JP5177149B2 - Adhesive composition and heat-fusible member using the same - Google Patents
Adhesive composition and heat-fusible member using the same Download PDFInfo
- Publication number
- JP5177149B2 JP5177149B2 JP2009548844A JP2009548844A JP5177149B2 JP 5177149 B2 JP5177149 B2 JP 5177149B2 JP 2009548844 A JP2009548844 A JP 2009548844A JP 2009548844 A JP2009548844 A JP 2009548844A JP 5177149 B2 JP5177149 B2 JP 5177149B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin resin
- adhesive composition
- resin
- polyolefin
- carboxyl group
- 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.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims description 74
- 230000001070 adhesive effect Effects 0.000 title claims description 74
- 239000000203 mixture Substances 0.000 title claims description 68
- 229920005672 polyolefin resin Polymers 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- -1 isocyanate compound Chemical class 0.000 claims description 48
- 239000012948 isocyanate Substances 0.000 claims description 35
- 239000003960 organic solvent Substances 0.000 claims description 32
- 239000011888 foil Substances 0.000 claims description 29
- 239000012790 adhesive layer Substances 0.000 claims description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 229920000098 polyolefin Polymers 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 230000035699 permeability Effects 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000126 substance Substances 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000007654 immersion Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 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 4
- 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 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003097 polyterpenes Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 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
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- MEZLKOACVSPNER-GFCCVEGCSA-N selegiline Chemical compound C#CCN(C)[C@H](C)CC1=CC=CC=C1 MEZLKOACVSPNER-GFCCVEGCSA-N 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
- B29C65/50—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
- B29C65/50—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
- B29C65/5007—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like
- B29C65/5021—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like being multi-layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/45—Joining of substantially the whole surface of the articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/74—Joining plastics material to non-plastics material
- B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2305/00—Use of metals, their alloys or their compounds, as reinforcement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
- B29L2009/003—Layered products comprising a metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、接着剤組成物及びこの接着剤組成物を用いた熱融着性部材に関する。更に詳しくは、優れた接着性、耐温水性及び耐薬品性等を有し、ポリオレフィン樹脂フィルム等のポリオレフィン樹脂成形体と他部材との接着に有用な接着剤組成物、及びこの接着剤組成物によりアルミニウム箔等の金属箔と熱融着性樹脂フィルムとが接合されてなる熱融着性部材に関する。 The present invention relates to an adhesive composition and a heat-fusible member using the adhesive composition. More specifically, an adhesive composition having excellent adhesion, hot water resistance, chemical resistance, and the like, and useful for bonding a polyolefin resin molded article such as a polyolefin resin film and other members, and the adhesive composition It is related with the heat-fusible member formed by joining metal foil, such as aluminum foil, and a heat-fusible resin film.
従来、接着性に乏しいポリオレフィン樹脂からなる成形体を、他部材に接合させるための各種の接着剤組成物が提案されている。例えば、塩素化ポリオレフィンと、末端にイソシアネート官能基を有する特定の樹脂と、少なくとも1個の遊離イソシアネート基を含有するポリウレタン樹脂を、鎖延長剤により反応させて得られる樹脂組成物を主成分とする接着剤用等のバインダーが知られている(例えば、特許文献1参照。)。また、所定量の、ポリエチレン、エチレン・(メタ)アクリレート共重合体等のベースポリマー、粘着付与剤及びポリオレフィンにスチレン系単量体をグラフト共重合してなる変性ポリオレフィンを含むホットメルト接着剤が知られている(例えば、特許文献2参照。)。 Conventionally, various adhesive compositions have been proposed for joining a molded body made of a polyolefin resin having poor adhesion to other members. For example, the main component is a resin composition obtained by reacting a chlorinated polyolefin, a specific resin having an isocyanate functional group at the terminal, and a polyurethane resin containing at least one free isocyanate group with a chain extender. Binders for adhesives and the like are known (for example, see Patent Document 1). Also known is a hot melt adhesive containing a predetermined amount of a base polymer such as polyethylene, an ethylene / (meth) acrylate copolymer, a tackifier, and a modified polyolefin obtained by graft copolymerizing a styrene monomer with a polyolefin. (For example, see Patent Document 2).
更に、イソシアネート基を有するポリエステル系ウレタン、クロロプレンゴム、ポリイソシアネート、ハロゲン化剤及び2−エチルヘキソエート類からなる接着剤組成物が知られている(例えば、特許文献3参照。)。また、カルボキシル基含有熱可塑性エラストマー、ポリオレフィンポリオール及び粘着付与剤を有機溶媒に溶解又は分散せしめた液状組成物、並びに多官能イソシアネートからなる接着剤組成物が知られている(例えば、特許文献4参照。)。 Furthermore, an adhesive composition comprising a polyester-based urethane having an isocyanate group, a chloroprene rubber, a polyisocyanate, a halogenating agent and 2-ethylhexoates is known (for example, see Patent Document 3). Further, a liquid composition in which a carboxyl group-containing thermoplastic elastomer, a polyolefin polyol and a tackifier are dissolved or dispersed in an organic solvent, and an adhesive composition comprising a polyfunctional isocyanate are known (see, for example, Patent Document 4). .)
特許文献1に記載された接着剤用等のバインダーでは、塗装等が困難なポリオレフィン系樹脂であっても、例えば、塗膜を形成したときに、耐ガソリン性、耐候性及び耐湿性等を向上させることができると説明されている。しかし、塩素化ポリオレフィンが含有されるため、環境への配慮という観点で、用途等が制限されることがある。また、特許文献2に記載されたホットメルト接着剤では、ベースポリマーの種類によっては、ポリオレフィン系樹脂に用いることができるものの、ホットメルト型であるため耐熱性が必ずしも十分であるとは言えない。更に、適正な粘度を有するため、良好な作業性が維持されると記載されているが、溶剤型と比べてフィルム表面等に薄く且つ高速で塗工することはできず、工業的な生産性及び量産性に劣るという問題がある。
The binder for adhesives described in
また、特許文献3に記載された接着剤組成物では、ポリエステル系ウレタンを用いているため、コロナ放電処理等の前処理を施すことなく、ポリオレフィン系材料に対し強固に接着することができると説明されている。しかし、ポリエステル系ウレタンは加水分解し易く、耐久性、耐薬品性等に劣り、吸水率も高いため、耐水性(透湿性)に劣る。更に、特許文献4に記載された接着剤組成物では、ポリオレフィン系樹脂の接着において、高い初期接着強度及び最終接着強度を有し、接着耐久性に優れると説明されている。しかし、この接着剤組成物では、その組成からみて、結晶性がない、又は少なくとも結晶性が低いため、溶剤に侵され易く、溶剤と接触したときに接着剤層が膨潤し易く、その結果、接着強度が低下するという問題がある。 Moreover, in the adhesive composition described in Patent Document 3, since polyester-based urethane is used, it can be firmly bonded to a polyolefin-based material without performing pretreatment such as corona discharge treatment. Has been. However, polyester-based urethane is easily hydrolyzed, inferior in durability, chemical resistance, and the like, and has a high water absorption rate, and therefore inferior in water resistance (moisture permeability). Furthermore, the adhesive composition described in Patent Document 4 is described as having high initial adhesive strength and final adhesive strength and excellent adhesion durability in the adhesion of polyolefin-based resins. However, in this adhesive composition, there is no crystallinity or at least low crystallinity in view of the composition, so that it is easily attacked by the solvent, and the adhesive layer easily swells when contacted with the solvent. There is a problem that the adhesive strength is lowered.
本発明は、上記の従来の問題に鑑みてなされたものであり、本来接着性に劣るポリオレフィン素材の接着に用いたときに、十分な強度で接着させることができ、且つ耐温水性、耐薬品性等に優れ、ポリオレフィン素材用の接着剤として有用な接着剤組成物、及びこの接着剤組成物によりアルミニウム箔等の金属箔とポリオレフィン樹脂フィルム等の熱融着性樹脂フィルムとが接合されてなる熱融着性部材を提供することを目的とする。 The present invention has been made in view of the above-described conventional problems, and can be bonded with sufficient strength when used for bonding a polyolefin material that is inherently inferior in adhesiveness, and is resistant to warm water and chemicals. An adhesive composition that is excellent in properties and useful as an adhesive for polyolefin materials, and a metal foil such as an aluminum foil and a heat-fusible resin film such as a polyolefin resin film are joined by this adhesive composition An object is to provide a heat-fusible member.
本発明は以下のとおりである。
1.有機溶媒と、該有機溶媒に溶解又は分散されているカルボキシル基を有するポリオレフィン樹脂と、該有機溶媒に含有されている多官能イソシアネート化合物と、を有し、該多官能イソシアネート化合物は1分子中に3個以上のイソシアネート基を有する変性イソシアネート化合物であり、ポリオレフィン素材の接着に用いられる接着剤組成物であって、上記ポリオレフィン樹脂は、ポリオレフィンにエチレン性不飽和カルボン酸又はその無水物をグラフト重合させた変性ポリオレフィン樹脂、及びオレフィンモノマーとエチレン性不飽和カルボン酸との共重合樹脂の少なくとも一方であり、該ポリオレフィン樹脂のJIS K 7121に準拠して測定した融解エネルギーが5〜15mJ/mgであり、上記有機溶媒と該ポリオレフィン樹脂との合計を100質量%とした場合に、該ポリオレフィン樹脂は10〜20質量%であり、上記接着剤組成物のJIS Z 0208に準拠して測定した透湿度が10〜50g/m 2 /24hであり、金属箔と熱融着性樹脂フィルム層との接合に用いられることを特徴とする接着剤組成物。
2.上記カルボキシル基を有するポリオレフィン樹脂に含まれる上記カルボキシル基の含有量が、該カルボキシル基を有するポリオレフィン樹脂1g当たり0.10〜0.70mmolである上記1.に記載の接着剤組成物。
3.上記多官能イソシアネート化合物が有するイソシアネート基(NCO)と、上記カルボキシル基を構成するヒドロキシル基(OH)との当量比(NCO/OH)が1.0〜10.0である上記1.又は2.に記載の接着剤組成物。
4.上記1.乃至3.のうちのいずれか1項に記載の接着剤組成物が硬化してなる接着剤層と、該接着剤層の一面に接合された金属箔と、該接着剤層の他面に接合された熱融着性樹脂フィルム層と、を備えることを特徴とする熱融着性部材。
The present invention is as follows.
1. An organic solvent, a polyolefin resin having a carboxyl group dissolved or dispersed in the organic solvent, and a polyfunctional isocyanate compound contained in the organic solvent, wherein the polyfunctional isocyanate compound is contained in one molecule. A modified isocyanate compound having three or more isocyanate groups, which is an adhesive composition used for bonding a polyolefin material , wherein the polyolefin resin is obtained by graft polymerization of an ethylenically unsaturated carboxylic acid or its anhydride to a polyolefin. Modified polyolefin resin, and at least one of a copolymer resin of an olefin monomer and an ethylenically unsaturated carboxylic acid, the melting energy of the polyolefin resin measured in accordance with JIS K 7121 is 5 to 15 mJ / mg, The organic solvent and the polyolefin resin Total is 100% by weight, the polyolefin resin is 10 to 20 wt%, moisture permeability, as measured in accordance with JIS Z 0208 of the adhesive composition is in 10~50g / m 2 / 24h And an adhesive composition characterized by being used for joining a metal foil and a heat-fusible resin film layer .
2. The content of the carboxyl group contained in the polyolefin resin having a carboxyl group is from 0.10 to 0.70 mmol per 1 g of the polyolefin resin having a carboxyl group. The adhesive composition described in 1.
3. 1. The equivalent ratio (NCO / OH) between the isocyanate group (NCO) of the polyfunctional isocyanate compound and the hydroxyl group (OH) constituting the carboxyl group is 1.0 to 10.0. Or 2 . The adhesive composition described in 1.
4). Above 1. Thru 3 . An adhesive layer formed by curing the adhesive composition according to any one of the above, a metal foil bonded to one surface of the adhesive layer, and heat bonded to the other surface of the adhesive layer A heat-fusible member comprising: a fusible resin film layer.
本発明の接着剤組成物は、ポリオレフィン樹脂フィルム等のポリオレフィン樹脂成形体と他部材との接着、例えば、ポリオレフィン樹脂以外の樹脂からなるフィルムとポリオレフィン樹脂フィルムとの接着に好適であり、硬化後の接着剤層は、優れた耐温水性、耐薬品性等を有する。この接着剤組成物は、例えば、建築物の建材及び外装品、特に海浜地区等における建築物の建材等に用いられたときなどの耐塩水性、輸液等の医療用液の容器に用いられたときの耐電解質性、融雪剤が撒かれた道路を走行する車両の部品等に用いられたときの耐食性等に優れ、建築、医療、自動車などの各種の産業分野において有用である。
また、カルボキシル基を有するポリオレフィン樹脂におけるカルボキシル基の含有量が、このポリオレフィン樹脂1g当たり0.10〜0.70mmolである場合は、親水性が抑えられ、接着剤組成物をポリオレフィン樹脂フィルム等を用いた密封容器などの接着に用いたときに、湿分の侵入を抑えることができる。
更に、多官能イソシアネート化合物が有するイソシアネート基(NCO)と、カルボキシル基を構成するヒドロキシル基(OH)との当量比(NCO/OH)が1.0〜10.0である場合は、接着性をより向上させることができる。
本発明の熱融着性部材によれば、この熱融着性部材を用いて食品、薬品等を収容する密封容器としたときに、湿分の侵入が抑えられ、内容物の変質等を防止することができる。
The adhesive composition of the present invention is suitable for adhesion between a polyolefin resin molded article such as a polyolefin resin film and other members, for example, adhesion between a film made of a resin other than a polyolefin resin and a polyolefin resin film, and after curing. The adhesive layer has excellent hot water resistance, chemical resistance, and the like. When this adhesive composition is used, for example, in a container for medical fluids such as salt water resistance and infusion, such as when used for building materials and exterior products of buildings, especially building materials of buildings in the beach area, etc. It has excellent anti-electrolytic properties and corrosion resistance when used in parts of vehicles traveling on roads where snow melting agents are spread, and is useful in various industrial fields such as architecture, medical care, and automobiles.
When the carboxyl group content in the polyolefin resin having a carboxyl group is 0.10 to 0.70 mmol per 1 g of the polyolefin resin, the hydrophilicity is suppressed, and the adhesive composition is made of a polyolefin resin film or the like. When used for bonding a sealed container or the like, it is possible to suppress moisture from entering.
Furthermore , when the equivalent ratio (NCO / OH) of the isocyanate group (NCO) of the polyfunctional isocyanate compound to the hydroxyl group (OH) constituting the carboxyl group is 1.0 to 10.0, It can be improved further.
According to the heat-fusible member of the present invention, when the heat-fusible member is used as a sealed container for containing food, medicine, etc., moisture can be prevented from entering and contents can be prevented from being altered. can do.
1;熱融着性部材、11;熱融着性樹脂フィルム層、12;接着剤層、13;金属箔(アルミニウム箔)、14;樹脂層。
DESCRIPTION OF
以下、本発明を詳しく説明する。
[1]接着剤組成物
本発明の接着剤組成物は、有機溶媒と、有機溶媒に溶解又は分散されているカルボキシル基を有するポリオレフィン樹脂と、多官能イソシアネート化合物と、を有し、多官能イソシアネート化合物は1分子中に3個以上のイソシアネート基を有する変性イソシアネート化合物であり、ポリオレフィン素材の接着に用いられる接着剤組成物であって、ポリオレフィン樹脂は、ポリオレフィンにエチレン性不飽和カルボン酸又はその無水物をグラフト重合させた変性ポリオレフィン樹脂、及びオレフィンモノマーとエチレン性不飽和カルボン酸との共重合樹脂の少なくとも一方であり、ポリオレフィン樹脂のJIS K 7121に準拠して測定した融解エネルギーが5〜15mJ/mgであり、有機溶媒とポリオレフィン樹脂との合計を100質量%とした場合に、ポリオレフィン樹脂は10〜20質量%であり、接着剤組成物のJIS Z 0208に準拠して測定した透湿度が10〜50g/m 2 /24hであり、金属箔と熱融着性樹脂フィルム層との接合に用いられる。
The present invention will be described in detail below.
[1] Adhesive composition The adhesive composition of the present invention comprises an organic solvent, a polyolefin resin having a carboxyl group dissolved or dispersed in the organic solvent, and a polyfunctional isocyanate compound, and is a polyfunctional isocyanate. The compound is a modified isocyanate compound having three or more isocyanate groups in one molecule, and is an adhesive composition used for bonding a polyolefin material . The polyolefin resin is an ethylenically unsaturated carboxylic acid or its anhydride. And at least one of a modified polyolefin resin obtained by graft polymerization of a product and a copolymer resin of an olefin monomer and an ethylenically unsaturated carboxylic acid, and the melting energy of the polyolefin resin measured in accordance with JIS K 7121 is 5 to 15 mJ / mg, organic solvent and polyolefin resin Total is 100% by weight, the polyolefin resin is 10 to 20 wt%, moisture permeability, as measured in accordance with JIS Z 0208 of the adhesive composition is a 10~50g / m 2 / 24h, Used for joining the metal foil and the heat-fusible resin film layer .
(1)カルボキシル基を有するポリオレフィン樹脂
上記「カルボキシル基を有するポリオレフィン樹脂」(以下、「ポリオレフィン樹脂」という。)としては、ポリオレフィンにエチレン性不飽和カルボン酸又はその無水物をグラフト重合させた変性ポリオレフィン樹脂、及びオレフィンモノマーとエチレン性不飽和カルボン酸との共重合樹脂が用いられる。ポリオレフィンとしては、エチレン、プロピレン、ブテン等のオレフィンモノマーの単独重合体又は共重合体、及びこれらのオレフィンモノマーと、ジシクロペンタジエン、4−メチルペンテン−1、酢酸ビニル等との共重合体などを用いることができる。エチレン性不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、5−ノルボルネン−2,3−ジカルボン酸等が挙げられ、接着剤組成物の硬化後の特性及びコストの点からマレイン酸が好ましい。これらのエチレン性不飽和カルボン酸は1種のみ用いてもよいし、2種以上を併用してもよい。ポリオレフィン樹脂としては、プロピレンの単独重合体又はエチレンとの共重合体を変性した樹脂、特にプロピレン単独重合体を変性した樹脂が好ましい。
(1) Polyolefin resin having a carboxyl group The above-mentioned “polyolefin resin having a carboxyl group” (hereinafter referred to as “polyolefin resin”) is a modified polyolefin obtained by graft-polymerizing an ethylenically unsaturated carboxylic acid or its anhydride to a polyolefin. Resins and copolymer resins of olefin monomers and ethylenically unsaturated carboxylic acids are used . Examples of polyolefins include homopolymers or copolymers of olefin monomers such as ethylene, propylene, and butene, and copolymers of these olefin monomers with dicyclopentadiene, 4-methylpentene-1, vinyl acetate, and the like. Can be used. Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, and the like. Maleic acid is preferred from the standpoint of properties after curing and cost. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. The polyolefin resin is preferably a resin obtained by modifying a propylene homopolymer or a copolymer with ethylene, particularly a resin obtained by modifying a propylene homopolymer.
ポリオレフィン樹脂のJIS K7121に準拠して測定した融解エネルギー5〜15mJ/mgである。融解エネルギーが5〜15mJ/mgであれば、有機溶媒への溶解性に優れ、且つ十分な耐温水性、耐薬品性等の接着耐久性を有する接着剤組成物とすることができるため好ましい。また、このポリオレフィン樹脂は、上記の融解エネルギーを有し、且つ融解温度が80℃以下、特に60〜80℃であることがより好ましい。このようなポリオレフィン樹脂であれば、低温接着性に優れ、硬化後の接着剤層が十分な耐温水性、耐薬品性等の接着耐久性を有する接着剤組成物とすることができる。 The melting energy measured in accordance with JIS K7121 of polyolefin resin is 5 to 15 mJ / mg. A melting energy of 5 to 15 mJ / mg is preferable because it can be used as an adhesive composition having excellent solubility in an organic solvent and sufficient adhesion durability such as warm water resistance and chemical resistance. . Further, this polyolefin resin has the melting energy described above and has a melting temperature of 80 ° C. or lower, particularly 60 to 80 ° C. If it is such a polyolefin resin, it can be set as the adhesive composition which is excellent in low-temperature adhesiveness, and has adhesive durability, such as warm water resistance and chemical resistance with sufficient adhesive layer after hardening.
更に、ポリオレフィン樹脂におけるカルボキシル基の含有量は特に限定されないが、ポリオレフィン樹脂1g当たり0.10〜0.70mmolであることが好ましい。この含有量は特に0.15〜0.24mmolであることがより好ましい。カルボキシル基の含有量が0.10〜0.70mmolであれば、湿分との親和性が高くなり過ぎず、接着剤組成物を食品、薬品等を収容する密封容器等の形成に用いられる熱融着性部材の接着剤層として使用したときに、湿分の透過を十分に抑えることができる。
尚、カルボキシル基の含有量は、赤外線スペクトルの検量線より算出したポリオレフィン樹脂中の酸含量をカルボキシル基の式量(45)で除し、樹脂1g当たりの値として求めることができる。Furthermore, although content of the carboxyl group in polyolefin resin is not specifically limited, It is preferable that it is 0.10-0.70 mmol per g of polyolefin resin. This content is particularly preferably 0.15 to 0.24 mmol. If the content of the carboxyl group is 0.10 to 0.70 mmol, the affinity for moisture does not become too high, and the adhesive composition is used for forming a sealed container or the like that contains food, medicine, etc. When used as the adhesive layer of the fusible member, moisture permeation can be sufficiently suppressed.
The carboxyl group content can be obtained as a value per gram of resin by dividing the acid content in the polyolefin resin calculated from the calibration curve of the infrared spectrum by the formula amount (45) of the carboxyl group.
(2)有機溶媒
上記「有機溶媒」は、ポリオレフィン樹脂を溶解又は分散させることができればよく、特に限定されないが、より多くのポリオレフィン樹脂を溶解させることができる溶媒であることが好ましい。また、この有機溶媒は、接着剤組成物から加熱等により揮発させ、除去することが容易な有機溶媒であることが好ましい。このような有機溶媒としては、トルエン、キシレン等の芳香族系有機溶媒、n−ヘキサン等の脂肪族系有機溶媒、シクロヘキサン、メチルシクロヘキサン等の脂環族系有機溶媒、及びメチルエチルケトン等のケトン系有機溶媒などを用いることができる。これらの有機溶媒は1種のみ用いてもよいし、2種以上を併用してもよい。(2) Organic solvent The “organic solvent” is not particularly limited as long as it can dissolve or disperse the polyolefin resin, but is preferably a solvent capable of dissolving more polyolefin resin. Moreover, this organic solvent is preferably an organic solvent that can be easily volatilized and removed from the adhesive composition by heating or the like. Examples of such organic solvents include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as n-hexane, alicyclic organic solvents such as cyclohexane and methylcyclohexane, and ketone organics such as methyl ethyl ketone. A solvent or the like can be used. These organic solvents may be used alone or in combination of two or more.
有機溶媒とポリオレフィン樹脂との質量割合は、より多くのポリオレフィン樹脂が有機溶媒に溶解される割合であることが好ましく、ポリオレフィン樹脂の全量が溶解されることがより好ましい。この質量割合は、有機溶媒及びポリオレフィン樹脂の各々の種類等により設定することができ、有機溶媒とポリオレフィン樹脂との合計を100質量%とした場合に、ポリオレフィン樹脂が10〜20質量%である。このような質量割合であれば、より多くのポリオレフィン樹脂を容易に溶解させることができる。
尚、ポリオレフィン樹脂の全量が溶解したことは、ポリエチレンテレフタレート等のフィルム上に、接着剤組成物(樹脂濃度20質量%)をバーコーターで塗工して厚さ150〜200μmの塗膜を形成し(塗膜を乾燥した後の皮膜の厚さは30〜40μmになる。)、この塗膜の表面粗さが50μm以下であることにより判定することができる。塗膜の表面粗さはJIS B0651に規定される触針式表面粗さ計により測定することができる。
Mass ratio of organic solvent and the polyolefin resin is preferably more polyolefin resin is a fraction which is soluble in an organic solvent, it is more preferable that the polyolefin resin the total amount is dissolved. This mass ratio can be set according to the type of each of the organic solvent and the polyolefin resin, and the polyolefin resin is 10 to 20% by mass when the total of the organic solvent and the polyolefin resin is 100% by mass. With such a mass ratio, more polyolefin resin can be dissolved easily.
The fact that the total amount of polyolefin resin is dissolved means that an adhesive composition (resin concentration: 20% by mass) is coated on a film such as polyethylene terephthalate with a bar coater to form a coating film having a thickness of 150 to 200 μm. (The thickness of the coating after drying the coating is 30 to 40 μm), and the surface roughness of this coating can be determined by 50 μm or less. The surface roughness of the coating film can be measured by a stylus type surface roughness meter defined in JIS B0651.
(3)多官能イソシアネート化合物
上記「多官能イソシアネート化合物」は、ポリオレフィン樹脂と反応し、接着剤組成物を硬化させる作用を有する。この多官能イソシアネート化合物としては、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート等の化合物をイソシアヌレート変性、ビュレット変性、トリメチロ−ルプロパン等の多価アルコールでアダクト変性した変性物などを用いることができる。これらの多官能イソシアネート化合物は1種のみ用いてもよいし、2種以上を併用してもよい。この多官能イソシアネート化合物としても、通常、上記(2)に記載された有機溶媒に溶解する多官能イソシアネート化合物が用いられる。
(3) Polyfunctional isocyanate compound The “polyfunctional isocyanate compound” has an action of reacting with a polyolefin resin to cure the adhesive composition. As this polyfunctional isocyanate compound, it is possible to use a modified product obtained by adduct-modifying a compound such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or the like with an isocyanurate-modified, burette-modified, or a polyhydric alcohol such as trimethylolpropane. it can. These polyfunctional isocyanate compounds may be used alone or in combination of two or more. Also as this polyfunctional isocyanate compound, the polyfunctional isocyanate compound which melt | dissolves in the organic solvent described in said (2) is used normally.
多官能イソシアネート化合物は、1分子中に3個以上のイソシアネート基を有する変性イソシアネート化合物であり、イソシアヌレート変性された市販品として日本ポリウレタン工業社製の商品名「コロネ−トHX」、旭化成ケミカルズ社製の商品名「デュラネートTPA−100」、三井武田ケミカル社製の商品名「タケネートD−170N」等が挙げられる。また、ビュレット変性された市販品として三井武田ケミカル社製の商品名「タケネートD−165NN」等、及びトリメチロールプロパンアダクト変性された市販品として日本ポリウレタン工業社製の商品名「コロネートL」、三井武田ケミカル社製の商品名「タケネ-トD−102」、「タケネートD−140N」等が挙げられる。 The polyfunctional isocyanate compound is a modified isocyanate compound having three or more isocyanate groups in one molecule. As a commercial product modified with isocyanurate, the product name “Coloneto HX” manufactured by Nippon Polyurethane Industry Co., Ltd., Asahi Kasei Chemicals Corporation Product name “Duranate TPA-100” manufactured by Mitsui Takeda Chemical Co., Ltd., and “Takenate D-170N” are examples. In addition, as a commercial product modified by burette, the trade name “Takenate D-165NN” manufactured by Mitsui Takeda Chemical Co., Ltd., and as a commercial product modified by trimethylolpropane adduct, the product name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd., Mitsui Trade name “Takenet D-102”, “Takenate D-140N” manufactured by Takeda Chemical Co.
ポリオレフィン樹脂と、多官能イソシアネート化合物との質量割合は特に限定されないが、多官能イソシアネート化合物が有するイソシアネート基(NCO)と、ポリオレフィン樹脂が有するカルボキシル基を構成するヒドロキシル基(OH)との当量比(NCO/OH)が1.0〜10.0となる質量割合であることが好ましい。この当量比は1.5〜10.0、特に1.8〜9.0、更に3.5〜9.0であることがより好ましい。当量比が1.0〜10.0であれば、特に初期の接着性に優れた接着剤組成物とすることができるとともに、十分な架橋密度を有し、且つ柔軟性等に優れた接着剤層を形成することができる。 The mass ratio of the polyolefin resin and the polyfunctional isocyanate compound is not particularly limited, but the equivalent ratio of the isocyanate group (NCO) of the polyfunctional isocyanate compound and the hydroxyl group (OH) constituting the carboxyl group of the polyolefin resin ( NCO / OH) is preferably in a mass ratio of 1.0 to 10.0. The equivalent ratio is 1.5 to 10.0, particularly 1.8 to 9.0, and more preferably 3.5 to 9.0. When the equivalent ratio is 1.0 to 10.0, an adhesive composition having excellent initial adhesiveness can be obtained, and the adhesive has a sufficient crosslinking density and excellent flexibility and the like. A layer can be formed.
(4)その他の成分
接着剤組成物には、ポリオレフィン樹脂、多官能イソシアネート化合物の他に、反応促進剤が配合され、粘着付与樹脂、酸変性されていない熱可塑性エラストマー、酸変性されていない熱可塑性樹脂、可塑剤等を含有させることもできる。
(a)反応促進剤
ポリオレフィン樹脂と、多官能イソシアネート化合物との反応を促進するため反応促進剤が配合される。この反応促進剤としては、各種の有機スズ化合物及び第3級アミンが挙げられる。反応促進剤は1種のみ用いてもよいし、2種以上を併用してもよく、有機スズ化合物と第3級アミンとを併用することもできる。(4) Other components In the adhesive composition, in addition to the polyolefin resin and the polyfunctional isocyanate compound, a reaction accelerator is blended, tackifying resin, non-acid-modified thermoplastic elastomer, non-acid-modified heat. A plastic resin, a plasticizer, etc. can also be contained.
(A) Reaction accelerator A reaction accelerator is blended in order to accelerate the reaction between the polyolefin resin and the polyfunctional isocyanate compound. Examples of the reaction accelerator include various organotin compounds and tertiary amines. Only 1 type of reaction accelerator may be used, 2 or more types may be used together, and an organotin compound and a tertiary amine can also be used together.
(b)粘着付与剤
粘着付与剤としては、ポリテルペン系樹脂、ロジン系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、共重合系石油樹脂及び水添石油樹脂等が挙げられる。ポリテルペン系樹脂としては、α−ピネン重合体、β−ピネン重合体、及びこれらとフェノール又はビスフェノールA等との共重合体が挙げられ、例えば、ヤスハラケミカル社製の商品名「YSレジンPX」、「YSレジンA」、「YSポリスターT」等の市販品を用いることができる。ロジン系樹脂としては、天然ロジン、重合ロジン及びこれらのエステル誘導体等が挙げられ、例えば、荒川化学工業社製の商品名「ペンセルD」、「スーパーエステルA」等の市販品を用いることができる。脂肪族系石油樹脂はC5系樹脂ともいわれ、一般に石油のC5留分より合成される樹脂であり、トーネックス社製の商品名「エスコレッツ」、日本ゼオン社製の商品名「クイントン」、グッドイヤー社製の商品名「ウィングタック」等の市販品を用いることができる。脂環族系石油樹脂はC9系樹脂ともいわれ、一般に石油のC9留分より合成される樹脂であり、丸善石油化学社製の商品名「マルカレッツ」等の市販品を用いることができる。共重合石油樹脂はC5/C9共重合樹脂ともいわれ、東邦化学工業社製の商品名「トーホーハイレジン」等の市販品を用いることができる。水添炭化水素樹脂は、一般に上記の各種の石油樹脂の水素添加により製造されており、荒川化学工業社製の商品名「エステルガムH」、「アルコン」、ヤスハラケミカル社製の商品名「クリアロン」、トーネックス社製の商品名「エスコレッツ」等を用いることができる。これらの粘着付与剤は1種のみ用いてもよいし、2種以上を併用してもよい。(B) Tackifiers Examples of tackifiers include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, and hydrogenated petroleum resins. Examples of the polyterpene resin include α-pinene polymers, β-pinene polymers, and copolymers thereof with phenol or bisphenol A. For example, trade names “YS Resin PX”, “Yasuhara Chemical Co., Ltd.” Commercial products such as “YS Resin A” and “YS Polyster T” can be used. Examples of the rosin resin include natural rosin, polymerized rosin, and ester derivatives thereof. For example, commercially available products such as trade names “Pencel D” and “Superester A” manufactured by Arakawa Chemical Industries, Ltd. can be used. . Aliphatic petroleum resin is also referred to as C 5 resin, typically a resin which is synthesized from C 5 fraction of petroleum, Tonex Co., Ltd. under the trade name "Escorez", Nippon Zeon Co., Ltd. under the trade name "Quinton", Goodyear Commercial products such as a trade name “Wingtack” manufactured by the company can be used. Alicyclic petroleum resins said to be C 9 resins, generally a resin synthesized from C 9 fraction of the oil, it can be used by Maruzen Petrochemical Co., Ltd. under the trade name commercial products such as "MARUKAREZ". The copolymerized petroleum resin is also referred to as a C 5 / C 9 copolymer resin, and commercially available products such as “Toho High Resin” manufactured by Toho Chemical Industry Co., Ltd. can be used. Hydrogenated hydrocarbon resins are generally produced by hydrogenation of the above-mentioned various petroleum resins. Trade names “Ester gum H” and “Arcon” manufactured by Arakawa Chemical Industries, Ltd. and “Clearon” manufactured by Yashara Chemical Co., Ltd. The trade name “Escollet” manufactured by Tonex Co., Ltd. can be used. These tackifiers may be used alone or in combination of two or more.
(c)その他
酸変性されていない熱可塑性エラストマーとしては、好ましくはSEBS、SEPS等が挙げられる。また、酸変性されていない熱可塑性樹脂としては、好ましくはエチレン−酢酸ビニル共重合樹脂、エチレン−エチルアクリレート共重合樹脂、ワックス等が挙げられる。更に、可塑剤としては、好ましくはポリイソプレン、ポリブテン等の液状ゴム、プロセスオイル等が挙げられる。
上記(a)〜(c)のその他の成分の含有量は、ポリオレフィン樹脂、多官能イソシアネート化合物及びその他の成分の合計を100質量%とした場合に、70質量%以下、特に60〜10質量%、更に50〜20質量%であることが好ましい。その他の成分の含有量が70質量%以下であれば、十分な接着性、耐温水性、耐薬品性等を有する接着剤組成物とすることができる。(C) Others Examples of the thermoplastic elastomer that is not acid-modified include SEBS and SEPS. The thermoplastic resin that is not acid-modified is preferably an ethylene-vinyl acetate copolymer resin, an ethylene-ethyl acrylate copolymer resin, a wax, or the like. Furthermore, the plasticizer is preferably a liquid rubber such as polyisoprene or polybutene, or process oil.
The content of the other components (a) to (c) is 70% by mass or less, particularly 60 to 10% by mass, when the total of the polyolefin resin, the polyfunctional isocyanate compound and the other components is 100% by mass. Furthermore, it is preferable that it is 50-20 mass%. When the content of other components is 70% by mass or less, an adhesive composition having sufficient adhesion, hot water resistance, chemical resistance, and the like can be obtained.
本発明の接着剤組成物は、食品、薬品等を収容するための樹脂フィルム製密封容器などの接着剤層として用いることができる。例えば、金属箔と熱融着性樹脂フィルムとを接合する接着剤層として用いることができる。このように金属箔と接着剤層と熱融着性樹脂フィルム層とを有する熱融着性部材では、熱融着性樹脂フィルムを透過した湿分が更に接着剤層を透過し、金属箔にまで達した場合、この界面での剥離強度が低下したり、剥離したりすることがある。このような強度低下及び剥離を抑えるため、接着剤層は透湿性が低いことが好ましい。従って、接着剤組成物のJIS Z 0208に準拠して測定した透湿度は10〜50g/m2・24hである。透湿度が10〜50g/m2・24hであれば、湿分の透過を十分に抑えることができ、接着剤層と金属箔との界面における剥離強度の低下及び剥離の発生を十分に抑えることができる。 The adhesive composition of the present invention can be used as an adhesive layer for a sealed container made of a resin film for containing foods, medicines and the like. For example, it can be used as an adhesive layer for joining a metal foil and a heat-fusible resin film. Thus, in the heat-fusible member having the metal foil, the adhesive layer, and the heat-fusible resin film layer, the moisture that has passed through the heat-fusible resin film further passes through the adhesive layer, When reaching the above, the peel strength at this interface may be lowered or peeled off. In order to suppress such strength reduction and peeling, the adhesive layer preferably has low moisture permeability. Therefore, the moisture permeability measured according to JIS Z 0208 of the adhesive composition is 10 to 50 g / m 2 · 24 h. If the moisture permeability is 10 to 50 g / m 2 · 24 h, moisture permeation can be sufficiently suppressed, and the decrease in the peel strength and the occurrence of peeling at the interface between the adhesive layer and the metal foil are sufficiently suppressed. be able to.
[2]熱融着性部材
本発明の熱融着性部材は、図1のように、本発明の接着剤組成物が硬化してなる接着剤層と、接着剤層の一面に接合された金属箔と、接着剤層の他面に接合された熱融着性樹脂フィルム層とを備える。[2] Heat-fusible member As shown in FIG. 1, the heat-fusible member of the present invention is bonded to an adhesive layer formed by curing the adhesive composition of the present invention and one surface of the adhesive layer. A metal foil and a heat-fusible resin film layer bonded to the other surface of the adhesive layer are provided.
上記「接着剤層12」は、上記[1]に記載された接着剤組成物を金属箔13及び熱融着性樹脂フィルム層11となる樹脂フィルムのうちの少なくとも一方の表面に塗布し、その後、有機溶媒を除去し、次いで、金属箔13と樹脂フィルムとを接着剤組成物が塗布された面を対向させて積層し、加熱、圧着することにより形成することができ、これと同時に熱融着性部材1が形成される。接着剤層12の厚さは材質等にもより、特に限定されないが、1〜20μm、特に2〜10μmであることが好ましい。接着剤層12の厚さが1〜20μmであれば、熱融着性部材の折り曲げ等の加工が容易である。尚、接着剤組成物は、金属箔13の表面に塗布されることが多いが特に限定はされない。接着剤組成物は通常の方法により塗布することができ、例えば、バーコーター、グラビアコーター等を用いて塗布することができる。加熱、圧着の条件は特に限定されず、金属箔13及び熱融着性樹脂フィルム層11となる樹脂フィルムの各々の材質等、並びに接着剤組成物の組成などにより設定することが好ましい。
The “
上記「金属箔13」の材質は特に限定されないが、加工性に優れるため、通常、アルミニウム箔が用いられる。金属箔13の厚さは材質等にもより、特に限定されないが、例えば、アルミニウム箔の場合、20〜100μm、特に20〜80μm、更に30〜60μmであることが好ましい。アルミニウム箔の厚さが20〜100μmであれば、容易に破損することがなく、熱融着性部材1を容易に形成することができる。また、金属箔13の接着剤層12が形成される面とは反対面には、金属箔13を保護し、且つ密封容器等の外観を向上させるため、樹脂層14を設けることもできる。この樹脂層14の材質は特に限定されず、ポリアミド樹脂、ポリエステル樹脂等からなる樹脂層14とすることができる。樹脂層14の厚さも特に限定されず、30〜60μm、特に30〜50μmとすることができる。
The material of the “
上記「熱融着性樹脂フィルム層11」は、ポリオレフィン樹脂フィルムを用いて形成することができる。更に、ポリオレフィン樹脂フィルムのうちでもポリプロピレンフィルム、特に熱融着時の寸法変化(収縮)が少ない無延伸ポリプロピレンフィルムがより好ましい。ポリオレフィン樹脂フィルムからなる熱融着性樹脂フィルム層11であれば、熱融着させ易く、熱融着性部材1の所定箇所を容易に、且つ十分な強度で熱融着させることができる。熱融着性樹脂フィルム層11の厚さは材質等にもより、特に限定されないが、例えば、無延伸ポリプロピレンフィルムの場合、10〜200μm、特に20〜100μm、更に60〜100μmであることが好ましい。無延伸ポリプロピレンフィルムの厚さが10〜200μmであれば、容易に破損することがなく、耐久性の高い密封容器等とすることができる。
The “heat-fusible
以下、実施例により本発明を具体的に説明する。
[1]接着剤組成物の製造
実験例1
コンデンサ及び攪拌装置が付設された容量500mlのフラスコに、有機溶媒(質量比でメチルシクロヘキサン:メチルエチルケトン=8:2の混合溶剤)を170g投入し、その後、ポリオレフィン樹脂(マレイン酸変性ポリプロピレン、日本製紙ケミカル社製、商品名「S−5212」(融解エネルギー;5mJ/mg、融解温度;77℃、酸価;10KOHmg/g、カルボキシル基含有量;0.33mmol/g、酸含量;1.5質量%)を30g仕込んだ。次いで、フラスコ内の温度を50℃とし、3時間加熱撹絆し、樹脂を溶解させた。その後、室温まで冷却し、反応促進剤としてジブチル錫ジラウレートを樹脂に対して100ppm添加し、溶液粘度が30mPa・s(25℃)であり、樹脂濃度が15質量%の淡黄色の液状接着剤を得た。
次いで、この液状接着剤を主剤とし、この主剤に多官能イソシアネート化合物(旭化成ケミカルズ社製、商品名「デュラネートTPA−100」)を当量比(NCO/OH)が1.8になるように配合して混合し、接着剤組成物を得た。この接着剤組成物は、多官能イソシアネート化合物を配合後、1時間以内に後記の試験片の作製に供した。配合組成等を表1に示す。Hereinafter, the present invention will be described specifically by way of examples.
[1] Production Example 1 of Adhesive Composition
170 g of organic solvent (mixed solvent of methylcyclohexane: methylethylketone = 8: 2 by mass ratio) was put into a 500 ml flask equipped with a condenser and a stirrer, and then polyolefin resin (maleic acid-modified polypropylene, Nippon Paper Chemicals) Product name “S-5212” (melting energy: 5 mJ / mg, melting temperature: 77 ° C., acid value: 10 KOH mg / g, carboxyl group content: 0.33 mmol / g, acid content: 1.5 mass% Next, the temperature in the flask was set to 50 ° C. and heated and stirred for 3 hours to dissolve the resin, and then cooled to room temperature, and dibutyltin dilaurate was added to the resin as 100 ppm as a reaction accelerator. Added, the solution viscosity is 30 mPa · s (25 ° C.), and the resin concentration is 15% by mass of light yellow liquid. It was obtained Chakuzai.
Next, this liquid adhesive is used as a main agent, and a polyfunctional isocyanate compound (trade name “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Co., Ltd.) is blended with this main agent so that the equivalent ratio (NCO / OH) is 1.8. To obtain an adhesive composition. This adhesive composition was subjected to the preparation of test pieces described later within 1 hour after blending the polyfunctional isocyanate compound. The composition and the like are shown in Table 1.
実験例2
多官能イソシアネート化合物を表1のように増量して当量比を5.0とした他は、実験例1と同様にして接着剤組成物を得た。
実験例3
有機溶媒を160gとし、ポリオレフィン樹脂として日本製紙ケミカル社製、商品名「S−5183」(マレイン酸変性ポリプロピレン、融解エネルギー;10mJ/mg、融解温度;67℃、酸価;13KOHmg/g、カルボキシル基含有量;0.44mmol/g、酸含量;2.0質量%)を26.7g、及び粘着付与剤として荒川化学社製、商品名「アルコンP−100」(完全水添C9樹脂、軟化点;100℃)を13.2g仕込み、多官能イソシアネート化合物を表1のように増量して当量比を2.5とした他は、実験例1と同様にして接着剤組成物を得た。
実験例4
多官能イソシアネート化合物を表1のように増量して当量比を9.0とした他は、実験例1と同様にして接着剤組成物を得た。Experimental example 2
An adhesive composition was obtained in the same manner as in Experimental Example 1 except that the amount of the polyfunctional isocyanate compound was increased as shown in Table 1 so that the equivalent ratio was 5.0.
Experimental example 3
160 g of organic solvent, manufactured by Nippon Paper Chemical Co., Ltd. as a polyolefin resin, trade name “S-5183” (maleic acid-modified polypropylene, melting energy: 10 mJ / mg, melting temperature: 67 ° C., acid value: 13 KOH mg / g, carboxyl group Content: 0.44 mmol / g, acid content: 2.0% by mass) 26.7 g, and Arakawa Chemical Co., Ltd., trade name “Arcon P-100” (completely hydrogenated C9 resin, softening point) as a tackifier ; 100 ° C), and an adhesive composition was obtained in the same manner as in Experimental Example 1, except that the polyfunctional isocyanate compound was added as shown in Table 1 so that the equivalent ratio was 2.5.
Experimental Example 4
An adhesive composition was obtained in the same manner as in Experimental Example 1 except that the amount of the polyfunctional isocyanate compound was increased as shown in Table 1 so that the equivalent ratio was 9.0.
実験例5
表2のように、多官能イソシアネート化合物を配合しなかった他は、実験例1と同様にして接着剤組成物を得た。
実験例6
ポリオレフィン樹脂を三洋化成工業社製、商品名「ユーメックス1010」(マレイン酸変性ポリプロピレン、融解エネルギー;52mJ/mg、融解温度;137℃、酸価;52KOHmg/g、カルボキシル基含有量;2.22mmol/g、酸含量;10質量%)とし、且つ増量し、多官能イソシアネート化合物を表2のように当量比が2.0となる配合量とした他は、実験例1と同様にして接着剤組成物を得た。
実験例7
マレイン酸変性ポリプロピレンに変えて酸変性SEBS(旭化成ケミカルズ社製、商品名「タフテックM−1913」(非晶性)を使用し、多官能イソシアネート化合物を表2のように当量比が2.5となる配合量とした他は、実験例1と同様にして接着剤組成物を得た。Experimental Example 5
As shown in Table 2, an adhesive composition was obtained in the same manner as in Experimental Example 1 except that no polyfunctional isocyanate compound was blended.
Experimental Example 6
Polyolefin resin manufactured by Sanyo Chemical Industries, trade name “Yumex 1010” (maleic acid-modified polypropylene, melting energy: 52 mJ / mg, melting temperature: 137 ° C., acid value: 52 KOH mg / g, carboxyl group content: 2.22 mmol / g, acid content; 10% by mass), and the amount was increased, and the adhesive composition was the same as in Experimental Example 1 except that the polyfunctional isocyanate compound was blended in an equivalent ratio of 2.0 as shown in Table 2. I got a thing.
Experimental Example 7
In place of maleic acid-modified polypropylene, acid-modified SEBS (manufactured by Asahi Kasei Chemicals Corporation, trade name “Tuftec M-1913” (amorphous) was used, and the polyfunctional isocyanate compound had an equivalent ratio of 2.5 as shown in Table 2. An adhesive composition was obtained in the same manner as in Experimental Example 1 except that the blending amount was as follows.
[2]性能評価
(1)粘度
B型回転粘度計を用いて25℃で測定した。
(2)透湿度
接着剤組成物を、乾燥後の厚さが50μmとなるようにバーコーターを用いて剥離紙の剥離剤面に塗工し、その後、室温下で有機溶剤を揮散させた。次いで、40℃に温度設定された熱風循環式オーブン中で5日間エージングさせたものを試験片とし、JIS Z 0208に準拠して測定した。[2] Performance evaluation (1) Viscosity The viscosity was measured at 25 ° C. using a B-type rotational viscometer.
(2) Moisture permeability The adhesive composition was applied to the release agent surface of the release paper using a bar coater so that the thickness after drying was 50 μm, and then the organic solvent was volatilized at room temperature. Subsequently, the test piece was aged for 5 days in a hot-air circulating oven set at 40 ° C., and measured according to JIS Z 0208.
(3)はく離接着強さ
(A)試験片の作製
厚さ40μmのアルミニウム箔に、接着剤組成物をバーコーターで塗布し、その後、100℃に調温された熱風循環式オーブンに収容して60秒間乾燥させ、接着剤組成物に含有されていた有機溶媒を除去して膜厚6〜8μmの接着剤層を形成した。次いで、接着剤層に熱融着性樹脂フィルムとして厚さ80μmの無延伸ポリプロピレンフィルム(以下、CPPと略記する。)を貼合し、熱傾斜試験機を用いて接着させた。このときの接着条件は、温度80℃、圧力0.3MPa、圧着時間3秒とし、アルミ面より加圧して圧着した。接着面積10×25mmとした。次いで、この試験片を40℃に調温された熱風循環式オーブンに収容し、5日間エージングした。(3) Peeling adhesive strength (A) Preparation of test piece The adhesive composition was applied to an aluminum foil having a thickness of 40 μm with a bar coater, and then housed in a hot-air circulating oven adjusted to 100 ° C. The organic solvent contained in the adhesive composition was removed by drying for 60 seconds to form an adhesive layer having a film thickness of 6 to 8 μm. Next, an unstretched polypropylene film having a thickness of 80 μm (hereinafter abbreviated as CPP) was bonded to the adhesive layer as a heat-fusible resin film, and bonded using a thermal inclination tester. At this time, the bonding conditions were a temperature of 80 ° C., a pressure of 0.3 MPa, and a pressure bonding time of 3 seconds. The adhesion area was 10 × 25 mm. Subsequently, this test piece was stored in a hot-air circulating oven adjusted to 40 ° C. and aged for 5 days.
(B)Tはく離接着強さ
(a)常態(初期)
エージング終了後、試験片を15mm幅に裁断し、アルミニウム箔とCPP間のTはく離接着強さ(N/15mm)を測定した。
(b)温水浸漬後
上記(a)で15mm幅に裁断した試験片を85℃の温水に7日間浸漬した。浸漬後、23℃の水で洗浄し、洗浄後、直ちにアルミニウム箔とCPP間のTはく離接着強さ(N/15mm)を測定した。
尚、Tはく離接着強さは(a)、(b)ともに引張り試験機(東洋精機社製)を使用し、温度23℃、引張速度100mm/分の条件で測定した。
結果を表1、2に併記する。(B) T peel adhesion strength (a) Normal state (initial)
After the aging was completed, the test piece was cut to a width of 15 mm, and the T peel adhesion strength (N / 15 mm) between the aluminum foil and the CPP was measured.
(B) After immersion in warm water The test piece cut to a width of 15 mm in (a) above was immersed in warm water at 85 ° C. for 7 days. After immersion, the substrate was washed with water at 23 ° C., and immediately after the washing, the T peel adhesion strength (N / 15 mm) between the aluminum foil and the CPP was measured.
The T peel adhesion strength was measured using a tensile tester (manufactured by Toyo Seiki Co., Ltd.) for both (a) and (b) at a temperature of 23 ° C. and a tensile speed of 100 mm / min.
The results are shown in Tables 1 and 2.
表1の結果によれば、酸変性ポリプロピレンの融解エネルギー及び当量比(NCO/OH)がともに好ましい範囲にある実験例1〜4では、初期及び温水浸漬後のいずれのはく離接着強さも十分に大きく、優れた接着性と耐温水性とを併せて有していることが分かる。特に、より当量比が大きい実験例2では温水浸漬後のはく離接着強さが大きく、より優れた耐温水性を有していることが分かる。また、当量比が更に大きい実験例4では初期及び温水浸漬後のはく離接着強さがともにより大きく、特に優れた低温接着性及び耐温水性を有していることが分かる。 According to the results of Table 1, in Experimental Examples 1 to 4 in which both the melting energy and the equivalent ratio (NCO / OH) of the acid-modified polypropylene are in the preferred range, both the initial and the peel adhesion strength after immersion in warm water are sufficiently large. It can be seen that it has both excellent adhesion and hot water resistance. In particular, in Experimental Example 2 with a larger equivalent ratio, it can be seen that the peel adhesion strength after immersion in warm water is large, and that it has better warm water resistance. Moreover, in Experimental Example 4 in which the equivalence ratio is larger, it can be seen that the peel adhesion strength at the initial stage and after immersion in warm water is larger, and particularly, it has excellent low-temperature adhesion and hot water resistance.
また、表2の結果によれば、多官能イソシアネート化合物が含有されていない実験例5では、温水浸漬後のはく離接着強さが小さく、耐温水性が劣っている。更に、酸変性ポリプロピレンの融解エネルギーが過大である実験例6では、酸変性ポリプロピレンが有機溶媒に溶解しないため、はく離接着強さの測定そのものができなかった。また、非晶性の酸変性SEBSを用いた実験例7では、初期及び温水浸漬後のはく離接着強さがともに小さく、接着性、耐温水性ともに劣っていることが分かる。
尚、実験例1〜7の各々の接着剤組成物の透湿度の値によれば、この透湿度が50g/m2・24h以下であれば、接着剤組成物のはく離接着強さに特に影響は及ぼさないことが分かる。また、同様に接着剤組成物の粘度もはく離接着強さに特に影響を及ぼさないことが分かる。Moreover, according to the result of Table 2, in Experimental example 5 which does not contain a polyfunctional isocyanate compound, the peeling adhesive strength after warm water immersion is small, and warm water resistance is inferior. Furthermore, in Experimental Example 6 where the melting energy of the acid-modified polypropylene is excessive, the acid-modified polypropylene does not dissolve in the organic solvent, and thus the peel adhesion strength itself cannot be measured. Further, in Experimental Example 7 using amorphous acid-modified SEBS, it can be seen that both the initial peel strength after immersion in hot water and that after hot water immersion are small, and the adhesiveness and hot water resistance are poor.
In addition, according to the value of the moisture permeability of each adhesive composition of Experimental Examples 1 to 7, if this moisture permeability is 50 g / m 2 · 24 h or less, it particularly affects the peel adhesion strength of the adhesive composition. It is understood that does not reach. Similarly, it can be seen that the viscosity of the adhesive composition does not particularly affect the peel adhesion strength.
Claims (4)
該有機溶媒に溶解又は分散されているカルボキシル基を有するポリオレフィン樹脂と、
該有機溶媒に含有されている多官能イソシアネート化合物と、を有し、該多官能イソシアネート化合物は1分子中に3個以上のイソシアネート基を有する変性イソシアネート化合物であり、ポリオレフィン素材の接着に用いられる接着剤組成物であって、
上記ポリオレフィン樹脂は、ポリオレフィンにエチレン性不飽和カルボン酸又はその無水物をグラフト重合させた変性ポリオレフィン樹脂、及びオレフィンモノマーとエチレン性不飽和カルボン酸との共重合樹脂の少なくとも一方であり、
該ポリオレフィン樹脂のJIS K 7121に準拠して測定した融解エネルギーが5〜15mJ/mgであり、
上記有機溶媒と該ポリオレフィン樹脂との合計を100質量%とした場合に、該ポリオレフィン樹脂は10〜20質量%であり、
上記接着剤組成物のJIS Z 0208に準拠して測定した透湿度が10〜50g/m 2 /24hであり、
金属箔と熱融着性樹脂フィルム層との接合に用いられることを特徴とする接着剤組成物。An organic solvent,
A polyolefin resin having a carboxyl group dissolved or dispersed in the organic solvent;
A polyfunctional isocyanate compound contained in the organic solvent, and the polyfunctional isocyanate compound is a modified isocyanate compound having three or more isocyanate groups in one molecule, and is used for adhesion of polyolefin materials. a composition,
The polyolefin resin is at least one of a modified polyolefin resin obtained by graft polymerization of an ethylenically unsaturated carboxylic acid or an anhydride thereof to a polyolefin, and a copolymer resin of an olefin monomer and an ethylenically unsaturated carboxylic acid,
The melting energy of the polyolefin resin measured according to JIS K 7121 is 5 to 15 mJ / mg,
When the total of the organic solvent and the polyolefin resin is 100% by mass, the polyolefin resin is 10 to 20% by mass,
Moisture permeability was measured according to JIS Z 0208 of the adhesive composition is a 10~50g / m 2 / 24h,
An adhesive composition used for joining a metal foil and a heat-fusible resin film layer .
該接着剤層の一面に接合された金属箔と、
該接着剤層の他面に接合された熱融着性樹脂フィルム層と、を備えることを特徴とする熱融着性部材。An adhesive layer formed by curing the adhesive composition according to any one of claims 1 to 3 ,
A metal foil bonded to one surface of the adhesive layer;
And a heat-fusible resin film layer bonded to the other surface of the adhesive layer.
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