JP2907488B2 - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JP2907488B2 JP2907488B2 JP2122266A JP12226690A JP2907488B2 JP 2907488 B2 JP2907488 B2 JP 2907488B2 JP 2122266 A JP2122266 A JP 2122266A JP 12226690 A JP12226690 A JP 12226690A JP 2907488 B2 JP2907488 B2 JP 2907488B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- carboxylic acid
- resin
- acid
- polyolefin
- 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.)
- Expired - Fee Related
Links
- 239000000853 adhesive Substances 0.000 title description 22
- 230000001070 adhesive effect Effects 0.000 title description 22
- 239000000203 mixture Substances 0.000 title description 13
- 239000003822 epoxy resin Substances 0.000 claims description 29
- 229920000647 polyepoxide Polymers 0.000 claims description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 24
- 229920005672 polyolefin resin Polymers 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- -1 polyethylene Polymers 0.000 description 11
- 239000000178 monomer Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 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 5
- 238000002360 preparation method Methods 0.000 description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-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
- 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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-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
- YTNUOGWCFLMGLF-UHFFFAOYSA-N 5-methylbenzene-1,2,3,4-tetrol Chemical compound CC1=CC(O)=C(O)C(O)=C1O YTNUOGWCFLMGLF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-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
- 238000005452 bending Methods 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
- 239000004566 building material Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- 150000003951 lactams Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用分野） 本発明は、接着剤組成物に関し、詳しくはポリオレフ
ィンと金属とのラミネートに用いられる接着剤組成物で
あって、特に短時間の接着条件でも優れた接着性を示
し、耐湿性、耐食性、耐アルカリ性に優れた接着剤組成
物に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to an adhesive composition, and more particularly to an adhesive composition used for laminating a polyolefin and a metal. The present invention relates to an adhesive composition exhibiting excellent adhesiveness even under adhesive conditions for a long time, and having excellent moisture resistance, corrosion resistance and alkali resistance.
（従来の技術） ポリオレフィンフィルムにより被覆されたラミネート
金属板は、ポリオレフィンの持つ耐薬品性、耐汚染性、
耐水性、衛生性という特長を生かして製缶用素材、建築
物の内装用素材、厨房機械器具素材として使用されてい
る。(Prior art) Laminated metal sheet covered with polyolefin film has the chemical resistance, stain resistance,
Utilizing the features of water resistance and hygiene, it is used as a material for cans, materials for building interiors, and kitchen equipment.
金属板とポリオレフィンフィルムとの接着剤として
は、従来、エポキシ−フェノール系の有機溶剤溶液にカ
ルボキシル基含有ポリオレフィン樹脂の粒子を分散させ
たものが知られている（特開昭53-13342号公報）。この
接着剤は一次接着力については非常に良好であるが、煮
沸水処理、アルカリ、酸、塩類等の腐蝕性環境下におけ
る接着耐久性に劣るという問題点があった。As an adhesive between a metal plate and a polyolefin film, there is conventionally known an adhesive obtained by dispersing carboxyl group-containing polyolefin resin particles in an epoxy-phenol-based organic solvent solution (JP-A-53-13342). . Although this adhesive has a very good primary adhesive strength, it has a problem in that it has poor adhesion durability in a corrosive environment such as boiling water treatment, alkalis, acids and salts.
（発明が解決しようとする課題） 本発明者は、ポリオレフィンフィルムラミネート金属
板を連続して高速で製造する短時間接着条件においても
優れた接着性を示す接着剤組成物を提供するものであ
る。(Problem to be Solved by the Invention) The present inventor provides an adhesive composition which exhibits excellent adhesiveness even under short-time bonding conditions for continuously producing a polyolefin film-laminated metal plate at a high speed.
本発明は、又、折り曲げ、張り出し等の過酷な加工を
施した場合でも加工密着性を示すポリオレフィンフィル
ムラミネート金属板を提供するものである。Another object of the present invention is to provide a polyolefin film-laminated metal sheet that exhibits processing adhesion even when subjected to severe processing such as bending and overhanging.
本発明は、又、耐湿性、耐食性、耐アルカリ性等に対
する二次密着性の優れたポリオレフィンフィルムラミネ
ート金属板を提供するものである。Another object of the present invention is to provide a polyolefin film-laminated metal sheet having excellent secondary adhesion to moisture resistance, corrosion resistance, alkali resistance and the like.
（課題を解決するための手段） すなわち、本発明は、カルボン酸含有ポリオレフィン
樹脂（Ａ）と、カルボン酸含有エポキシ樹脂（Ｂ）と、
ポリイソシアネート化合物（Ｃ）と、必要に応じてエポ
キシ樹脂（Ｄ）とからなる成分を有機溶剤に溶解、分散
させてなり、固形分重量割合が（Ａ）／〔（Ｂ）＋
（Ｃ）＋（Ｄ）〕＝0.01〜2.0である接着剤組成物であ
る。(Means for Solving the Problems) That is, the present invention provides a carboxylic acid-containing polyolefin resin (A), a carboxylic acid-containing epoxy resin (B),
A component comprising a polyisocyanate compound (C) and, if necessary, an epoxy resin (D) is dissolved and dispersed in an organic solvent, and the solid content weight ratio is (A) / [(B) +
(C) + (D)] = 0.01 to 2.0.
本発明のカルボン酸含有ポリオレフィン樹脂（Ａ）
は、ポリオレフィンにエチレン性不飽和カルボン酸もし
くはその無水物をグラフト重合させた変性樹脂を代表的
なものとして挙げることができる。ポリオレフィンとし
ては、ポリエチレン、ポリプロピレン、ポリブテン等の
単独重合体あるいは共重合体、又は、上記オレフィンモ
ノマーとジシクロペンタジエン、４−メチルペンテン−
１、酢酸ビニル等の共重合体であってもよい。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
等がある。又、カルボン酸含有ポリオレフィン樹脂
（Ａ）として、ポリオレフィンを構成するモノマーとエ
チレン性不飽和カルボン酸との共重合体を用いてもよ
い。このようなカルボン酸含有ポリオレフィン樹脂中の
カルボン酸含有量は、0.001〜2.0重量％の範囲が好まし
い。Carboxylic acid-containing polyolefin resin (A) of the present invention
As a typical example, a modified resin obtained by graft-polymerizing an ethylenically unsaturated carboxylic acid or an anhydride thereof with a polyolefin can be mentioned. As the polyolefin, a homopolymer or a copolymer such as polyethylene, polypropylene, and polybutene, or the olefin monomer and dicyclopentadiene, 4-methylpentene-
1, may be a copolymer such as vinyl acetate. As ethylenically unsaturated carboxylic acids, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid,
Citraconic acid, 5-norbornene-2,3-dicarboxylic acid and the like. Further, as the carboxylic acid-containing polyolefin resin (A), a copolymer of a monomer constituting the polyolefin and an ethylenically unsaturated carboxylic acid may be used. The carboxylic acid content in such a carboxylic acid-containing polyolefin resin is preferably in the range of 0.001 to 2.0% by weight.
カルボン酸含有ポリオレフィン樹脂（Ａ）は、有機溶
媒中に分散せしめたものを溶剤分散体の形で使用するこ
とができる。カルボン酸含有ポリオレフィンの分散体
は、カルボン酸含有ポリオレフィン樹脂を物理的に粉砕
し溶媒中に分散させるか、またはポリオレフィンを溶解
する有機溶剤中に熱時溶解し、冷却して溶剤中に樹脂を
析出、分散させる方法によっても得ることができる。The carboxylic acid-containing polyolefin resin (A) can be used by dispersing it in an organic solvent in the form of a solvent dispersion. Dispersion of carboxylic acid-containing polyolefin is obtained by physically pulverizing the carboxylic acid-containing polyolefin resin and dispersing it in the solvent, or dissolving it in an organic solvent that dissolves the polyolefin while heating and cooling to precipitate the resin in the solvent. Can also be obtained by a method of dispersing.
カルボン酸含有ポリオレフィン樹脂（Ａ）の他の樹脂
成分中に占める含有量は、重量比で0.01〜2.0であり、
この比率が0.01より小さいとポリオレフィン面に対する
接着性に乏しくなり、2.0より大きくなると接着剤の流
動性が乏しくなり塗工性が悪くなる他、接着剤の耐湿
性、耐食性、耐アルカリ性が著しく低下するため好まし
くない。The content of the carboxylic acid-containing polyolefin resin (A) in the other resin components is 0.01 to 2.0 by weight,
If this ratio is less than 0.01, the adhesiveness to the polyolefin surface becomes poor, and if it is more than 2.0, the fluidity of the adhesive becomes poor and the coating property deteriorates, and the moisture resistance, corrosion resistance, and alkali resistance of the adhesive are significantly reduced. Therefore, it is not preferable.
本発明のカルボン酸含有エポキシ樹脂（Ｂ）は、ビス
フェノール型エポキシ樹脂、ノボラック型エポキシ樹
脂、テトラヒドロキシフェニルメタンエポキシ樹脂、グ
リセリントリエーテル型エポキシ樹脂のようなエポキシ
樹脂（Ｄ）を化学的変性によりカルボン酸を導入したも
のである。好ましくは、数平均分子量型3200〜12000、
エポキシ当量が1600〜6000のエポキシ樹脂（Ｄ）を使用
する。The carboxylic acid-containing epoxy resin (B) of the present invention is obtained by chemically modifying an epoxy resin (D) such as a bisphenol type epoxy resin, a novolak type epoxy resin, a tetrahydroxyphenylmethane epoxy resin, or a glycerin triether type epoxy resin. An acid is introduced. Preferably, the number average molecular weight type 3200-12000,
An epoxy resin (D) having an epoxy equivalent of 1600 to 6000 is used.
カルボン酸含有エポキシ樹脂（Ｂ）は、種々の方法で
得ることができる。例えば、エポキシ樹脂を含む溶液中
に、過酸化物の存在下、上述したエチレン性不飽和カル
ボン酸の単独あるいはエチレン性不飽和単量体カルボン
酸を含むモノマー混合物を反応させるとエポキシ樹脂に
不飽和カルボン酸がグラフトしたエポキシ樹脂が得られ
る。エチレン性不飽和カルボン酸と共重合できるモノマ
ーとしては、（メタ）アクリル酸エチル、（メタ）アク
リル酸ブチル等の（メタ）アクリル酸アルキルエステ
ル、（メタ）アクリルアミド、（メタ）アクリロニトリ
ル、スチレン、α−メチルスチレン等がある。場合によ
っては共重合モノマーとして、２−ヒドロキシメチル
（メタ）アクリレート等の水酸基含有モノマーを使用し
てもよい。The carboxylic acid-containing epoxy resin (B) can be obtained by various methods. For example, in a solution containing an epoxy resin, the reaction of the above-mentioned ethylenically unsaturated carboxylic acid alone or a monomer mixture containing an ethylenically unsaturated monomeric carboxylic acid in the presence of a peroxide causes the epoxy resin to become unsaturated. An epoxy resin grafted with a carboxylic acid is obtained. Monomers that can be copolymerized with the ethylenically unsaturated carboxylic acid include (meth) acrylic acid alkyl esters such as ethyl (meth) acrylate and butyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, styrene, α -Methylstyrene and the like. In some cases, a hydroxyl-containing monomer such as 2-hydroxymethyl (meth) acrylate may be used as the copolymerized monomer.
又、カルボン酸含有エポキシ樹脂（Ｂ）は、エチレン
性不飽和カルボン酸と共重合性モノマーとを含むアクリ
ル系樹脂を、エステル触媒の存在下、エポキシ樹脂と反
応させて得た変性樹脂（Ｂ）であってもよい。又、エポ
キシ樹脂のエポキシ基を一部に予め、アクリル酸、メタ
クリル酸等によりエステル化し、このビニル基を有する
エポキシ樹脂にエチレン性不飽和カルボン酸あるいはこ
れを含むモノマーを付加重合して変性樹脂（Ｂ）を得て
もよい。The carboxylic acid-containing epoxy resin (B) is a modified resin (B) obtained by reacting an acrylic resin containing an ethylenically unsaturated carboxylic acid and a copolymerizable monomer with an epoxy resin in the presence of an ester catalyst. It may be. In addition, the epoxy group of the epoxy resin is partially esterified in advance with acrylic acid, methacrylic acid, or the like, and an ethylenically unsaturated carboxylic acid or a monomer containing the vinyl group is addition-polymerized to the epoxy resin having a vinyl group to form a modified resin ( B) may be obtained.
又、エポキシ樹脂の水酸基に、無水フタル酸、無水ト
リメリット酸、無水ピロメリット酸等の多価酸無水物を
反応させて得た変性樹脂（Ｂ）であってもよい。Further, a modified resin (B) obtained by reacting a hydroxyl group of an epoxy resin with a polyhydric anhydride such as phthalic anhydride, trimellitic anhydride, or pyromellitic anhydride may be used.
カルボン酸含有エポキシ樹脂（Ｂ）の含有量は、0.3
≦（Ｂ）／〔（Ｂ）＋（Ｃ）＋（Ｄ）〕≦0.95であり、
上記最小量より少ないと、金属との密着性、耐湿性、耐
食性、耐アルカリ性等が共に低下する。The content of the carboxylic acid-containing epoxy resin (B) is 0.3
≦ (B) / [(B) + (C) + (D)] ≦ 0.95,
If the amount is less than the above minimum amount, the adhesion to metal, moisture resistance, corrosion resistance, alkali resistance and the like are all reduced.
ポリイソシアネート化合物（Ｃ）としては、イソシア
ネート基をオキシムなどのブロック剤で保護して不活性
としておき、加熱によりイソシアネート基が活性となる
ブロック化イソシアネート化合物が、１液型の接着剤組
成物を得る上で望ましいが、１液型の制約がなければこ
のような処理をしないポリイソシアネートを使用するこ
とは勿論可能である。As the polyisocyanate compound (C), the isocyanate group is protected with a blocking agent such as an oxime to make it inactive, and the blocked isocyanate compound which becomes active by heating to obtain a one-pack type adhesive composition. Although it is desirable above, it is of course possible to use a polyisocyanate which does not undergo such treatment unless there is a restriction of a one-pack type.
ポリイソシアネートとしては、トリレンジイソシアネ
ート（TDI）、4,4−ジフェニルメタンジイソシアネート
（MDI）、キシレンジイソシアネート（XDI）、メタキシ
レンジイソシアネート（MXDI）、ヘキサメチレンジイソ
シアネート（HMDI）、リジンジイソシアネート（LD
I）、水素化MDI、水素化TDI、水素化XDI、イソホロンジ
イソシアネート（IPDI）、トリメチルヘキサジイソシア
ネート（TMDI）、ダイマー酸ジイソシアネート（DDI）
等、又は、上記ポリイソシアネートとトリメチロールプ
ロパンあるいはネオペンチルグリコール等の多価アルコ
ール化合物とのアダクト体がある。Polyisocyanates include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), meta-xylene diisocyanate (MXDI), hexamethylene diisocyanate (HMDI), and lysine diisocyanate (LD
I), hydrogenated MDI, hydrogenated TDI, hydrogenated XDI, isophorone diisocyanate (IPDI), trimethylhexadiisocyanate (TMDI), dimer acid diisocyanate (DDI)
Or an adduct of the above polyisocyanate and a polyhydric alcohol compound such as trimethylolpropane or neopentyl glycol.
ブロック剤としては、フェノール、クレゾール、芳香
族第２アミン、第３級アルコール、ラクタム、オキシ
ム、マロン酸ジエチルエステル、アセト酢酸エチル、ア
セチルアセトン、青酸、酸性亜硫酸ナトリウム等がある
が、メチルエチルケトンオキシムのようなオキシムが好
ましい。Examples of the blocking agent include phenol, cresol, aromatic secondary amine, tertiary alcohol, lactam, oxime, malonic acid diethyl ester, ethyl acetoacetate, acetylacetone, hydrocyanic acid, sodium acid sulfite, and the like. Oximes are preferred.
ポリイソシアネート化合物（Ｃ）の配合量は、0.05≦
（Ｃ）／〔（Ｂ）＋（Ｃ）＋（Ｃ）〕≦0.40であり、上
記配合量の上限は架橋が進み過ぎて加工性、密着性等を
低下させない理由により制限を受け、上記量の下限は、
架橋が不十分のために耐湿性、耐食性、耐アルカリ性等
の低下により制限を受ける。The blending amount of the polyisocyanate compound (C) is 0.05 ≦
(C) / [(B) + (C) + (C)] ≦ 0.40, and the upper limit of the compounding amount is limited by the reason that the crosslinking does not proceed too much to lower the workability, adhesion, etc. Is the lower limit of
Insufficient cross-linking limits the reduction in moisture resistance, corrosion resistance, alkali resistance, and the like.
本発明の接着剤組成物は、有機溶剤に溶解および分散
した形で使用する。この有機溶剤としてはアセトン、メ
チルエチルケトン、メチルイソブチルケトン、シクロヘ
キサノン、イソホロン等のケトン類、ベンゼン、トルエ
ン、キシレン、他のアルキルベンゼン等の芳香族類、メ
チルセルソルブ、エチルセルソルブ、ブチルセルソルブ
等のセロソルブ類、メチルセロソルブアセテート、ブチ
ルセルソロブアセテート、酢酸エチル、酢酸ブチル等の
エステル類、イソプロピルアルコール、ブチルアルコー
ル、ジアセトンアルコール等のアルコール類など、また
はこれらの混合溶媒を用いることができる 本発明の接着剤組成物は、アルミニウム板あるいは鋼
板上にローラー塗装、スプレー塗装等の方法により、乾
燥膜厚として３〜10g/m2程度の塗布量で塗布し、約180
〜250℃、30秒〜15分で焼付ける。乾燥した接着剤は、
ポリプロピレン等のポリオレフィンのフィルムあるいは
溶融ポリオレフィンと接着性を有する。The adhesive composition of the present invention is used in a form dissolved and dispersed in an organic solvent. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; aromatics such as benzene, toluene, xylene, and other alkylbenzenes; , Alcohols such as isopropyl alcohol, butyl alcohol, diacetone alcohol, and the like, or a mixed solvent thereof can be used. The agent composition is applied on an aluminum plate or a steel plate by a method such as roller coating or spray coating at a coating amount of about 3 to 10 g / m 2 as a dry film thickness.
Bake at ~ 250 ° C for 30 seconds to 15 minutes. The dried adhesive is
It has adhesiveness to films of polyolefin such as polypropylene or molten polyolefin.
以下、本発明を実施例をもって説明する。 Hereinafter, the present invention will be described with reference to examples.
（実施例） 製造例１ 変性エポキシ樹脂B1の調製 反応缶にビスフェノールＡ型エポキシ樹脂（油化シェ
ル社製エピコート1010）360部、セロソルブアセテート3
60部を仕込み、窒素気流下、加熱溶解し溶液温度を110
〜120℃に保つ。無水マレイン酸20部、スチレン20部、
および、過酸化ベンゾイル４部をセロソルブアセテート
236部に溶解したものを滴下缶より２時間かけて滴下
し、滴下終了後更に１時間その温度で反応を続けカルボ
ン酸変性エポキシ樹脂B1を得た。(Example) Production Example 1 Preparation of Modified Epoxy Resin B1 In a reaction vessel, 360 parts of bisphenol A type epoxy resin (Epicoat 1010 manufactured by Yuka Shell Co., Ltd.), cellosolve acetate 3
Charge 60 parts, heat and melt under a nitrogen stream, and raise the solution temperature to 110.
Keep at ~ 120 ° C. 20 parts of maleic anhydride, 20 parts of styrene,
And 4 parts of benzoyl peroxide in cellosolve acetate
The solution dissolved in 236 parts was dropped from the dropping can over 2 hours, and after the completion of dropping, the reaction was continued at that temperature for 1 hour to obtain a carboxylic acid-modified epoxy resin B1.
製造例２ 変性エポキシ樹脂B2の調製 製造例１において滴下モノマー溶液をアクリル酸20
部、スチレン20部、および、過酸化ベンゾイル２部をセ
ロソルブアセテート238部に溶解したものを使用した他
は製造例１と同様にして変性エポキシ樹脂B2を得た。Preparation Example 2 Preparation of Modified Epoxy Resin B2
Parts, styrene 20 parts, and benzoyl peroxide 2 parts dissolved in cellosolve acetate 238 parts were used in the same manner as in Production Example 1 to obtain a modified epoxy resin B2.
製造例３ 変性エポキシ樹脂B3 反応缶にビスフェノールＡ型エポキシ樹脂（油化シェ
ル社製エピコート1010）380部、セロソルブアセテート3
80部を仕込み、窒素気流下、加熱溶解し溶液温度を120
〜130℃に保つ。無水トリメリット酸20部を加え、５時
間反応し変性エポキシ樹脂B3を得た。Production Example 3 Modified epoxy resin B3 In a reaction vessel, 380 parts of bisphenol A type epoxy resin (Epicoat 1010 manufactured by Yuka Shell Co., Ltd.), cellosolve acetate 3
Charge 80 parts, heat and melt under a nitrogen stream, and raise the solution temperature to 120.
Keep at ~ 130 ° C. 20 parts of trimellitic anhydride were added and reacted for 5 hours to obtain a modified epoxy resin B3.
調製例４ イソシアネート化合物の調製 反応缶にクルード4,4′−ジフェニルメタンジイソシ
アネート（日本ポリウレタン社製スプラセックＴ）300
部、シクロヘキサノン300部、キシレン290部、メチルエ
チルケトンオキシム110部を仕込み、窒素気流下、徐々
に温度をあげて80℃で３時間反応してブロック化イソシ
アネート化合物を得た。Preparation Example 4 Preparation of Isocyanate Compound In a reaction vessel, crude 4,4'-diphenylmethane diisocyanate (Nippon Polyurethane Co., Suprasek T) 300 was prepared.
Parts, 300 parts of cyclohexanone, 290 parts of xylene, and 110 parts of methyl ethyl ketone oxime were charged, and the temperature was gradually increased under a nitrogen stream at 80 ° C. for 3 hours to obtain a blocked isocyanate compound.
表１に示すような樹脂固型分比の接着剤を20％固形分
として調製した。この接着剤組成物を板厚0.5mmの電気
亜鉛メッキ鋼板にロールコーターにて6.5g/m2になるよ
うに塗布し、続いてガスオーブンによって240℃で60秒
間加熱乾燥を行い、その直後に膜厚0.15mmのポリプロピ
レンフィルムを電動ロールで加圧しポリプロピレンフィ
ルムラミネート金属板を得た。An adhesive having a resin solid fraction ratio as shown in Table 1 was prepared as a 20% solid content. The adhesive composition was coated so as to 6.5 g / m 2 by a roll coater to electro-galvanized steel sheet having a thickness of 0.5 mm, followed for 60 seconds heated and dried at 240 ° C. by a gas oven, immediately thereafter A polypropylene film having a thickness of 0.15 mm was pressed with an electric roll to obtain a polypropylene film-laminated metal plate.
こうして得たラミネート金属板のサンプルを各種の試
験に供した。試験方法と評価は下記のとおりである。Samples of the laminated metal plate thus obtained were subjected to various tests. The test method and evaluation are as follows.
（１）接着力（状態）:JIS K6744-8.2項に基づくエリク
セン剥離試験を行った。(1) Adhesive strength (state): An Erichsen peel test based on JIS K6744-8.2 was performed.
○・・・刻線をナイフエッジ強制剥離し、剥離のないも
の △・・・刻線をナイフエッジ強制剥離し、剥離が3mm以
下のもの ×・・・刻線をナイフエッジ強制剥離し、剥離が3mm以
上のもの （２）接着力（ボイル後）：煮沸水中に１時間浸漬後、
取り出してJIS K6744-8.2項に基づくエリクセン剥離試
験を行った。・ ・ ・: Marked line is forcibly peeled off by knife edge and no peeling ・ ・ ・: Marked line is forcibly peeled off by knife edge and peeling is 3 mm or less ×: Marked line is forcibly peeled off by knife edge and peeled (3) Adhesion (after boiling): After immersion in boiling water for 1 hour,
The sample was taken out and subjected to an Erichsen peeling test based on JIS K6744-8.2.
〔発明の効果〕 本発明の接着剤組成物は、短時間接着性に優れている
ので、塗布、乾燥、ラミネ−ト処理をインラインで一貫
して行っても優れた接着力を発揮することができる。こ
の場合、金属板上の接着剤組成物を加熱乾燥した熱量を
利用することができるので、ラミネート金属板の製造
上、また、省エネルギーの点においても好ましく、本発
明の接着剤組成物の利点を最大に利用することができ
る。 [Effect of the Invention] Since the adhesive composition of the present invention has excellent short-time adhesiveness, it can exhibit excellent adhesive strength even when coating, drying and laminating are performed inline and consistently. it can. In this case, since the amount of heat obtained by heating and drying the adhesive composition on the metal plate can be used, the production of the laminated metal plate is also preferable in terms of energy saving, and the advantages of the adhesive composition of the present invention can be obtained. Can be used to the maximum.
また、耐食性、耐薬品性に優れるので、一般建材から
高度の加工密着性を要求される用途においても適用可能
である。Further, since it is excellent in corrosion resistance and chemical resistance, it can be applied to applications requiring high processing adhesion from general building materials.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C08G 18/62,18/58 C09J 175/04 C09J 163/00 - 163/10 C09J 123/26 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C08G 18 / 62,18 / 58 C09J 175/04 C09J 163/00-163/10 C09J 123/26
Claims (1)
と、カルボン酸含有エポキシ樹脂（Ｂ）と、ポリイソシ
アネート化合物（Ｃ）と、必要に応じてエポキシ樹脂
（Ｄ）とからなる成分を有機溶剤に溶解、分散させてな
り、固形分重量割合が（Ａ）／〔（Ｂ）＋（Ｃ）＋
（Ｄ）〕＝0.01〜2.0である接着剤組成物。1. A carboxylic acid-containing polyolefin resin (A)
And a component comprising a carboxylic acid-containing epoxy resin (B), a polyisocyanate compound (C), and, if necessary, an epoxy resin (D) are dissolved and dispersed in an organic solvent. A) / [(B) + (C) +
(D)] = 0.01 to 2.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2122266A JP2907488B2 (en) | 1990-05-11 | 1990-05-11 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2122266A JP2907488B2 (en) | 1990-05-11 | 1990-05-11 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0418480A JPH0418480A (en) | 1992-01-22 |
| JP2907488B2 true JP2907488B2 (en) | 1999-06-21 |
Family
ID=14831705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2122266A Expired - Fee Related JP2907488B2 (en) | 1990-05-11 | 1990-05-11 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2907488B2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5177149B2 (en) * | 2008-01-10 | 2013-04-03 | 東亞合成株式会社 | Adhesive composition and heat-fusible member using the same |
| JP5343408B2 (en) * | 2008-06-02 | 2013-11-13 | 横浜ゴム株式会社 | Metal / olefin resin adhesive composition with excellent salt water adhesion |
| US20110159379A1 (en) | 2008-09-11 | 2011-06-30 | Nec Corporation | Secondary battery |
| JP5385620B2 (en) * | 2009-01-19 | 2014-01-08 | 三井化学株式会社 | Adhesive composition |
| TWI507494B (en) | 2010-12-28 | 2015-11-11 | Toagosei Co Ltd | An adhesive composition and a hot melt adhesive member using the composition |
| JP5954283B2 (en) * | 2013-09-20 | 2016-07-20 | Dic株式会社 | Adhesive composition for laminate laminate, laminate using the same, and secondary battery |
| KR20160047468A (en) * | 2014-09-17 | 2016-05-02 | 디아이씨 가부시끼가이샤 | Adhesive for the laminating, the laminate using it and rechargeable battery |
| TWI754073B (en) | 2017-06-26 | 2022-02-01 | 日商東亞合成股份有限公司 | Adhesive composition and heat-adhesive member using the same |
| TWI804552B (en) | 2018-01-09 | 2023-06-11 | 日商東亞合成股份有限公司 | Adhesive composition, and material for battery, material for lithium ion battery, thermal fusible member, and packging material for lithium ion battery, each using adhesive composition |
| TWI835903B (en) | 2018-10-29 | 2024-03-21 | 日商東亞合成股份有限公司 | Adhesive composition and thermally fusible member using thereof |
| JPWO2021106849A1 (en) * | 2019-11-27 | 2021-06-03 | ||
| JPWO2021131812A1 (en) | 2019-12-23 | 2021-07-01 | ||
| CN114068119A (en) * | 2021-11-15 | 2022-02-18 | 南京泰瑞新材料科技有限公司 | Formula and preparation method of bonded magnet formed by anisotropic magnetic powder |
-
1990
- 1990-05-11 JP JP2122266A patent/JP2907488B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0418480A (en) | 1992-01-22 |
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