない傾向がある。 The content of the epoxy group-containing vinyl monomer in the modified ethylene-α-olefin copolymer is preferably 0.1 to 5% by weight with respect to 100 parts by weight of the base resin. If it is less than 0.1% by weight, the adhesiveness is insufficient, and if it exceeds 5% by weight, the graft chain reacts during melt-kneading to cause partial crosslinking, resulting in poor moldability and at the same time due to fish eyes, butts, etc. The appearance of the product deteriorates and the adhesiveness also decreases. (A) It is preferable that the addition amount of an epoxy group containing vinyl monomer is 0.5-10 weight part with respect to 100 weight part of ethylene-alpha olefin copolymers. If the addition amount is too small, the adhesiveness tends not to be improved sufficiently. If the addition amount is too large, the by-product of free polymer that does not contribute to the graft tends to increase, and a film-like adhesive resin composition having a suitable shape and appearance. There is a tendency that it cannot be acquired as a thing.
ラジカル重合開始剤としては、有機過酸化物が一般的に用いられ、例えば水素引き抜き能が高いものとして、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキシ）バレレート、２，２−ビス（ｔ−ブチルパーオキシ）ブタンなどのパーオキシケタール；ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、α，α´−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、ｔ−ブチルクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３などのジアルキルパーオキサイド；ベンゾイルパーオキサイドなどのジアシルパーオキサイド；ｔ−ブチルパーオキシオクテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシイソプロピルカーボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレートなどのパーオキシエステルが好ましい。これらは、２種以上を組み合わせて用いてもよい。 前記ラジカル重合開始剤の添加量は、エチレン−αオレフィン共重合体１００重量部に対して、０．０１〜１０重量部の範囲内にあることが好ましく、０．０５〜５重量部の範囲内にあることがさらに好ましい。０．０１重量部未満では変性が充分に進行せず、１０重量部を超えると架橋反応による流動性の低下やゲル分の増加により、接着性が低下することがある。 As the radical polymerization initiator, an organic peroxide is generally used. For example, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, Peroxyketals such as 1,2-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide Dialkyl peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as yl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate , T-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate Peroxyesters such as are preferred. You may use these in combination of 2 or more type. The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight, and in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the ethylene-α-olefin copolymer. More preferably. If the amount is less than 0.01 parts by weight, the modification does not proceed sufficiently. If the amount exceeds 10 parts by weight, the adhesiveness may be lowered due to a decrease in fluidity due to a crosslinking reaction or an increase in gel content.
（a）エポキシ基含有ビニル単量体のグラフト率を向上させる目的で、（ｂ）芳香族ビニル単量体を添加することが好ましい。また、芳香族ビニル単量体を共存させることで、ポリオレフィンの主鎖切断による機械的特性が低下するのを抑えることができ、接着剤組成物の耐熱性を保つことができる。 For the purpose of improving the graft ratio of (a) the epoxy group-containing vinyl monomer, it is preferable to add (b) an aromatic vinyl monomer. In addition, the coexistence of the aromatic vinyl monomer can suppress the deterioration of the mechanical properties due to the main chain cleavage of the polyolefin, and the heat resistance of the adhesive composition can be maintained.
（ｂ）芳香族ビニル単量体としては、特に制限されないが、好ましくは炭素数４〜２０、より好ましくは６〜１５の芳香族ビニル単量体である。例示するならば、スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、β−メチルスチレン、ジメチルスチレン、トリメチルスチレンなどのメチルスチレン；ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、α−クロロスチレン、β−クロロスチレン、ジクロロスチレン、トリクロロスチレンなどのクロロスチレン；ｏ−ブロモスチレン、ｍ−ブロモスチレン、ｐ−ブロモスチレン、ジブロモスチレン、トリブロモスチレンなどのブロモスチレン；ｏ−フルオロスチレン、ｍ−フルオロスチレン、ｐ−フルオロスチレン、ジフルオロスチレン、トリフルオロスチレンなどのフルオロスチレン；ｏ−ニトロスチレン、ｍ−ニトロスチレン、ｐ−ニトロスチレン、ジニトロスチレン、トリニトロスチレンなどのニトロスチレン；ｏ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシスチレン、ジヒドロキシスチレン、トリヒドロキシスチレンなどのビニルフェノール；ｏ−ジビニルベンゼン、ｍ−ジビニルベンゼン、ｐ−ジビニルベンゼンなどのジビニルベンゼン；ｏ−ジイソプロペニルベンゼン、ｍ−ジイソプロペニルベンゼン、ｐ−ジイソプロペニルベンゼンなどのジイソプロペニルベンゼン；などの１種または２種以上が挙げられる。これらのうちスチレン、α−メチルスチレン、ｐ−メチルスチレンなどのメチルスチレン、ジビニルベンゼン単量体またはジビニルベンゼン異性体混合物が安価であるという点で好ましい。 (B) Although it does not restrict | limit especially as an aromatic vinyl monomer, Preferably it is C4-C20, More preferably, it is a C6-C15 aromatic vinyl monomer. For example, styrene; methyl styrene such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene, trimethyl styrene; o-chloro styrene, m-chloro Chlorostyrene such as styrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene; o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, tribromostyrene, etc. Bromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinitrostyrene, Nitrostyrene such as renitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene; o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, etc. 1 type, or 2 or more types, such as divinylbenzene; diisopropenylbenzene, such as o-diisopropenylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene; Of these, methylstyrene such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene monomer or divinylbenzene isomer mixture is preferable in that it is inexpensive.
前記（ｂ）芳香族ビニル単量体の添加量は、エチレン−αオレフィン共重合体１００重量部に対して、０．１〜１０重量部であることが好ましく、１〜５重量部であることがさらに好ましい。添加量が少なすぎるとエチレン−αオレフィン共重合体に対する（a）エポキシ基含有ビニル単量体のグラフト率が劣る傾向がある。一方、添加量が１０重量部を超えると（a）エポキシ基含有ビニル単量体のグラフト効率が飽和域に達するとともに、過剰な架橋反応が進行して、接着性が低下する恐れがある。 溶融混練時の添加順序及び方法については、エチレン−αオレフィン共重合体とラジカル重合開始剤を溶融混練した混合物に不飽和カルボン酸及び／又はその誘導体、あるいは芳香族ビニル単量体を加え溶融混練する添加順序がよく、この添加順序で行うことでグラフトに寄与しない低分子量体の生成を抑制することができる。なお、そのほか必要に応じ添加される材料の混合や溶融混練の順序及び方法はとくに制限されるものではない。 The amount of the (b) aromatic vinyl monomer added is preferably 0.1 to 10 parts by weight, and 1 to 5 parts by weight with respect to 100 parts by weight of the ethylene-α-olefin copolymer. Is more preferable. If the amount added is too small, the graft ratio of the (a) epoxy group-containing vinyl monomer to the ethylene-α-olefin copolymer tends to be poor. On the other hand, when the addition amount exceeds 10 parts by weight, the graft efficiency of the (a) epoxy group-containing vinyl monomer reaches a saturation region, and an excessive crosslinking reaction proceeds, whereby the adhesiveness may be lowered. Regarding the order and method of addition at the time of melt kneading, an unsaturated carboxylic acid and / or a derivative thereof, or an aromatic vinyl monomer is added to the mixture obtained by melting and kneading an ethylene-α olefin copolymer and a radical polymerization initiator. The order of addition is good, and the formation of low molecular weight substances that do not contribute to grafting can be suppressed by carrying out in this order of addition. In addition, the order and method of mixing and melt-kneading the materials added as necessary are not particularly limited.
溶融混練時の加熱温度は、エチレン−αオレフィン共重合体が充分に溶融し、過剰な熱分解、架橋反応、およびフィッシュアイの増加が抑えられるという点で、１８０〜２００℃が好ましい。また前記の溶融混練の装置としては、一軸又は多軸押出機、バンバリーミキサー、プラストミル、加熱ロールニーダー、などを使用することができるが、生産性の面から減圧装置を装備した単軸あるいは二軸押出機を用いる方法が好ましい。溶融混練の時間（ラジカル重合開始剤を混合してからの時間）は、通常３０秒間〜６０分間である。 The heating temperature at the time of melt kneading is preferably 180 to 200 ° C. from the viewpoint that the ethylene-α-olefin copolymer is sufficiently melted and excessive thermal decomposition, crosslinking reaction, and increase of fish eyes are suppressed. As the melt kneading apparatus, a single-screw or multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, and the like can be used. A method using an extruder is preferred. The melt kneading time (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.
（２）スチレン共役ジエン系ブロック共重合体
本発明の（Ｂ）成分のスチレン共役ジエン系ブロック共重合体とは、ビニル芳香族化合物を主成分とする重合体ブロックからなるハードセグメントと、共役ジエン化合物を主成分とする重合体からなるソフトセグメントを有するブロック共重合体であり、ブロックＡがビニル芳香族化合物、ブロックＢが共役ジエン化合物であるとしたときに、一般式Ａ−Ｂ、Ａ−Ｂ−Ａ、Ｂ−Ａ−Ｂ−Ａ、Ａ−Ｂ−Ａ−Ｂ−Ａ等で表される。ブロック共重合体を用いることで、各種粘着付与剤との併用で、低温加工での各種基材との接着性が得られると共に、低タック性、耐熱性のバランスの取れた接着性樹脂組成物の製造が可能である。
(2) Styrene conjugated diene block copolymer The styrene conjugated diene block copolymer of the component (B) of the present invention is a hard segment composed of a polymer block mainly composed of a vinyl aromatic compound, and a conjugated diene. A block copolymer having a soft segment composed of a polymer having a compound as a main component, wherein the block A is a vinyl aromatic compound and the block B is a conjugated diene compound, the general formulas AB, A- It is represented by B-A, B-A-B-A, A-B-A-B-A, and the like. By using a block copolymer, it is possible to obtain adhesiveness with various base materials in low temperature processing in combination with various tackifiers, and an adhesive resin composition with a balance between low tack and heat resistance. Can be manufactured.
スチレン共役ジエン系ブロック共重合体の好ましい例としては、スチレン−ブタジエンジブロックコポリマー、スチレンーブタジエントリブロックコポリマー、スチレンーイソプレンジブロックコポリマー、スチレンーイソプレントリブロックコポリマー、水素添加スチレン−ブタジエンジブロックコポリマー、水素添加スチレンーブタジエントリブロックコポリマー、水素添加スチレンーイソプレンジブロックコポリマー、水素添加スチレンーイソプレントリブロックコポリマーなどが挙げられ、耐熱性および耐候性が良好なものとなる点から、水素添加スチレン−イソプレントリブロックコポリマー（ＳＥＰＳ）、水素添加スチレン−ブタジエントリブロックコポリマー（ＳＥＢＳ）、が特に好ましい。 Preferred examples of the styrene conjugated diene block copolymer include styrene-butadiene diblock copolymer, styrene-butadiene triblock copolymer, styrene-isoprene block copolymer, styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer. , Hydrogenated styrene-butadiene triblock copolymer, hydrogenated styrene-isoprene diblock copolymer, hydrogenated styrene-isoprene triblock copolymer, etc., and hydrogenated styrene- Isoprene triblock copolymer (SEPS), hydrogenated styrene-butadiene triblock copolymer (SEBS) are particularly preferred.
（３）粘着付与剤
（Ｃ）成分の粘着付与剤としては、種々のものがあるが、変性エチレンーαオレフィン中のエポキシ基と反応する構造を含まない脂環族系石油樹脂、テルペン樹脂（α−ピネン、β-ピネン、リモネンなどの重合体）、芳香族変性テルペン樹脂が好ましく、中でも濡れ性、ハンドリング性、耐熱性の観点から芳香族変性テルペン樹脂がより好ましく、入手のしやすさからスチレン変性テルペン樹脂が特に好ましい。テルペンフェノール樹脂や、ロジン系樹脂は、その構造上、低酸価、低水酸基価とすることが困難であるため、溶融混練、変性樹脂中のエポキシ基と反応して、フィッシュアイ、ゲルが増加するだけでなく、樹脂組成物が増粘し、フィルム成形性が悪く傾向がある。低温加工での接着性、耐熱性、接着剤樹脂組成物のハンドリングの観点から、環球法による軟化点が９０℃以上、好ましくは１００〜１７０℃より好ましくは、１３０〜１６０℃の範囲ものを用いることが好ましい。軟化点が９０℃よりも低いものであると接着剤組成物の耐熱性が低下するとともに、スチレン系熱可塑性エラストマーやエチレン−αオレフィン共重合体との溶融混練が困難となるばかりか、接着剤樹脂組成物の常温タックが強くなりすぎてフィルム成形が困難となる。粘着付与剤としては、単独あるいは２種以上をあわせて用いることができる。
(3) Tackifiers There are various types of tackifiers for component (C), but alicyclic petroleum resins and terpene resins that do not contain a structure that reacts with the epoxy group in the modified ethylene-α-olefin (α -Polyene, β-pinene, limonene, and the like) and aromatic modified terpene resins are preferred. Among them, aromatic modified terpene resins are more preferred from the viewpoint of wettability, handling properties, and heat resistance, and styrene is easily available. A modified terpene resin is particularly preferred. Because terpene phenol resin and rosin resin are difficult to have low acid value and low hydroxyl value due to their structure, fish eyes and gel increase due to reaction with epoxy groups in melt-kneaded and modified resins In addition, the resin composition tends to thicken and the film moldability tends to be poor. From the viewpoint of adhesion at low temperature processing, heat resistance, and handling of the adhesive resin composition, a softening point by the ring and ball method is 90 ° C. or higher, preferably 100 to 170 ° C., more preferably 130 to 160 ° C. It is preferable. When the softening point is lower than 90 ° C., the heat resistance of the adhesive composition is lowered, and not only the melt-kneading with a styrene-based thermoplastic elastomer or an ethylene-α-olefin copolymer is difficult, but the adhesive The room temperature tack of the resin composition becomes too strong, making film formation difficult. As a tackifier, it can use individually or in combination of 2 or more types.
（４）第一層の接着性樹脂組成物
本発明のホットメルト型接着フィルムをなす第一層の接着性樹脂組成物の配合割合としては、（１）変性エチレン−αオレフィン共重合体６０〜９０重量部および（２）スチレン共役ジエン系ブロック共重合体４０〜１０重量部［ただし、（Ａ）＋（Ｂ）＝１００重量部］のベース樹脂に対し、粘着付与剤３０〜６０重量部である。（C）成分の粘着付与剤の配合量としては、４０〜５０重量部であることがより好ましい。（Ｃ）成分の粘着付与剤の配合量が、３０重量部より少ないと被着体へのぬれ性が乏しくなり接着性が低下し、６０重量部より多いと凝集力が乏しくなり接着性、耐熱性が低下するとともに、接着性樹脂組成物のタックが強くなりすぎて、配合およびフィルム成形時の取り扱いが困難となる。一方で、ベース樹脂中（Ａ）変性エチレン−αオレフィン共重合体と（Ｂ）スチレン系熱可塑性エラストマーの配合比としては、（Ａ）６５〜８５重量部、（Ｂ）３５〜１５重量部がより好ましく、（A）７０〜８０重量部、（B）３０〜２０重量部であることがさらに好ましい。この配合比とすることで、低温接着加工での被着体への充分な濡れ性と、常温でのタックのバランスが取れた接着剤樹脂組成物を得ることができる。
(4) Adhesive resin composition of first layer As a blending ratio of the adhesive resin composition of the first layer forming the hot melt adhesive film of the present invention, (1) modified ethylene-α-olefin copolymer 60 to 90 to 60 parts by weight and (2) 40 to 10 parts by weight of a styrene conjugated diene block copolymer [provided that (A) + (B) = 100 parts by weight] of the base resin is 30 to 60 parts by weight. is there. (C) As a compounding quantity of the tackifier of a component, it is more preferable that it is 40-50 weight part. When the blending amount of the component (C) tackifier is less than 30 parts by weight, the wettability to the adherend is poor and the adhesiveness is lowered, and when it is more than 60 parts by weight, the cohesive force is poor and the adhesiveness and heat resistance are reduced. In addition, the tackiness of the adhesive resin composition becomes too strong and handling during compounding and film forming becomes difficult. On the other hand, (A) 65 to 85 parts by weight and (B) 35 to 15 parts by weight of (A) modified ethylene-α-olefin copolymer and (B) styrene-based thermoplastic elastomer in the base resin. More preferably, (A) 70 to 80 parts by weight and (B) 30 to 20 parts by weight are more preferable. By setting it as this compounding ratio, the adhesive resin composition with sufficient wettability to the to-be-adhered body in a low-temperature-adhesion process and the tack | tuck at normal temperature can be obtained.
なお、接着性樹脂組成物には必要に応じて、エチレン重合体（ＰＥ）、αオレフィン重合体、エチレン−αオレフィン共重合体、エチレン−アクリル酸エチル共重合体（ＥＥＡ）、ＥＶＡなどの樹脂、酸化防止剤、金属不活性剤、燐系加工安定剤、紫外線吸収剤、紫外線安定剤、蛍光増白剤、金属石鹸、制酸吸着剤などの安定剤、または架橋剤、連鎖移動剤、核剤、滑剤、可塑剤、充填材、強化材、顔料、染料、難燃剤、帯電防止剤などの添加剤を本発明の効果を損なわない範囲内で添加してもよい。これらの樹脂、安定剤および添加剤を用いる場合は、予めスチレン系熱可塑性エラストマーまたは、エチレン−αオレフィン共重合体に添加されているものであってもよく、これらの溶融変性の際に添加されるものであってもよく、接着性樹脂組成物を溶融混錬により製造する際に添加されるものであってもよく、後述のホットメルト型接着フィルムの製造の際に添加されるものであってもよい。 The adhesive resin composition may be made of resin such as ethylene polymer (PE), α-olefin polymer, ethylene-α olefin copolymer, ethylene-ethyl acrylate copolymer (EEA), EVA, if necessary. , Antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal soaps, stabilizers such as antacid adsorbents, or crosslinking agents, chain transfer agents, nuclei Additives such as agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants and antistatic agents may be added within a range that does not impair the effects of the present invention. When these resins, stabilizers and additives are used, they may be added in advance to the styrenic thermoplastic elastomer or ethylene-α olefin copolymer, and are added during the melt modification. May be added when the adhesive resin composition is produced by melt kneading, or may be added during the production of a hot-melt adhesive film described later. May be.
（４）第二層の接着性樹脂組成物
本発明のホットメルト型接着フィルムをなす第二層の接着性樹脂組成物は、第一層では必須成分となる（Ｃ）成分の粘着付与剤を含まない熱可塑性樹脂組成物である。粘着付与剤を含む第一層は比較的低温条件での接着が可能であるのに対し、第二層は第一層よりも高温度で接着性を発現させる目的で、（Ｃ）成分の粘着付与剤を含まない熱可塑性樹脂であることが好ましい。一般的に、ホットメルト型接着フィルムを用いて加飾シートと基材となる成形品とを複合化する際は、第一ステップとして加飾シートとホットメルト型接着フィルムを複合化し、次いで第二ステップで基材と複合化する。このように段階的に複合化を行うため、それぞれの加工温度も異なる場合が多い。特に、加飾フィルム表面にエンボス加工しながらホットメルト型接着フィルムを複合化する際は、高温度での加工が必要となる。例えば、加飾シートと接する面を本発明の第二層側、基材と接する面を第一層側に配置し、第一ステップが高温度、第二ステップが低温度で加工する際、第二層に粘着付与剤が含まれていると、粘着付与剤が接着表面にブリードアウトし接着強度が低下したり、接着ムラが生じることがある。また、自動車分野向けの成形品などでは、高温下において加飾フィルムが剥離しないことが要求され、接着層の耐熱性が必要な場合もある。そのため第二層に粘着付与剤が含まれていると耐熱性が低下することもあり好ましくない。
(4) Adhesive resin composition of the second layer The adhesive resin composition of the second layer forming the hot melt adhesive film of the present invention comprises the tackifier of component (C), which is an essential component in the first layer. It is a thermoplastic resin composition not containing. While the first layer containing a tackifier can be bonded at a relatively low temperature, the second layer has a component (C) adhesive for the purpose of exhibiting adhesiveness at a higher temperature than the first layer. A thermoplastic resin containing no imparting agent is preferable. Generally, when a decorative sheet and a molded article to be a base material are combined using a hot-melt adhesive film, the decorative sheet and the hot-melt adhesive film are combined as a first step, and then the second Composite with substrate in steps. Since compounding is performed step by step, the processing temperatures are often different. In particular, when a hot melt adhesive film is combined while embossing the decorative film surface, processing at a high temperature is required. For example, when the surface that contacts the decorative sheet is disposed on the second layer side of the present invention, the surface that contacts the base material is disposed on the first layer side, the first step is processed at a high temperature, and the second step is processed at a low temperature, When the tackifier is contained in the two layers, the tackifier may bleed out on the adhesion surface, resulting in a decrease in adhesive strength or uneven adhesion. In addition, in a molded product for the automobile field, it is required that the decorative film does not peel off at high temperatures, and the heat resistance of the adhesive layer may be required. Therefore, when the tackifier is contained in the second layer, the heat resistance may decrease, which is not preferable.
本発明のホットメルト型接着フィルムをなす第二層の接着性樹脂組成物は以下に制限されるものではないが、例えば、前記の（Ｂ）成分のスチレン共役ジエン系ブロック共重合体、変性エチレン−αオレフィン共重合体、エチレン重合体（ＰＥ）、αオレフィン重合体、エチレン−αオレフィン共重合体、エチレン−アクリル酸エチル共重合体（ＥＥＡ）、ＥＶＡ、マレイン酸変性オレフィン重合体等の酸変性オレフィン重合体、（メタ）アクリル酸エステル重合体、ポリエステル系重合体、ポリカーボネート系重合体、ウレタン系重合体などの群から選ばれる一つ以上の熱可塑性樹脂組成物が挙げられる。中でも、前記の変性エチレン−αオレフィン共重合体を含む熱可塑性樹脂組成物を用いることが好ましい。 The adhesive resin composition of the second layer forming the hot melt type adhesive film of the present invention is not limited to the following. For example, the styrene conjugated diene block copolymer of component (B), modified ethylene Acids such as α-olefin copolymer, ethylene polymer (PE), α-olefin polymer, ethylene-α-olefin copolymer, ethylene-ethyl acrylate copolymer (EEA), EVA, maleic acid-modified olefin polymer One or more thermoplastic resin compositions selected from the group of modified olefin polymers, (meth) acrylic acid ester polymers, polyester polymers, polycarbonate polymers, urethane polymers and the like can be mentioned. Among them, it is preferable to use a thermoplastic resin composition containing the modified ethylene-α olefin copolymer.
（５）ホットメルト型接着フィルムの製造方法
本発明のホットメルト型接着フィルムの製造方法は、特に限定されるものではないが、例えば接着性樹脂組成物を溶融混練により得た後に、各種の押出成形機、インフレーション成形機などを用いて二層構成のシート状成形体に加工することが可能である。中でも、先端に共押出可能なＴ型ダイスを備えた押出機を使う方法が汎用的で好ましい。共押出ダイスはマルチマニホールド方式やフィードブロック方式などが好適である。溶融混錬の装置としては、一軸又は多軸押出機、バンバリーミキサー、プラストミル、加熱ロールニーダー、などを使用することができる。生産性の面から減圧装置を装備した単軸あるいは二軸押出機を用いる方法が好ましい。また、各々の材料を充分に均一に混合するために、前記溶融混練を複数回繰返してもよい。
(5) Manufacturing method of hot melt type adhesive film The manufacturing method of the hot melt type adhesive film of the present invention is not particularly limited. For example, after the adhesive resin composition is obtained by melt kneading, various extrusions are performed. Using a molding machine, an inflation molding machine, etc., it is possible to process into a two-layered sheet-like molded body. Among these, a method using an extruder equipped with a T-die that can be co-extruded at the tip is versatile and preferable. The co-extrusion die is preferably a multi-manifold method or a feed block method. As an apparatus for melt kneading, a single-screw or multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, or the like can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder equipped with a pressure reducing device is preferable. Moreover, in order to mix each material sufficiently uniformly, the melt kneading may be repeated a plurality of times.
ホットメルト型接着フィルムを製造する場合、フィルム単体をロール状に製造すると、フィルム同士がブロッキングするため、ホットメルト型接着フィルムの両面に離型ＰＥＴなどのセパレーターフィルムを貼り合せる必要があり、生産コストが高いといった課題がある。ところが本発明のホットメルト型接着フィルムの第二層には粘着付与剤が含まれないため、常温下における第二層の表面はタックが少なく、フィルム生産工程のロールへの貼り付きが小さく、第二層表面側には貼り付き防止用のセパレーターがなくても生産可能であり、大幅に生産コストを削減でき有用である。 When manufacturing a hot-melt adhesive film, if a single film is manufactured in a roll shape, the films block each other. Therefore, it is necessary to bond a separator film such as a release PET to both sides of the hot-melt adhesive film, and the production cost There is a problem that is high. However, since the second layer of the hot-melt adhesive film of the present invention does not contain a tackifier, the surface of the second layer at room temperature is less tacky, less sticking to the roll in the film production process, It can be produced without a separator for preventing sticking on the surface of the two layers, which is useful because it can greatly reduce production costs.
本発明のホットメルト型接着フィルムの厚みは特に制限はないが、１０〜２００μｍが好ましく、２０〜１５０μｍがより好ましい。また、本発明のホットメルト型接着フィルムの第一層と第二層の厚み比率は特に制限はく、用途によって第一層と第二層の厚みを任意に決定すればよい。 Although there is no restriction | limiting in particular in the thickness of the hot-melt-type adhesive film of this invention, 10-200 micrometers is preferable and 20-150 micrometers is more preferable. Moreover, the thickness ratio of the first layer and the second layer of the hot melt adhesive film of the present invention is not particularly limited, and the thickness of the first layer and the second layer may be arbitrarily determined depending on the application.
（６）ホットメルト型接着フィルムを含む積層体 本発明のホットメルト型接着フィルムの第一層側は、比較的低い処理温度で種々の基材と接着可能であり、第二層側は、第一層側よりも高い処理温度で種々の加飾シートと接着可能であり、加飾シート／ホットメルト型接着フィルム／基材といった積層体が二段階成形により容易に得られる。本発明のホットメルト型接着フィルムの第二層側と加飾シートを接着する際の処理温度としては、１２０〜２５０℃が好ましく、第一層側と基材を接着する際の処理温度としては、９０〜１３０℃が好ましい。本発明の積層体を構成する材料としては、紙、木綿，麻，布、木板などのセルロース系高分子材料、ポリプロピレン，ポリエチレンなどのポリオレフィン系樹脂、ポリスチレン，スチレン−ブタジエンブロック共重合体（ＳＢＳ樹脂），スチレン−アクリロニトリル共重合体（ＡＳ樹脂），アクリロニトリル−エチレン／プロピレン−スチレン共重合体（ＡＥＳ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）などのスチレン系樹脂、ポリカーボネート系樹脂、（メタ）アクリル系樹脂、ポリエステル系樹脂、ナイロン、ポリウレタンなどのポリアミド系樹脂、フェノール樹脂、エポキシ樹脂等の合成高分子材料、金、銀、銅、鉄、錫、鉛、アルミニウムなどの金属材料が挙げられる。これら材料は、異なる２種類以上の材料を混合、複合してもよい。また、積層体が本発明の接着性フィルムを介して、異なる２つの被着体が接着してなるものである場合、２つの基材を構成する材料は、同じ種類の材料でも異なる種類の材料のいずれでもよい。本発明のホットメルト型接着フィルムは、材料の接着面を処理することなく、強力な接着が可能であるが、必要に応じて、プラズマやレーザーなどによる表面改質、表面酸化、エッチングなどの表面処理等を実施してもよい。 (6) Laminate including hot melt adhesive film The first layer side of the hot melt adhesive film of the present invention can be bonded to various substrates at a relatively low processing temperature, and the second layer side It can be bonded to various decorative sheets at a higher processing temperature than the one-layer side, and a laminate such as a decorative sheet / hot-melt adhesive film / substrate can be easily obtained by two-stage molding. As processing temperature at the time of bonding the second layer side of the hot melt type adhesive film of the present invention and the decorative sheet, 120 to 250 ° C. is preferable, and as processing temperature at the time of bonding the first layer side and the substrate, 90-130 ° C is preferred. The material constituting the laminate of the present invention includes cellulosic polymer materials such as paper, cotton, hemp, cloth, and wood board, polyolefin resins such as polypropylene and polyethylene, polystyrene, styrene-butadiene block copolymer (SBS resin). ), Styrene-acrylonitrile copolymer (AS resin), acrylonitrile-ethylene / propylene-styrene copolymer (AES resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and other styrene resins, polycarbonate resins, (Meth) acrylic resins, polyester resins, polyamide resins such as nylon and polyurethane, synthetic polymer materials such as phenolic resins and epoxy resins, metal materials such as gold, silver, copper, iron, tin, lead, and aluminum Can be mentioned. These materials may be a mixture or composite of two or more different materials. When the laminate is formed by adhering two different adherends via the adhesive film of the present invention, the materials constituting the two substrates may be the same type of materials or different types of materials. Either of these may be used. The hot melt adhesive film of the present invention can be strongly bonded without treating the bonding surface of the material, but if necessary, the surface such as surface modification by plasma or laser, surface oxidation, etching, etc. Processing may be performed.
（７）用途 本発明の積層体の用途の具体例としては特に限定されないが、基材として表皮材及び成形品を使用する用途、例えば自動車等の内装材料（自動車内装用天井材，自動車内装用ドア部材，自動車内装用ダッシュボード部材、インパネ等）、家電部品（パソコン筺体、薄型テレビのフレーム等）、住居資材（内装壁板、化粧フィルム等）として好適に使用することができる。ここで用いられる表皮材とは、予めフィルム、シート、発泡体、各種不織物、織物に成形されたものであり、例えば、ポリ塩化ビニル、各種ポリオレフィン、ＡＢＳから製造される高分子製加飾シート、ポリエステル不織布、起毛ニット、ファブリック、ポリウレタンレザー、ポリプロピレン、ポリエチレン、ポリブチレン、およびこれらオレフィンの共重合体を主成分として製造されるポリオレフィン系発泡体などが挙げられる。また、ここで用いられる成形品としては、ＡＢＳ、ＰＣ／ＡＢＳ、ポリオレフィン、ガラス繊維強化ポリオレフィン、ガラス繊維強化ナイロンなどの各種高分子材料の射出成形品、木材チップ、木質粉などを熱硬化性樹脂やポリオレフィン樹脂で熱プレス成形により固めた木質成形品や木質ボードが挙げられる。
本発明のホットメルト型接着フィルムは、耐熱性が要求され、かつ第二層側と加飾フィルムを貼り合せると同時に表面を高温度でエンボス加工した後、第一層側と基材を比較的低い温度で接着させる加工法で得られるエンボス加工成形品加飾の用途に好適である。
(7) Uses Although it is not particularly limited as a specific example of the use of the laminate of the present invention, it is used for using a skin material and a molded product as a base material, for example, interior materials for automobiles (ceiling materials for automobile interiors, automobile interiors) It can be suitably used as a door member, a dashboard member for automobile interior, an instrument panel, etc., a home appliance part (a personal computer housing, a frame of a thin TV, etc.) and a housing material (an interior wall board, a decorative film, etc.). The skin material used here is a film, sheet, foam, various non-woven fabrics, woven fabrics, for example, a polymer decorative sheet manufactured from polyvinyl chloride, various polyolefins, ABS, for example. Polyester non-woven fabric, raised knit, fabric, polyurethane leather, polypropylene, polyethylene, polybutylene, and polyolefin-based foams produced mainly from copolymers of these olefins. In addition, as molded products used here, ABS, PC / ABS, polyolefin, glass fiber reinforced polyolefin, injection molded products of various polymer materials such as glass fiber reinforced nylon, wood chips, wood powder, etc. are thermosetting resins. And wood molded products and wood boards hardened by hot press molding with polyolefin resin.
The hot-melt adhesive film of the present invention is required to have heat resistance, and after the surface of the second layer is embossed at a high temperature, the first layer side and the substrate are relatively It is suitable for embossed molded product decoration obtained by a processing method of bonding at a low temperature.
本発明に関わる多層積層体を製造するにあたっては、熱ラミネート、真空成形、真空圧空成形、熱プレス、熱ロール、ホットスタンプ成形など、種々の成形方法を採用できる。中でも真空成形、真空圧空成形、ホットスタンプ成形は、表皮材とアールを有する成形品の接着に適用できる点で好ましい。アールを有する成形品とは、上に例示したような材質の成形品のうち、表皮材と接着する面として、平面円弧状の面を有する成形品を指し、自動車内装や家電筐体の形状骨格をなす成形品である。積層体の製造方法としては、例えば表皮材に接着フィルムを加熱ラミネートしておき、これを各成形に付すことで、成形体の形状に沿って表皮材を積層することができる。熱プレスや熱ロールは、このような成形品の円弧形状を損なう可能性があり好ましくない。特に、真空圧空成形は、表皮と成形品の接着の際、圧空圧をかけることにより、成形品の端部から成形品裏側にかけて表皮材を巻き込ませることができ、さらには、深絞り形状の成形品を被着体とした積層体を製造にも適用できる。 In producing the multilayer laminate according to the present invention, various molding methods such as thermal lamination, vacuum forming, vacuum / pressure forming, hot pressing, hot roll, hot stamping, etc. can be employed. Among these, vacuum forming, vacuum pressure forming, and hot stamping are preferable in that they can be applied to the bonding of a molded product having a skin material and a rounded shape. A molded product having a round shape refers to a molded product having a plane arc-shaped surface as a surface to be bonded to a skin material among molded products of the materials exemplified above, and is a shape skeleton of an automobile interior or home appliance housing. This is a molded product. As a manufacturing method of a laminated body, for example, an adhesive film is heated and laminated on a skin material, and this is applied to each molding, whereby the skin material can be laminated along the shape of the molded body. A hot press or a hot roll is not preferable because it may impair the arc shape of such a molded product. In particular, in vacuum / pressure forming, the skin material can be wound from the end of the molded product to the back side of the molded product by applying compressed air pressure when the skin and the molded product are bonded. A laminate having the product as an adherend can also be applied to production.
以下に具体的な実施例および比較例によって本発明をさらに詳細に示すが、本発明は下記実施例に限定されるものではない。下記実施例および比較例中「部」および「％」は、それぞれ「重量部」および「重量％」を表す。 Hereinafter, the present invention will be described in more detail by way of specific examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
１．変性エチレン−αオレフィンの製造
変性エチレン−αオレフィンの物性測定は以下のようにして行った。
（変性エチレン−αオレフィン共重合体中のメタクリル酸グリシジル、無水マレイン酸含量の分析）メタクリル酸グリシジル、無水マレイン酸含量は、得られた変性エチレンープロピレン共重合体ペレットを１１０℃に加熱したクロロベンゼンに溶解した後、そのクロロベンゼン溶液をアセトン中に滴下し再沈殿物させ、得られた再沈殿物について滴定を行うことにより得た。
（変性エチレン−αオレフィン共重合体中ＤＳＣ測定法）
示差走査型熱量計（ＳＨＩＭＡＤＺＵ社製、ＤＴＧ−５０）を用い、試料を窒素雰囲気下、２４０℃まで、２０℃／分で昇温させ、直ちに４０℃以下まで降温した後、２４０℃まで再度２０℃／分で昇温下時に得られた融解吸熱カーブから観測されるピークのピークトップとして定義される温度を融点（Ｔｍ）、その融解熱量をΔＨ（Ｊ／ｇ）とした。
（製造例１）
エチレン−プロピレン共重合体（（株）ダウ製ヴァーシファイ３４０１、ＭＦＲ８、エチレン含量１５重量％、密度０．８６３ｇ/ｃｍ３）１００部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（１分間半減期１７５℃）０.５部をシリンダー温度２００℃、回転数１５０ｒｐｍに設定した二軸押出機（４４ｍｍφ、Ｌ／Ｄ＝３８．５、（株）日本製鋼所製、製品名ＴＥＸ４４ＸＣＴ）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル３部、スチレン３部加え溶融混練した後、脱揮してストランド状に押出し、水冷後カッティングして、変性エチレン−プロピレン共重合体（Ａ１）を得た。得られた変性エチレン−プロピレン共重合体（A１）の物性は、表１の通りであった。（製造例２）
エチレン−プロピレン共重合体（（株）ダウ製ヴァーシファイ４３０１、ＭＦＲ２５、エチレン含量１２重量％、密度０．８６７ｇ/ｃｍ３）１００部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（１分間半減期１７５℃）０.５部をシリンダー温度２００℃、回転数１５０ｒｐｍに設定した二軸押出機（４４ｍｍφ、Ｌ／Ｄ＝３８．５、（株）日本製鋼所製、製品名ＴＥＸ４４ＸＣＴ）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル３部、スチレン３部加え溶融混練した後、脱揮してストランド状に押出し、水冷後カッティングして、変性エチレン−プロピレン共重合体（Ａ２）を得た。得られた変性エチレン−プロピレン共重合体（Ａ２）の物性は、表１の通りであった。
1. Production of modified ethylene-α olefin The physical properties of the modified ethylene-α olefin were measured as follows.
(Analysis of Glycidyl Methacrylate and Maleic Anhydride Content in Modified Ethylene-α Olefin Copolymer) The glycidyl methacrylate and maleic anhydride contents were measured by heating the obtained modified ethylene-propylene copolymer pellets to 110 ° C. Then, the chlorobenzene solution was dropped into acetone to cause reprecipitation, and the obtained reprecipitate was titrated.
(DSC measurement method in modified ethylene-α-olefin copolymer)
Using a differential scanning calorimeter (manufactured by SHIMADZU, DTG-50), the sample was heated up to 240 ° C. at 20 ° C./min in a nitrogen atmosphere, immediately cooled to 40 ° C. or lower, and then again up to 240 ° C. The temperature defined as the peak top of the peak observed from the melting endothermic curve obtained when the temperature was raised at 0 ° C./min was the melting point (Tm), and the heat of fusion was ΔH (J / g).
(Production Example 1)
100 parts of ethylene-propylene copolymer (Varfi 3401, MFR8, ethylene content 15% by weight, density 0.863 g / cm 3 ) manufactured by Dow Co., Ltd., 1,3-di (t-butylperoxyisopropyl) benzene (1 In a twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name TEX44XCT) in which 0.5 part is set to a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm. After supplying and melt-kneading, next, 3 parts of glycidyl methacrylate and 3 parts of styrene were added and melt-kneaded from the middle of the cylinder, then devolatilized, extruded into a strand shape, water-cooled and cut to obtain a modified ethylene-propylene copolymer. (A1) was obtained. Table 1 shows the physical properties of the obtained modified ethylene-propylene copolymer (A1). (Production Example 2)
Ethylene-propylene copolymer (Varphi 4301, MFR25, ethylene content 12% by weight, density 0.867 g / cm 3 ) 100 parts, 1,3-di (t-butylperoxyisopropyl) benzene (1) In a twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name TEX44XCT) in which 0.5 part is set to a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm. After supplying and melt-kneading, next, 3 parts of glycidyl methacrylate and 3 parts of styrene were added and melt-kneaded from the middle of the cylinder, then devolatilized, extruded into a strand shape, water-cooled and cut to obtain a modified ethylene-propylene copolymer. (A2) was obtained. Table 1 shows the physical properties of the modified ethylene-propylene copolymer (A2).
２．ホットメルト型接着フィルムの製造
表２の実施例１〜３及び、比較例１〜３の配合比率に従って、上述の製造例１〜２で得られた変性エチレンープロピレン共重合体（Ａ１）〜（Ａ２）および未変性エチレンーαオレフィン共重合体（Ａ３）〜（Ａ４）、下記原料（Ｂ１）、（Ｃ１）、（Ｄ１）を、水中カットペレタイザーを取り付けた、シリンダー温度１８０℃に設定した上記二軸押出機で溶融混練して、第一層接着性樹脂ペレットおよび第二層接着性樹脂を得た。なお、（Ａ１）〜（Ａ４）を単独で第一層または第二層として用いる場合は、上記の二軸押出機による溶融混練を省略した。得られたそれぞれの接着性樹脂ペレットを、シリンダー温度２００℃に設定した２台の単軸押出機（４０ｍｍφ、Ｌ／Ｄ＝２２）の先端に二種二層フィードブロック方式のＴ型ダイス（６００ｍｍ幅）を取り付けた共押出フィルム成形機を用いて、幅約５００ｍｍ、厚み５０μｍの二層構成フィルムを成形した。
（Ａ１）〜（Ａ２）変性エチレンーαオレフィン共重合体（製造例１〜２）
（Ａ３）エチレンーαオレフィン共重合体（ダウケミカル製、ヴァーシファイ３４０１、ＭＦＲ８）
（Ａ４）エチレンーαオレフィン共重合体（ダウケミカル製、ヴァーシファイ４３０１、ＭＦＲ２５）
（Ｂ１）水素添加スチレンイソプレントリブロックコポリマー（（株）クラレ製、ＳＥＰＴＯＮ２０６３）
（Ｃ１）スチレン変性テルペン樹脂（（株）ヤスハラケミカル製、ＹＳレジンTO１２５、軟化点１２５℃）
（D1）ポリエチレン（日本ユニカー（株）製、ＤＮＤＶ−０４０５Ｒ、軟化点１０５℃）
2. Production of hot-melt adhesive film According to the blending ratios of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, the modified ethylene-propylene copolymers obtained in the above Production Examples 1 and 2 ( A1) to (A2) and unmodified ethylene-α olefin copolymers (A3) to (A4), the following raw materials (B1), (C1), and (D1) were added to an underwater cut pelletizer at a cylinder temperature of 180 ° C. It melt-kneaded with the set said twin-screw extruder, and obtained the 1st layer adhesive resin pellet and the 2nd layer adhesive resin. In addition, when using (A1)-(A4) independently as a 1st layer or a 2nd layer, the melt-kneading by said twin-screw extruder was abbreviate | omitted. Each of the obtained adhesive resin pellets was placed on the tip of two single-screw extruders (40 mmφ, L / D = 22) set at a cylinder temperature of 200 ° C., and a T-type die (600 mm A two-layer film having a width of about 500 mm and a thickness of 50 μm was formed using a coextrusion film forming machine equipped with a width).
(A1) to (A2) Modified ethylene-α-olefin copolymer (Production Examples 1 and 2)
(A3) Ethylene-α-olefin copolymer (Dow Chemical, Versify 3401, MFR8)
(A4) Ethylene-α-olefin copolymer (Dow Chemical, Versify 4301, MFR25)
(B1) Hydrogenated styrene isoprene triblock copolymer (Kuraray Co., Ltd., SPTTON 2063)
(C1) Styrene-modified terpene resin (manufactured by Yashara Chemical Co., Ltd., YS resin TO125, softening point 125 ° C.)
(D1) Polyethylene (Nihon Unicar Co., Ltd., DNDV-0405R, softening point 105 ° C.)
３．ホットメルト型接着フィルムの評価 上述の実施例１〜３及び比較例１〜３のホットメルト型接着フィルムについて、接着性および耐熱接着性を評価し、表３に記載した。各評価は、下記の方法に従って行なった。
＜接着評価＞
ホットメルト接着フィルムを、厚み５０μｍのAESフィルムと厚み２ｍｍのＰＰプレートの間に、第一層側がＰＰプレートに接触するよう挟み、加熱温度１４０℃、０．２ＭＰａで４分間圧着して接着評価サンプルとした。この接着評価サンプルはＡＥＳフィルムの一端をＰＰプレートよりも１００ｍｍ長く切り出し挟みしろを設けた。得られた接着評価サンプルを２３℃雰囲気中において、引張り速度１００ｍｍ／分でＡＥＳフィルムを１８０度ピールし、強度（Ｎ／２５ｍｍ）と破壊状態を評価した。破壊状態としては、接着フィルムの破壊、界面剥離（ＰＰプレートと接着フィルム界面での界面剥離）で表記した。評価判定は以下の基準で行った。
○：接着強度が２０Ｎ／ｃｍ以上であった。
△：接着強度が５Ｎ／ｃｍ以上であった。
×：接着強度が５Ｎ／ｃｍ未満であった。
＜耐熱接着評価（クリープテスト）＞ ホットメルト接着フィルムを、厚み５０μｍのAESフィルムと厚み２ｍｍのＰＰプレートの間に、第一層側がＰＰプレートに接触するよう挟み、加熱温度１４０℃、０．２ＭＰａで４分間圧着し複合材料を得た。このときＡＥＳフィルムの一端をＰＰプレートよりも長く切り出し挟みしろを設けた。得られた複合材料を幅２５ｍｍのサイズに切断し、ＡＥＳフィルム面側が下方になるよう水平に固定し、ＡＥＳフィルムの一端の挟みしろに１００ｇの分銅を取り付け、７０℃の雰囲気下で２４時間放置後の剥離距離を測定した。評価判定は以下の基準で行った。
○：剥離距離が１０ｍｍ未満
×：剥離距離が１０ｍｍ以上
3. Evaluation of Hot Melt Type Adhesive Film The hot melt type adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3 described above were evaluated for adhesiveness and heat resistant adhesive properties and listed in Table 3. Each evaluation was performed according to the following method.
<Adhesion evaluation>
A hot-melt adhesive film is sandwiched between an AES film with a thickness of 50 μm and a PP plate with a thickness of 2 mm so that the first layer side is in contact with the PP plate, and pressure-bonded for 4 minutes at a heating temperature of 140 ° C. and 0.2 MPa, and an adhesion evaluation sample It was. In this adhesion evaluation sample, one end of the AES film was cut 100 mm longer than the PP plate and provided with a margin. The obtained adhesion evaluation sample was peeled 180 degrees at a pulling speed of 100 mm / min in an atmosphere of 23 ° C., and the strength (N / 25 mm) and the fracture state were evaluated. As the destruction state, it was expressed by the destruction of the adhesive film and the interfacial peeling (interfacial peeling at the interface between the PP plate and the adhesive film). Evaluation was made according to the following criteria.
○: Adhesive strength was 20 N / cm or more.
Δ: Adhesive strength was 5 N / cm or more.
X: Adhesive strength was less than 5 N / cm.
<Heat-resistant adhesion evaluation (creep test)> A hot melt adhesive film is sandwiched between an AES film having a thickness of 50 μm and a PP plate having a thickness of 2 mm so that the first layer side is in contact with the PP plate, and a heating temperature of 140 ° C. and 0.2 MPa. For 4 minutes to obtain a composite material. At this time, one end of the AES film was cut longer than the PP plate and provided with a margin. The obtained composite material is cut to a size of 25 mm in width, fixed horizontally so that the AES film surface side is downward, a 100 g weight is attached to the end of one end of the AES film, and left in an atmosphere at 70 ° C. for 24 hours. The subsequent peel distance was measured. Evaluation was made according to the following criteria.
○: Peeling distance is less than 10 mm ×: Peeling distance is 10 mm or more
表３に示すとおり、実施例１〜３の請求範囲内のホットメルト型接着フィルムは、良好な接着性、耐熱接着性を有するのに対して、比較例に示したホットメルト型接着フィルムは、評価項目のいずれか、または全てがより低い評価結果となった。 As shown in Table 3, the hot melt adhesive films in the claims of Examples 1 to 3 have good adhesiveness and heat resistant adhesiveness, whereas the hot melt adhesive films shown in the comparative examples are: Any or all of the evaluation items resulted in lower evaluation results.
Claims (8)
（Ｅ）前記（Ｃ）を含まない熱可塑性樹脂を含有する第二層からなるホットメルト型接着フィルムであって、
前記（Ｄ）が、（Ａ）（a）エポキシ基含有ビニル単量体および（ｂ）芳香族ビニル単量体で変性された、変性エチレンーαオレフィン共重合体６０〜９０重量部と、
（Ｂ）スチレン共役ジエン系ブロック共重合体４０〜１０重量部を含有するものである、
ホットメルト型接着フィルム。 (D) a first layer containing 100 parts by weight of a base resin and (C) 30 to 60 parts by weight of a tackifier;
(E) A hot melt adhesive film comprising a second layer containing a thermoplastic resin not containing (C),
60 to 90 parts by weight of the modified ethylene-α-olefin copolymer modified with (A) (a) an epoxy group-containing vinyl monomer and (b) an aromatic vinyl monomer,
(B) It contains 40 to 10 parts by weight of a styrene conjugated diene block copolymer.
Hot melt adhesive film.
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| WO2017200059A1 (en) * | 2016-05-18 | 2017-11-23 | 株式会社クラレ | Multilayer film |
| CN107868626A (en) * | 2017-12-11 | 2018-04-03 | 苏州纽东精密制造科技有限公司 | A kind of ageing-resistant body of a motor car patch |
| CN109486445A (en) * | 2017-09-12 | 2019-03-19 | 丹阳市丹达防腐设备有限公司 | A kind of hot melt adhesive and preparation method thereof for steel lined plastic compound pipeline |
| WO2024014534A1 (en) * | 2022-07-15 | 2024-01-18 | 株式会社アイセロ | Thermoplastic multilayer adhesive film |
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