JPH0320321A - Resin composition for composite vibration-damping mateiral, composite vibration-damping material produced therefrom, and its production - Google Patents
Resin composition for composite vibration-damping mateiral, composite vibration-damping material produced therefrom, and its productionInfo
- Publication number
- JPH0320321A JPH0320321A JP2041509A JP4150990A JPH0320321A JP H0320321 A JPH0320321 A JP H0320321A JP 2041509 A JP2041509 A JP 2041509A JP 4150990 A JP4150990 A JP 4150990A JP H0320321 A JPH0320321 A JP H0320321A
- Authority
- JP
- Japan
- Prior art keywords
- vibration damping
- resin
- composite vibration
- polyester
- damping material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000013016 damping Methods 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 61
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 34
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 31
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000003466 welding Methods 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 description 40
- 230000001070 adhesive effect Effects 0.000 description 40
- 229910000831 Steel Inorganic materials 0.000 description 38
- 239000010959 steel Substances 0.000 description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 31
- 238000003475 lamination Methods 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- -1 isocyanate compound Chemical class 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 150000002334 glycols Chemical class 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004970 Chain extender Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentadiol Natural products OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QJGNSTCICFBACB-UHFFFAOYSA-N 2-octylpropanedioic acid Chemical compound CCCCCCCCC(C(O)=O)C(O)=O QJGNSTCICFBACB-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229930185605 Bisphenol Chemical group 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102100031480 Dual specificity mitogen-activated protein kinase kinase 1 Human genes 0.000 description 1
- 101710146526 Dual specificity mitogen-activated protein kinase kinase 1 Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 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
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- HNPDNOZNULJJDL-UHFFFAOYSA-N ethyl n-ethenylcarbamate Chemical compound CCOC(=O)NC=C HNPDNOZNULJJDL-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明は、２枚の鋼板の間に樹脂層を形成してなる複合
型制振鋼板のような制振材料に用いられる樹脂組成物お
よびこれを用いた複合型制振材料ならびにスポット溶接
可能な複合型制振材料およびその製造方法に関するもの
で、特に常温ないしはその近傍の温度において優れた制
振作用と高い接着性能、耐熱性を有する複合型制振材料
ならびに前記諸特性とスポット溶接性を有する複合型制
振材料の製造を可能にする樹脂組成物およびこれを用い
た複合型制振材料およびその製造方法に関するものであ
り、得られた複合型制振材料は騒音防止材料として、階
段、ドア、床材などの建材用途は勿論、自動車のオイル
バン、ボディー回゜りのダッシュバネル、フロアーパネ
ル、ルーフパネル等従来使用が困難であった用途、ある
いはモーター コンブレッサーのカバーなどにも使用で
きるものであって、自動車業界、土木建築業界、電機業
界において巾広く利用できるものである。Detailed Description of the Invention Industrial Field of Application The present invention relates to a resin composition and a vibration damping material used in a vibration damping material such as a composite vibration damping steel plate formed by forming a resin layer between two steel plates. This article relates to composite vibration damping materials using the same, spot weldable composite vibration damping materials, and methods for producing the same.In particular, composites that have excellent vibration damping properties, high adhesive performance, and heat resistance at or near room temperature. The present invention relates to a resin composition that enables the production of mold vibration damping materials and composite vibration damping materials having the above-mentioned properties and spot weldability, and a composite vibration damping material using the same and a method for manufacturing the same. Composite vibration damping materials are used as noise prevention materials not only for building materials such as stairs, doors, and flooring materials, but also for applications that were previously difficult to use, such as automobile oil vans, body rotation dash panels, floor panels, and roof panels. It can also be used as a cover for a motor compressor, etc., and can be widely used in the automobile industry, civil engineering and construction industry, and electrical machinery industry.
〈従来の技術〉
複合型制振鋼板は２枚の鋼板の間に粘弾性樹脂（以下中
間樹脂という）層を介在させ、その中間樹脂層により鋼
板に加えられる振動を熱エネルギーに変換する騒音防止
材料である。 この制振鋼板は、最近の騒音規制に対す
る二−ズに対応し、自動車のオイルバン、階段、ドア、
床材などの建材、モーター コンブレッサーのカバーな
どに使用もしくは検討されている．この制振鋼板の中間
樹脂として、従来よりポリウレタン（特開昭４７−１９
２７７） 、ビニルウレタン樹脂（特開昭５０−３９７
３７）、ポリエステル樹脂（特開昭５０−１４３８８０
）、ボリアミド樹脂（特開昭５１−７９１４６）、ポリ
イソブチレン（特開昭５４−４３２５１） エチレン／
αオレフィン（特開昭５５−８４６５５），ＥＶＡ （
特開昭５７−３４９４９） 、架橋ポリオレフィン（特
開昭５９−１ ５２８４７），ポリビニルアセタール（
特開昭６０−８８１４９）などが検討されており、アス
ファルト、合成ゴム、アクリル系粘着剤、エボキシ樹脂
なども制振性能を有することが知られている． これら
のうち，アクリル系粘着剤、イソブチレンゴム、ＥＶＡ
等の常温で柔軟な樹脂は常温付近の温度で、比較的高い
制振性を有するが、常温における樹脂の凝集力が弱いた
め、接着強度が弱く、当該樹脂を用いた制振鋼板は成形
加工に耐えられず、更に、プレス加工を受けた制振鋼板
材料は２００℃程度まで加熱される焼付塗装工程を経る
こともあり、上記の温度付近で中間樹脂の流失がないこ
とはもちろん、接着強度の低下が抑えられることも要求
され、従って、当然このような耐熱性もないため、これ
らの制振鋼板は平板に近い状態で使用される建材用途に
利用されるのみであった．
また、共重合、ブレンド等により変性されたポリオレフ
ィン系樹脂、例えば、エチレン／αオレフィン樹脂など
は、前者に比べ５０℃〜１００℃の高温側で比較的制振
性に優れ、常温における樹脂の凝集力が強く、成形加工
に対する対応もあるため、当該樹脂を用いた制振鋼板は
自動車のオイルバン等の高温で使用される用途の制振鋼
板に適しているといわれている。<Conventional technology> Composite vibration-damping steel plates have a viscoelastic resin (hereinafter referred to as intermediate resin) layer interposed between two steel plates, and the intermediate resin layer converts vibrations applied to the steel plates into thermal energy to prevent noise. It is the material. This vibration-damping steel plate meets the needs of recent noise regulations, and is used in automobile oil vans, stairs, doors, etc.
It is being used or being considered for building materials such as flooring and motor compressor covers. Conventionally, polyurethane (Japanese Unexamined Patent Publication No. 47-19
277), vinyl urethane resin (JP-A-50-397)
37), polyester resin (JP-A-50-143880
), polyamide resin (JP-A-51-79146), polyisobutylene (JP-A-54-43251), ethylene/
α-olefin (JP-A-55-84655), EVA (
JP-A-57-34949), cross-linked polyolefin (JP-A-59-1 52847), polyvinyl acetal (
JP-A-60-88149) has been studied, and it is known that asphalt, synthetic rubber, acrylic adhesives, epoxy resins, etc. also have vibration damping properties. Among these, acrylic adhesive, isobutylene rubber, EVA
Resins that are flexible at room temperature have relatively high vibration damping properties at temperatures around room temperature, but because the cohesive force of the resin is weak at room temperature, the adhesive strength is weak, and vibration damping steel plates using this resin are difficult to form. In addition, the vibration damping steel sheet material that has been press-formed may go through a baking process where it is heated up to about 200℃, so it is important that there is no loss of intermediate resin at around the above temperature, and that the adhesive strength is reduced. It is also required to suppress the decline in vibration damping steel plates, and therefore, naturally they do not have such heat resistance, so these damping steel plates have only been used as building materials where they are used in a state close to that of a flat plate. In addition, polyolefin resins modified by copolymerization, blending, etc., such as ethylene/α-olefin resins, have relatively superior vibration damping properties at high temperatures of 50°C to 100°C compared to the former, and the resin agglomerates at room temperature. Because it has strong strength and can be molded, damping steel sheets made of this resin are said to be suitable for use in high-temperature applications such as oil vans for automobiles.
しかしながら、両者ともその用途を限定したとしても、
制振性能や接着性能において十分に満足すべき水準に達
しているものとはいえず、さらに自動車ボディー回り部
品を初めとして常温付近の温度で高い制振性能を有し、
かつ成形加工に追随する強い接着性能と、高温下におけ
る接着耐熱性を要求される割振鋼板に適した樹脂はいま
だ見出されていない。However, even if both of them limit their uses,
It cannot be said that the vibration damping performance and adhesion performance have reached a fully satisfactory level, and furthermore, it has high vibration damping performance at temperatures around room temperature, including parts around the car body.
Moreover, a resin suitable for split steel plates, which requires strong adhesion performance that follows molding and heat resistance for adhesion at high temperatures, has not yet been found.
また、ポリエステル樹脂を制振鋼板用樹脂として検討し
た例として、
■分子量１８００以下のポリエステル樹脂とイソシアナ
ート化合物でウレタンブレボリマーを作り、硬化剤とし
てアミン化合物等を用いた、いわゆる発泡ウレタン樹脂
（特開昭４７−１９２７７）、
■グリコールとフタル酸類よりなるガラス転移温度Ｏ℃
〜６０℃のポリエステル樹脂（特開昭５０−１４３８８
０）、
■特定の伸び率、損失係数ピーク温度を有するポリエス
テル系樹脂（特開昭６１−２７７４３５〉、
■ポリエステル系樹脂とポリオレフィン系樹脂の混合物
（特開昭６１−８９８４２）、■組成の異なる２種類の
非品性ポリエステル樹脂を配合させた組戒物（特開昭６
２−２９５９４９）、
■分子量６００〜６０００でジカルボン酸成分の６０モ
ル％以上が芳香族ジカルポン酸成分とグリコールよりな
るポリエステルジオール（Ａ）と分子量６００〜６００
０の脂肪族ポリ，エステルジオール（Ｂ）とジイソシア
ナート化合物からなる組成物（特開昭６３−４８３２１
）、
■分子量６００〜６０００でジカルボン酸成分の６０モ
ル％以上が炭素数４〜２０よりなる脂肪族ジカルボン酸
からなるポリエステルジオール（Ａ）と分子量４００以
下の鎖延長剤（Ｂ）とジイソシアナート化合物からなる
組成物（特開昭６３−２０２６１３）、
■−４０℃〜１２０℃の間で損失正接
（ｔａｎδ）の極大値が０．５以上を示す非品性ポリエ
ステルと酸無水物およびエボキシ化合物からなる組成物
（特開昭６３−７５０５６）などがある．
しかし、■の発泡ウレタン樹脂は制振性が悪く、また接
着性能も十分でなく、
■の樹脂は常温における接着性能も十分でなく、また例
えば１００℃前後の耐熱性や耐久性にも欠け、いずれも
制振鋼板用樹脂としての十分な性能を有していない．
また、■、■およびＯは粘弾性を示す特定の温度域にお
いては、高い制振性を示すが、凝集力が不足するため、
実用上制振性を示す温度においてさえ、接着力が弱く、
勿論それ以上の温度においては十分な強度が得られず、
制振鋼板用樹脂としての十分な性能を有していない．ま
た、■の樹脂組成物は、上記の凝集力の不足が解決され
ることにより比較的高い接着強度と損失係数を示すが、
極大値を示す温度ピークが高く、したがって常温付近に
おける制振性に問題があり、常温付近、特に常温付近で
かつ低周波数域において、効果を発揮する制振材料用樹
脂としての十分な性能を有していない． さらに、２０
０℃程度の焼付塗装工程を経た後の接着力の低下が著し
い。In addition, as an example of investigating polyester resin as a resin for vibration-damping steel plates, there are the following: (1) A urethane foam polymer is made from a polyester resin with a molecular weight of 1800 or less and an isocyanate compound, and a so-called foamed urethane resin ( JP-A-47-19277), ■Glass transition temperature of glycol and phthalic acids O℃
~60℃ polyester resin (JP-A-50-14388
0), ■Polyester resin having a specific elongation rate and loss coefficient peak temperature (Japanese Patent Application Laid-Open No. 61-277435), ■Mixture of polyester resin and polyolefin resin (Japanese Patent Application Laid-open No. 61-89842), ■Different compositions Kumikaimono (Japanese Unexamined Patent Application Publication No. 1989-1999
2-295949), ■ Polyester diol (A) with a molecular weight of 600 to 6000 and 60 mol% or more of the dicarboxylic acid component consisting of an aromatic dicarboxylic acid component and glycol;
Composition consisting of 0 aliphatic poly, ester diol (B) and diisocyanate compound (Japanese Patent Application Laid-Open No. 63-48321
), ■ A polyester diol (A) consisting of an aliphatic dicarboxylic acid with a molecular weight of 600 to 6000 and at least 60 mol% of the dicarboxylic acid component having 4 to 20 carbon atoms, a chain extender (B) with a molecular weight of 400 or less, and a diisocyanate. A composition consisting of a compound (JP-A No. 63-202613), (1) A non-quality polyester, an acid anhydride, and an epoxy compound exhibiting a maximum value of loss tangent (tan δ) of 0.5 or more between -40°C and 120°C. (Japanese Patent Application Laid-Open No. 63-75056). However, the foamed urethane resin (①) has poor vibration damping properties and also has insufficient adhesive performance, and the resin (②) does not have sufficient adhesive performance at room temperature, and also lacks heat resistance and durability at temperatures around 100°C, for example. None of these resins have sufficient performance as a resin for damping steel plates. In addition, ■, ■, and O exhibit high vibration damping properties in a specific temperature range where they exhibit viscoelasticity, but because they lack cohesive force,
Even at temperatures where it exhibits practical vibration damping properties, the adhesive strength is weak.
Of course, sufficient strength cannot be obtained at temperatures higher than that,
It does not have sufficient performance as a resin for damping steel plates. In addition, the resin composition (2) exhibits relatively high adhesive strength and loss coefficient by solving the above-mentioned lack of cohesive force, but
The temperature peak showing the maximum value is high, so there is a problem with vibration damping properties near room temperature, but it has sufficient performance as a resin for vibration damping materials that is effective near room temperature, especially near room temperature and in the low frequency range. I haven't. In addition, 20
There is a significant decrease in adhesive strength after the baking process at around 0°C.
また、■の樹脂組成物は、常温付近で高い割振性を示す
が（Ａ）成分、（Ｂ）成分共に分子量が低く、さらに脂
肪族系で構成されるため、常温における接着性能が十分
でなく、また耐加水分解性に欠け、さらに例えば２００
℃前後の高温に曝した後の接着力の低下が著しく、制振
鋼板用樹脂として十分な性能を有しているとはいえない
．
■の樹脂組成物は、常温付近で高い接着強度と制振性を
示すことが示されているが、非晶質ポリエステル樹脂単
体あるいは、イソシアナート系架橋剤では、プレス加工
性に重要な影響を与える高い剪断接着強度を達成するこ
とが困難であるという記載があり、従ってポリエステル
とイソシアナート系からなる樹脂組成物は割振鋼板用樹
脂として満足すべき水準に達していない．
く発明が解決しようとする課題〉
本発明は上記問題点を解決し、常温付近、具体的には０
〜５０℃の範囲で高い制振性能を有し、かつ成形加工に
追随する優れた接着性能と、高い温度下、具体的には、
２００℃前後の高温に曝した後も高い耐熱安定性を有し
、積層加工性にも優れた複合型制振材料用樹脂組成物お
よびこれを用いた複合型制振材料ならびにスポット溶接
可能な複合型制振材料およびその製造方法を提供しよう
とするものである．く課題を解決するための手段〉
上記目的を達成するために、本発明者等は鋭意検討し、
特定の飽和共重合ポリエステルと重合ポリイソシアナー
ト化合物よりなる樹脂組成物を用い、さらに特定の導電
性物質を用いることにより、極めて優れた特性を有する
複合型制振材料が得られることを見出して、本発明に至
った。In addition, although the resin composition (■) exhibits high dissociation properties near room temperature, both components (A) and (B) have low molecular weights and are composed of aliphatic systems, so the adhesive performance at room temperature is insufficient. , also lacks hydrolysis resistance, and furthermore, for example 200
The adhesive strength decreased significantly after exposure to high temperatures around ℃, and it cannot be said that it has sufficient performance as a resin for vibration-damping steel plates. It has been shown that the resin composition (2) exhibits high adhesive strength and vibration damping properties at around room temperature. There is a statement that it is difficult to achieve the high shear adhesive strength given by polyester, and therefore resin compositions made of polyester and isocyanate do not reach a satisfactory level as resins for split steel plates. Problems to be Solved by the Invention> The present invention solves the above problems.
It has high vibration damping performance in the range of ~50℃, and has excellent adhesive performance that follows molding processing, and under high temperatures, specifically,
A resin composition for a composite vibration damping material that has high heat resistance stability even after being exposed to high temperatures of around 200°C and has excellent lamination workability, a composite vibration damping material using the same, and a composite that can be spot welded. This paper aims to provide a mold vibration damping material and its manufacturing method. Means for Solving the Problems> In order to achieve the above object, the inventors have diligently studied and
We have discovered that a composite vibration damping material with extremely excellent properties can be obtained by using a resin composition consisting of a specific saturated copolymerized polyester and a polymerized polyisocyanate compound, and further by using a specific conductive substance, This led to the present invention.
即ち、本発明の第１の態様によれば、重量平均分子量１
０，０００以上で軟化点が５０℃以上１５０℃以下の飽
和ポリエステルおよび架橋剤としての重合ポリイソシア
ナート化合物を含有することを特徴とする複合型制振材
料用樹脂組成物が提供される．
本発明の第２の態様によれば、重量平均分子量１０，０
００以上で軟化点が５０℃以上１５０℃以下の飽和ポリ
エステルおよび架橋剤としての重合ポリイソシアナート
化合物を含有し、さらに導電性物質を０．５〜ｌＱｖｏ
ｌ％含有することを特徴とする複合型制振材料用樹脂組
成物が提供される．
本発明の第３の態様によれば、重量平均分子量１０，０
００以上で軟化点が５０℃以上１５０℃以下の飽和ポリ
エステルおよび架橋剤としての重合ポリイソシアナート
化合物を含有する組或物を中間層として有することを特
徴とする複合型制振材料が提供される。That is, according to the first aspect of the present invention, the weight average molecular weight 1
Provided is a resin composition for a composite vibration damping material, which contains a saturated polyester having a softening point of 0,000 or higher and a softening point of 50 to 150 degrees Celsius, and a polymerized polyisocyanate compound as a crosslinking agent. According to a second aspect of the invention, weight average molecular weight 10,0
00 or more and a softening point of 50°C or more and 150°C or less, a polymerized polyisocyanate compound as a crosslinking agent, and a conductive substance of 0.5 to 1Qvo.
A resin composition for a composite vibration damping material is provided, which is characterized in that it contains 1%. According to a third aspect of the invention, weight average molecular weight 10,0
Provided is a composite vibration damping material characterized in that it has a composition as an intermediate layer containing a saturated polyester having a softening point of 50° C. or more and a softening point of 50° C. or more and 150° C. or less and a polymerized polyisocyanate compound as a crosslinking agent. .
本発明の第４の態様によれば、重量平均分子量１０，０
００以上で軟化点が５０℃以上１５０℃以下の飽和ポリ
エステルおよび架橋剤としての重合ポリイソシアナート
化合物を含有する組成物に対し、樹脂厚の０．５倍以上
の径を有する導電性物質を０．５〜ｌＱｖｏｌ％混合し
てなる中間層を有することを特徴とするスポット溶接可
能な複合型制振材料が提供される．
本発明の第５の態様によれば、重量平均分子量１０，０
００以上で軟化点が５０℃以上１５０℃以下の飽和ポリ
エステルと重合ポリイソシアナート化合物を混合して得
た混合物を金属板間に介在させることを特徴とする複合
型制振材料の製造方法が提供される．
本発明の第６の態様によれば、重量平均分子量１０，０
００以上で軟化点が５０℃以上１５０℃以下の飽和ポリ
エステルと重合ポリイソシアナート化合物と導電性物質
を０．５〜１０ｖｏｇ，％混合して得た混合物を金属板
間に介在させることを特徴とする複合型制振材料の製造
方法が提供される．
以下、本発明をさらに詳しく説明する。According to a fourth aspect of the invention, the weight average molecular weight is 10,0
For a composition containing a saturated polyester with a softening point of 50°C or more and 150°C or less and a polymerized polyisocyanate compound as a crosslinking agent, a conductive substance having a diameter of 0.5 times or more the resin thickness is added to the composition. A spot-weldable composite damping material is provided, which has an intermediate layer comprising a mixture of .5 to 1Qvol%. According to a fifth aspect of the invention, the weight average molecular weight is 10,0
Provided is a method for producing a composite vibration damping material, characterized in that a mixture obtained by mixing a saturated polyester with a softening point of 0.00° C. or higher and a softening point of 50° C. or higher and 150° C. or lower and a polymerized polyisocyanate compound is interposed between metal plates. It will be done. According to a sixth aspect of the invention, the weight average molecular weight is 10,0
A mixture obtained by mixing a saturated polyester having a softening point of 0.00° C. or more and a softening point of 50° C. or more and 150° C. or less, a polymerized polyisocyanate compound, and a conductive substance at 0.5 to 10 vog% is interposed between the metal plates. A method for manufacturing a composite vibration damping material is provided. The present invention will be explained in more detail below.
（Ａ）飽和共重合ポリエステル樹脂
本発明に用いる飽和共重合ポリエステル樹脂は、Ｒ＆Ｂ
軟化点（ＪＩＳ−Ｋ−２５３１）により測定した軟化点
が５０℃以上１５０℃以下のものであり、軟化点が５０
℃未満のものであると積層接着時の樹脂の流れ出しや樹
脂の粘着性に起因する加工時の汚れ、ベトツキによるト
ラブルを生じ、また軟化点が１５０℃を越えるものであ
ると積層加熱接着時に高温を必要とするばかりでなく、
接着性能そのものも低下する． 本発明にとり好ましい
ものは軟化点が８０℃以上１２０℃以下のものである。(A) Saturated copolymerized polyester resin The saturated copolymerized polyester resin used in the present invention is R&B
The softening point measured by softening point (JIS-K-2531) is 50°C or higher and 150°C or lower, and the softening point is 50°C or higher.
If the softening point is less than 150°C, problems may occur due to resin flowing out during lamination bonding, stains or stickiness during processing due to the adhesiveness of the resin, and if the softening point exceeds 150℃, high temperatures may occur during lamination heat bonding. Not only does it require
The adhesive performance itself also deteriorates. Preferred for the present invention are those having a softening point of 80°C or more and 120°C or less.
樹脂の分子量としては、液体ガスクロマトグラフィーに
よりボリスチレン換算で測定した重量平均分子量で１０
．０００以上のものであり、重量平均分子量が１０，０
００未満であると、制振性能が低下するばかりでなく、
接着性能も悪く、積層時の樹脂の流れ出しや、接着直後
の強度が著しく低いなどの問題を生じる．本発明にとり
好ましいものは重量平均分子量が２００００以上５００
００以下のものである．
飽和共重合ポリエステルは、ジメチルテレンタル酸、テ
レフタル酸、イソフタル酸、フタル酸などの芳香族二塩
基性酸、コハク酸、グルタル酸、アジビン酸、β−メチ
ルアジビン酸、ビメリン酸、１．６−ヘキサンジカルボ
ン酸、アゼライン酸、セバチン酸、ノナンジカルボン酸
、デカンジカルボン酸、ヘキサデカンジカルボン酸など
の脂肪族二塩基性酸とエチレングリコール、１，２−ブ
ロバンジオール、１．３−ブロバンジオール、１．３−
ブタンジオール、１．４−ブタンジオール、１．２−ペ
ンタジオール、１，５−ペンタジオール、３−メチルベ
ンタジオール、１．３−ヘキサンジオール、１．６−ヘ
キサンジオール、１．４−シクロヘキサンジ才−ル、水
添ビスフェノールＡ，ジエチレングリコール、トリエチ
レングリコール、ポリエチレングリコール、ジブロビレ
ングリコール、ボリブロビレングリコール、ポリテトラ
メチレングリコールなどのグリコールもしくはその残基
形成誘導体からなるポリエステルもしくはカブロラクト
ンよりなるものであるが、本発明の飽和共重合ポリエス
テルとして好ましいものは酸成分のうちテレフタル酸残
基が３０モル％以上９０モル％以下のものであり、テレ
フタル酸残基が３０モル％未満のもの．からなるポリエ
ステルは凝集力が不足し、接着強度が弱くなったり、積
層接着直後の強度が得ずらく、加工時のトラブルになる
場合がある。 また、９０モル％を越えるものは、同様
に接着性能が低下する恐れがあり好ましくはない． テ
レフタル酸残基を上記の範囲で用いた際に、併用される
二塩基性酸として前述の芳香族二塩基性酸または脂肪族
二塩基性酸が挙げられるが、好ましいものとしては、一
種以上の脂肪族二塩基性酸、特にアジビン酸、セバチン
酸のいずれかを挙げられる． グリコール成分としては
、エチレングリコール残基が３０モル％以上８０モル％
以下のものが好ましく、エチレングリコール残基が３０
モル％未満であると、接着性能が低下し、８０モル％を
越えると、同様に接着性能が低下するばかりか、良好な
制振性能が得られない恐れがあり、さらに好ましいもの
としては４０モル％以上７０モル％以下のものである。The molecular weight of the resin is 10 as the weight average molecular weight measured in terms of boristyrene by liquid gas chromatography.
．． 000 or more, and the weight average molecular weight is 10.0
If it is less than 00, not only will the damping performance deteriorate,
Adhesive performance is also poor, leading to problems such as resin flowing out during lamination and extremely low strength immediately after adhesion. Preferably for the present invention, the weight average molecular weight is 20,000 or more and 500
00 or less. Saturated copolymerized polyesters include aromatic dibasic acids such as dimethylterentalic acid, terephthalic acid, isophthalic acid, and phthalic acid, succinic acid, glutaric acid, adivic acid, β-methyladibic acid, bimelic acid, and 1,6-hexane. Aliphatic dibasic acids such as dicarboxylic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, hexadecanedicarboxylic acid and ethylene glycol, 1,2-brobanediol, 1.3-brobanediol, 1.3-
Butanediol, 1,4-butanediol, 1,2-pentadiol, 1,5-pentadiol, 3-methylbentadiol, 1,3-hexanediol, 1.6-hexanediol, 1,4-cyclohexanediol Polyesters made of glycols or their residue-forming derivatives, such as triethylene glycol, hydrogenated bisphenol A, diethylene glycol, triethylene glycol, polyethylene glycol, dibrobylene glycol, polybrobylene glycol, and polytetramethylene glycol, or cabrolactone. However, preferred saturated copolymerized polyesters of the present invention include those containing 30 mol% or more and 90 mol% or less of terephthalic acid residues among the acid components, and those containing less than 30 mol% of terephthalic acid residues. Polyesters made of polyesters lack cohesive strength, resulting in weak adhesive strength or difficulty in achieving sufficient strength immediately after lamination and adhesion, which may cause problems during processing. Moreover, if the content exceeds 90 mol%, the adhesive performance may similarly deteriorate, so it is not preferable. When the terephthalic acid residue is used within the above range, the dibasic acids used in combination include the above-mentioned aromatic dibasic acids or aliphatic dibasic acids, but preferably one or more Examples include aliphatic dibasic acids, particularly adibic acid and sebacic acid. As a glycol component, ethylene glycol residue is 30 mol% or more and 80 mol%
The following are preferred, and the ethylene glycol residue is 30
If it is less than mol %, the adhesive performance will deteriorate, and if it exceeds 80 mol %, the adhesive performance will similarly deteriorate, and there is a possibility that good vibration damping performance will not be obtained. More preferably, 40 mol % is used. % or more and 70 mol% or less.
エチレングリコール残基を上記の範囲で用いた際に、併
用されるグリコール成分としては前述のグリコールが挙
げられるが、より好ましいものとしては、炭素数６のヘ
キサンジオール系グリコールまたはポリエチレングリコ
ール、ポリテトラメチレングリコールなどのポリオキシ
アルキレングリコールを挙げることができる．本発明の
飽和共重合ポリエステルとして、たとえば、マレイン酸
、フマル酸、ダイマー酸などの不飽和脂肪酸、トリメリ
ット酸などの二官能性を越える脂肪酸、トリメチロール
ブロバン、ペンタエリスリトールなどの二官能性を越え
る水酸基を有する化合物を共重合したものも使用可能で
あるが゛、これらのモノマーは接着性能を低下したり、
接着耐久性を損なったり、制振性能そのものを低下せし
める恐れがあるため、本発明の特徴を損なわない範囲で
の使用が好ましい．
本発明の飽和共重合ポリエステルとして、粘弾性スペク
トロメーターにより測定したガラス転移温度が２０℃以
下のものが好ましく、ガラス転移温度が２０℃を越える
ものは、常温付近での制振性能が低いばかりでなく、接
着性能も低下する恐れがある。 さらに好ましくはガラ
ス転移温度が０℃以下のものである。When the ethylene glycol residue is used within the above range, the glycol components used in combination include the aforementioned glycols, but more preferred are hexanediol-based glycols having 6 carbon atoms, polyethylene glycol, and polytetramethylene. Examples include polyoxyalkylene glycols such as glycols. Examples of the saturated copolymerized polyester of the present invention include unsaturated fatty acids such as maleic acid, fumaric acid, and dimer acid, fatty acids exceeding bifunctionality such as trimellitic acid, and fatty acids exceeding bifunctionality such as trimethylolbroban and pentaerythritol. Copolymerized compounds with hydroxyl groups can also be used, but these monomers may reduce adhesive performance or
Since there is a risk of impairing adhesive durability or reducing vibration damping performance itself, it is preferable to use it within a range that does not impair the characteristics of the present invention. The saturated copolymerized polyester of the present invention preferably has a glass transition temperature of 20°C or less as measured by a viscoelastic spectrometer, and those whose glass transition temperature exceeds 20°C have poor vibration damping performance near room temperature. Therefore, there is a risk that the adhesive performance will also deteriorate. More preferably, the glass transition temperature is 0°C or lower.
また制振鋼板の積層加工性を考慮すると、本発明の飽和
共重合ポリエステルとしてはトルエン、ＭＥＫ．酢酸エ
チルなどの汎用溶剤に可溶であるものが好ましく、溶剤
に溶解することによ゜り、鋼板への塗工が容易になり、
積層部へのガスの巻き込みがなく、加工時スポット溶接
性付与のために必要な導電性粉末やフィラー、添加剤の
混合が容易になるなどの利点が生じる。In addition, considering the lamination processability of vibration damping steel plates, toluene, MEK. Preferably, it is soluble in a general-purpose solvent such as ethyl acetate, and by dissolving it in the solvent, it becomes easier to coat the steel plate.
Advantages include that there is no gas entrainment in the laminated parts, and that it is easier to mix conductive powder, fillers, and additives necessary for imparting spot weldability during processing.
（Ｂ）飽和共重合ポリエステルの合成方法本発明で用い
る飽和共重合ポリエステルは常法により合成することが
でき、一般には前述の二塩基性酸とグリコールとのエス
テル化反応、およびそれに引き続く高温減圧下で過剰の
グリコールを留去しながらのエステル交換反応により合
成するか、またはあらかじめ合成されたポリエチレンテ
レフタレート、・ポリブチレンテレフタレート等を所望
の二塩基性酸及び過剰のグリコールの存在下、解重合し
同様にエステル交換反応により合成することができる。(B) Synthesis method of saturated copolymerized polyester The saturated copolymerized polyester used in the present invention can be synthesized by a conventional method, and generally involves the esterification reaction of the dibasic acid and glycol described above, followed by the subsequent high temperature and reduced pressure. or by depolymerizing previously synthesized polyethylene terephthalate, polybutylene terephthalate, etc. in the presence of the desired dibasic acid and excess glycol. can be synthesized by transesterification reaction.
例 えば、１５０℃〜２２０℃に加熱しながら、常圧
下に二塩基性酸とグリコールを主原料とし、主として金
属塩よりなる触媒の存在下でエステル化反応によりオリ
ゴエステル化を行い、引き続き、常圧または減圧下２０
０℃〜２７０℃に加熱して過剰のグリコールな留去する
ことにより、高分子量化した飽和共重合ポリエステルが
合成される． この時、グリコールは所望するポリエス
テル組成における量の１．５倍〜２倍添加し、合戒する
ことが好ましく、この時生成するポリエステルの組成は
’Ｈ−ＮＭＲにより、七ノマー残基のモル比を測定す
ることにより調整される。 また、重合触媒はテトラー
ｎ−ブトキシチタン、酢酸亜鉛、三酸化アンチモン、蓚
酸チタン酸カリなどの金属塩よりなる通常の触媒から適
宜選択される．
（Ｃ）重合ポリイソシアナート
本発明で用いる重合ポリイソシアナートとしては、分子
内に少なくとも２個以上のイソシアナート基を有する化
合物、具体的にはあらかじめ反応せしめた重合ポリイソ
シアナート、例えば市販品として、スブラセツク３２４
０、３ ２ ５ ０，コロネー｝２０３０．２０３１、
ディスモジュールＩＬ，ＨＬ（住友バイエルウレタン）
などを挙げることができる。 これら以外の例えば、２
．４−トリレンジイソシアナート、２．６−｝リレンジ
イソシアナート（通称ＴＤＩ），メチレンービス−４−
フエニルイソシアナート（通称ＭＤＩ）およびこれらの
誘導体、さらにＴＤＩをトリメチロールプロパンなどに
付加したＴＩ）Ｉ系アダクトボリイソシアナート、例え
ば市販品としてコロネートし、コロネートＨＬ（以上、
日本ポリウレタン）、ディスモフェンＬ、ディスモジュ
ールＮ（住友バイエルウレタン）などを用いると、２０
０℃前後の高温に曝した後の熱安定性が十分でないため
好ましくない．
飽和共重合ポリエステルに対する重合ポリイソシアナー
トの添加量は、重量平均分子量より計算した飽和共重合
ポリエステル中の水酸基１当量に対し０．５当量以上２
０当量以下であることが好ましく、０．５当量未満であ
ると、接着性能が不足し、積層後の耐熱性が不足し、制
振性能が低下する恐れがある。 又、２０当量を超える
と、積層後の耐久性が低下したり、割振性能自体も満足
できないものとなる恐れがある。 さらに好ましくは２
当量以上１０当量以下、特には３当量以上８当量以下と
いう過剰の重合ポリイソシアナートの添加が好ましい。For example, oligoesterification is performed by an esterification reaction using dibasic acid and glycol as main raw materials under normal pressure while heating at 150°C to 220°C in the presence of a catalyst mainly consisting of a metal salt. under pressure or vacuum 20
By heating to 0°C to 270°C and distilling off excess glycol, a saturated copolymerized polyester with a high molecular weight is synthesized. At this time, it is preferable to add glycol 1.5 to 2 times the amount in the desired polyester composition and adjust the amount.The composition of the polyester produced at this time is determined by 'H-NMR, and the molar ratio of heptanomer residues is Adjusted by measuring. Further, the polymerization catalyst is appropriately selected from ordinary catalysts consisting of metal salts such as tetra-n-butoxytitanium, zinc acetate, antimony trioxide, and potassium oxalate titanate. (C) Polymerized polyisocyanate The polymerized polyisocyanate used in the present invention is a compound having at least two or more isocyanate groups in the molecule, specifically a polymerized polyisocyanate that has been reacted in advance, such as a commercially available product. , Suburasek 324
0, 3 2 5 0, Coronae}2030.2031,
Dismodule IL, HL (Sumitomo Bayer Urethane)
etc. can be mentioned. Other than these, for example, 2
．． 4-tolylene diisocyanate, 2.6-}lylene diisocyanate (commonly known as TDI), methylene bis-4-
Phenyl isocyanate (commonly known as MDI) and derivatives thereof, as well as TI) I-based adduct polyisocyanate in which TDI is added to trimethylolpropane etc., such as Coronate as a commercial product, Coronate HL (as above,
When using Nippon Polyurethane), Dismofen L, Dismodur N (Sumitomo Bayer Urethane), etc., 20
It is not desirable because it does not have sufficient thermal stability after being exposed to high temperatures around 0°C. The amount of polymerized polyisocyanate added to the saturated copolymerized polyester is 0.5 equivalent or more per 1 equivalent of hydroxyl group in the saturated copolymerized polyester calculated from the weight average molecular weight.
It is preferable that the amount is 0 equivalent or less, and if it is less than 0.5 equivalent, adhesive performance may be insufficient, heat resistance after lamination may be insufficient, and vibration damping performance may be deteriorated. Moreover, if the amount exceeds 20 equivalents, the durability after lamination may decrease, and the allocation performance itself may become unsatisfactory. More preferably 2
It is preferable to add an excess of polymerized polyisocyanate in an amount of at least 3 equivalents and at most 10 equivalents, particularly at least 3 equivalents and at most 8 equivalents.
この時、重合ポリイソシアナートの一部が前述のポリエ
ステルとあらかじめ反応させておいたものも、本発明が
奏する効果をあげることができる。At this time, the effects of the present invention can also be obtained by reacting a part of the polymerized polyisocyanate with the above-mentioned polyester in advance.
（Ｄ）その他の添加剤
本発明の樹脂組成物には種々の添加剤を併用することも
でき、併用できる添加剤の例とじて・は、本発明樹脂を
構成する飽和共重合ポリエステル以外のポリエステル、
末端水酸基を有するアクリル樹脂、ビスフェノール系エ
ボキシ樹脂、タレゾールノボラック系エボキシ樹脂など
のエボキシ樹脂、スチレン、αメチルスチレンなどのス
チレン系樹脂、テルペン樹脂、テルペンフェノール樹脂
、ロジン系樹脂、炭化水素系樹脂、芳香族系樹脂，フェ
ノール樹脂等の粘着性付与樹脂、ポリアルキレングリコ
ールポリエステル系可塑剤、メラミン樹脂、オルガノフ
ァンクショナルシラン（通称シランカップリング剤）
過酸化物などの架橋剤、金属塩例えばｎ−プチルスズジ
ラウレート、アミン、グリコールなどのイソシアナート
硬化触媒、鎖延長剤などを挙げることができ、又、フィ
ラーとして、炭酸カルシウム、タルク、ハードシールな
どの無機フィラーの添加も本発明の特徴をそこなわない
範囲で添加することは可能である。(D) Other additives Various additives can be used in combination with the resin composition of the present invention. Examples of additives that can be used in combination include polyesters other than the saturated copolymerized polyester constituting the resin of the present invention. ,
Acrylic resins with terminal hydroxyl groups, bisphenol-based epoxy resins, epoxy resins such as Talezol novolac-based epoxy resins, styrene-based resins such as styrene and α-methylstyrene, terpene resins, terpene-phenol resins, rosin-based resins, hydrocarbon-based resins, Aromatic resins, tackifying resins such as phenolic resins, polyalkylene glycol polyester plasticizers, melamine resins, organofunctional silanes (commonly known as silane coupling agents)
Examples include crosslinking agents such as peroxides, metal salts such as n-butyltin dilaurate, isocyanate curing catalysts such as amines and glycols, chain extenders, and fillers such as calcium carbonate, talc, hard seals, etc. It is also possible to add inorganic fillers as long as they do not impair the characteristics of the present invention.
また、上記組′成物に充填材として導電性固体物質を配
合することにより導電性を付与し、得られる制振材料を
スポット溶接可能な材料とすることもできる。 このよ
うな目的で使用される導電性物質としては、ステンレス
、亜鉛、銅、スズ、黄銅、ニッケル等の金属を粉末状、
フレーク状、ファイバー状、ワイヤー状等に加工した金
属物質や銅、あるいはニッケル等のメッキ処理した鉄系
金属や、カーボンブラック、グラファイト、カーボンフ
ァイバー等の導電性炭素物質等を挙げることができる。Furthermore, conductivity can be imparted to the composition by blending a conductive solid substance as a filler, and the resulting damping material can be made into a material that can be spot welded. Conductive materials used for this purpose include powdered metals such as stainless steel, zinc, copper, tin, brass, and nickel.
Examples include metal substances processed into flakes, fibers, wires, etc., iron-based metals plated with copper or nickel, and conductive carbon substances such as carbon black, graphite, and carbon fiber.
これらの導電性物質は単独で使用できるほか、２種以
上を組合せて使用することもできる。 これらの導電性
物質としては、良好な導電性を発現させるために金属物
質が好ましい。 金属物質が粉末状である場合にはその
最大粒径を、また、フレーク状である場合には、その最
大厚みを、さらにファイバー状やワイヤー状である場合
は、その最大直径をそれぞれの代表長さ（Ｌ）とすると
、より良好な導電性を発現させるため、（Ｌ）と樹脂中
間層の厚さ（Ｔ）との比（Ｌ）／ （Ｔ）を０．５以上
が好ましく、さらに好ましくは０．８以上にするのがよ
い。These conductive substances can be used alone or in combination of two or more. As these conductive substances, metal substances are preferable in order to exhibit good conductivity. If the metal substance is in the form of a powder, its maximum particle size, if it is in the form of flakes, its maximum thickness, and if it is in the form of fibers or wires, its maximum diameter is determined by its representative length. (L), the ratio (L)/(T) of (L) to the thickness (T) of the resin intermediate layer is preferably 0.5 or more, more preferably, in order to develop better conductivity. is preferably 0.8 or more.
（Ｌ）／ （Ｔ）の比が０．５未満ではスポット溶接性
能が低下する。 さらに導電性物質の充填量は０．５〜
ｌＯｖｏＩｌ％が好ましく、０．５ｖｏｌ％未満ではス
ポット溶接性能が低く、又１０ｖｏｌ％を越えるとスポ
ット溶接性は十分満足されるが、接着性能や制振性能が
低下し好ましくなく、さらに好ましいものとして１〜５
ｖｏｌ％である。When the ratio of (L)/(T) is less than 0.5, spot welding performance deteriorates. Furthermore, the filling amount of the conductive substance is 0.5~
1OvoIl% is preferable; if it is less than 0.5vol%, spot welding performance is low; if it exceeds 10vol%, spot weldability is sufficiently satisfied, but adhesive performance and vibration damping performance deteriorate, which is not preferable; ~5
It is vol%.
（Ｅ）制振材料への適用方法
制振材料製造のため本発明の樹脂組或物が適用される金
属板としては、冷間圧延鋼板、クロメート処理鋼板、亜
鉛処理鋼板、リン酸塩処理鋼板などの表面処理鋼板、銅
板、アルミ板、ステンレス板などのいずれであっても良
く、又、コイル状原板、切り板のいずれであっても良い
。 又、その板厚としては、成形加工性と保形性を考慮
すれば０．３ｍｍ以上２ｍｍ以下のものが好ましい。
前述の飽和共重合ポリエステルと重合ポリイソシアナー
トよりなる樹脂組成物は、飽和共重合ポリエステルと重
合ポリイソシアナートが別々に保管され、制振材料製造
の際に両者が混合されて使用される、いわゆる主剤と硬
化剤からなる二液型接着剤のように使用されるのが一般
的である。(E) Method of application to vibration damping materials Metal plates to which the resin assembly of the present invention is applied for producing vibration damping materials include cold rolled steel plates, chromate treated steel plates, zinc treated steel plates, and phosphate treated steel plates. It may be a surface-treated steel plate, a copper plate, an aluminum plate, a stainless steel plate, etc., or it may be a coiled original plate or a cut plate. Further, the thickness of the plate is preferably 0.3 mm or more and 2 mm or less in consideration of moldability and shape retention.
The above-mentioned resin composition consisting of a saturated copolymerized polyester and a polymerized polyisocyanate is a so-called resin composition in which the saturated copolymerized polyester and the polymerized polyisocyanate are stored separately and used as a mixture when producing vibration damping materials. It is generally used as a two-component adhesive consisting of a base agent and a curing agent.
より具体的には、例えば加熱溶融混合による押出フィル
ム、又は溶剤中で混合し離型シ一ト上にコーティングし
た後、溶剤を留去した、いわゆるキャスティングフィル
ムとして用い、二枚の鋼板の間に積層し、加熱ロール、
熱プレス接着もしくは引き続き冷却ロール又は冷却プレ
スにより積層接着することも可能であるが、好ましくは
、溶剤中で所定の飽和共重合ポリエステル、イソシアナ
ート及び添加剤を混合後、直接鋼板の少なくとも一方、
好ましくは両者の積層面に塗布し、室温ないし好ましく
は１００℃以上１５０℃以下の温度で加熱して溶剤を留
去した後、引き続きもしくは放置後、加熱積層接着され
る。 この時、樹脂の膜厚は鋼板の１／５０以上１７５
以下であることが好ましく、実質的に２０ａｍ以上１５
０μｍ以下であることが好ましい， ２０μｍ未満で
あると制振性及び接着性能が低下し、１５０μｍを超え
ると成形加工時、鋼板のズレやワレの原因となる場合が
ある．
積層接着温度は通常樹脂層に１３０℃以上２５０℃以下
の加熱が与えられるようにすれば良く、加熱プレスの場
合１０秒〜２分程度、加熱ロールの場合には０．５〜１
０秒程度の接触時間であれば良く、又金属板をあらかじ
め同温度に加熱し、冷却プレス又は冷却ロールにより積
層接着しても良い。このように本発明の樹脂は熱可塑性
樹脂と同等の加工条件により、接着温度以上の耐熱性が
得られ、積層接着後直ちに所定の接着性能が得られると
いう特徴を有し、さらに鋼板への塗工品のポットライフ
が実用上問題のない長さであるという特徴も有する。More specifically, for example, it is used as an extruded film by heating and melting mixing, or a so-called casting film in which the solvent is distilled off after being mixed in a solvent and coated on a release sheet. Laminated and heated rolls,
It is also possible to perform lamination adhesion by hot press adhesion or subsequent cooling roll or cooling press, but preferably, after mixing the predetermined saturated copolymer polyester, isocyanate, and additives in a solvent, at least one of the steel plates,
It is preferably applied to both laminated surfaces, heated at room temperature or preferably at a temperature of 100° C. or more and 150° C. or less to distill off the solvent, and subsequently or after being allowed to stand, heat lamination bonding is performed. At this time, the resin film thickness is 1/50 or more than the steel plate, 175
It is preferably less than or equal to 20 am or more, and substantially more than 15 am.
It is preferable that the thickness is 0 μm or less; if it is less than 20 μm, vibration damping properties and adhesive performance will deteriorate, and if it exceeds 150 μm, it may cause displacement or cracking of the steel plate during forming processing. The lamination adhesion temperature should normally be such that the resin layer is heated at 130°C or more and 250°C or less, about 10 seconds to 2 minutes in the case of a hot press, and 0.5 to 1 minute in the case of a heated roll.
The contact time may be about 0 seconds, or the metal plates may be heated to the same temperature in advance and laminated and bonded using a cooling press or a cooling roll. As described above, the resin of the present invention has the characteristics that it can obtain heat resistance higher than the bonding temperature under the same processing conditions as thermoplastic resins, and can obtain the desired adhesive performance immediately after lamination bonding. Another feature is that the pot life of the manufactured product is long enough to cause no practical problems.
又、積層加工時、樹脂を溶液状で塗工することができる
と、鋼板と樹脂との密着性を高めることができ、ガス層
の巻き込みを防止することができるばかりか、成形鋼板
のスポット溶接性を付与する目的で添加される導電性金
属粉、カーボンなどの添加を容易にするため、本発明に
とり最も好ましい方法であり、本発明の飽和共重合ポリ
エステルによれば容易に達或しうる方法である．
樹脂液の塗工方法は特に限定されないが、ロールコータ
ー スブレー カーテンフローコーター ドクターナイ
フコーターなどが好ましい。In addition, if resin can be applied in solution during lamination processing, it is possible to improve the adhesion between the steel plate and the resin, prevent gas layer entrainment, and improve spot welding of formed steel plates. This is the most preferred method for the present invention because it facilitates the addition of conductive metal powder, carbon, etc. that are added for the purpose of imparting properties, and the method can be easily achieved with the saturated copolymerized polyester of the present invention. It is. The method for applying the resin liquid is not particularly limited, but preferred are a roll coater, spray coater, curtain flow coater, doctor knife coater, and the like.
〈作用〉
従来、飽和共重合ポリエステルは、そのシャープな溶融
挙動から、樹脂そのものの粘弾性を示す温度域が狭く、
かつ粘弾性を示す温度域においては凝集力が不足するた
め、実用上割振性を示す温度においてさえ、接着強度が
弱く、勿論それ以上の温度においては十分な強度が得ら
れず、制振材料用樹脂としては使用できなかったが、本
発明者等によって、特定の飽和共重合ポリエステルと重
合ポリイソシアナート化合物の組み合わせが見出された
ことにより、制振材料として、前述の常温付近における
割振性能すなわち損失係数の値が大きく、かつ温度巾が
広く、成形加工時必要な接着性能にも優れ、さらには成
形後の高温下での接着安定性や耐薬品性、耐久性に極め
て高い性能を有するものを提供できるようになり、又、
本発明の樹脂は、二枚の金属板と積層加工される場合に
おいても、低分子量の通常液状のポリエステルやポリエ
ーテルとイソシアナート化合物よりなる二液ポリウレタ
ンや硬化型のエボキシ樹脂などの反応型の樹脂のように
、長い加熱時間を必要とせず、積層接着時の樹脂の流れ
出しなどの問題がなく、又ポリウレタン樹脂や変性ポリ
オレフィン樹脂などの樹脂そのものの熱可塑性を利用し
て接着する場合のように、使用時さらされる温度以上の
融点を必須とするため不可欠な高い積層温度と積層圧力
等を必要とせず、実用温度以下の積層温度においてさえ
も、尚高い接着強度が得られ、極めて優れた加工性を有
するなど優れた作用効果を奏するものである．さらに，
本発明の樹脂組成物に特定の導電性物質を充填させるこ
とにより、上記の特性以外に高いスポット溶接性能を付
与した制振材料が提供できるように”なった。<Function> Conventionally, saturated copolymerized polyester has a narrow temperature range in which the resin itself exhibits viscoelasticity due to its sharp melting behavior.
In addition, cohesive force is insufficient in the temperature range where viscoelasticity is exhibited, so even at temperatures where vibration damping properties are exhibited in practice, adhesive strength is weak, and of course sufficient strength cannot be obtained at higher temperatures, making it difficult to use for vibration damping materials. Although it could not be used as a resin, the present inventors discovered a combination of a specific saturated copolymerized polyester and a polymerized polyisocyanate compound, and as a result, it can be used as a vibration damping material to improve the above-mentioned vibration distribution performance near room temperature, i.e. It has a large loss coefficient value, a wide temperature range, excellent adhesive performance required during molding, and also has extremely high performance in adhesive stability, chemical resistance, and durability at high temperatures after molding. We are now able to provide
Even when the resin of the present invention is laminated with two metal plates, it is possible to use a reactive type resin such as a two-component polyurethane made of a low molecular weight normally liquid polyester or a polyether and an isocyanate compound, or a hardening type epoxy resin. Unlike resins, it does not require long heating times and there are no problems such as resin flowing out during lamination bonding, and unlike when bonding uses the thermoplasticity of the resin itself such as polyurethane resin or modified polyolefin resin. , it does not require high lamination temperatures and lamination pressures, which are essential because the melting point is higher than the temperature exposed during use, and even at lamination temperatures below practical temperatures, high adhesive strength can be obtained, resulting in extremely excellent processing. It has excellent functions and effects, such as its properties. moreover,
By filling the resin composition of the present invention with a specific conductive substance, it has become possible to provide a vibration damping material that has high spot welding performance in addition to the above characteristics.
く実施例〉 以下に本発明を実施例に基づいて具体的に説明する。Example The present invention will be specifically described below based on Examples.
実施例で用いたポリエステルの特性の測定方法、積層接
着方法、制振鋼板の特性の測定方法等は以下のとおりで
ある。The methods for measuring the properties of polyester, lamination adhesion method, and properties of the damping steel plate used in the examples are as follows.
■ポリエステルの軟化点
ＪＩＳＫ−２５３１に準じＲ＆Ｂ軟化点により測定し、
その温度を℃で表示した。■Softening point of polyester Measured by R&B softening point according to JISK-2531,
The temperature was expressed in °C.
■ポリエステルの重量平均分子量
ポリエステル樹脂をテトラハイドロフランに溶解し、液
体クロマトグラフィーにより測定し、ボリスチレン換算
により重量平均分子量を算出した。(2) Weight average molecular weight of polyester The polyester resin was dissolved in tetrahydrofuran, measured by liquid chromatography, and the weight average molecular weight was calculated in terms of boristyrene.
■ポリエステルのガラス転移温度
ポリエステルを１ｍｍ厚のシートとし、粘弾性スペクト
ロメーター（１０Ｈｚ）により動的弾性率（Ｅ′）を測
定し、弾性率が低下しはじめる温度を表示した。(2) Glass transition temperature of polyester Polyester was made into a 1 mm thick sheet, and its dynamic elastic modulus (E') was measured using a viscoelasticity spectrometer (10 Hz), and the temperature at which the elastic modulus began to decrease was indicated.
■重合ポリイソシアナートの添加量及び当量
ポリエステル１００重量部に対する重合ポリイソシアナ
ート添加量及びポリエステルの重量平均分子量より測定
した末端水酸基に基づいて重合ポリイソシアナート基の
当量部数を算出した。(2) Addition amount and equivalent of polymerized polyisocyanate The equivalent number of polymerized polyisocyanate groups was calculated based on the amount of polymerized polyisocyanate added to 100 parts by weight of polyester and the terminal hydroxyl group measured from the weight average molecular weight of the polyester.
■使用鋼板
０．６ｍｍ厚みの冷間圧延鋼板（ＳＰＣＣ−ＳＤ）を脱
脂して使用した。(2) Steel plate used A cold rolled steel plate (SPCC-SD) with a thickness of 0.6 mm was degreased and used.
■積層接着方法
あらかじめポリエステルをトルエン・ＭＥＫ混合溶剤中
に溶解し、固形分３０％の溶液とし、重合ポリイソシア
ナートを混合し、ロールコーターを用い、鋼板の片面に
樹脂膜厚２５μｍになるように塗布し，塗布後オーブン
（１００℃×１分）で溶剤を留去した． この後樹脂の
塗布面同士を重ね、熱プレス（２００”ＣＸＩ分×圧力
５ ｋｇ／ｃｍ”）で加熱接着し評価を行った。■ Lamination adhesion method: Dissolve polyester in a toluene/MEK mixed solvent in advance to make a solution with a solid content of 30%, mix with polymerized polyisocyanate, and use a roll coater to coat one side of a steel plate with a resin film thickness of 25 μm. After coating, the solvent was distilled off in an oven (100°C x 1 minute). Thereafter, the resin-coated surfaces were overlapped and bonded by heating using a heat press (200"CXI min x pressure 5 kg/cm") for evaluation.
■接着性能
上記で積層接着した鋼板を２５ｍｍ巾に裁断し、Ｔ一剥
離強度を測定した。 引張速度は２００ｍｍ／分で測定
した。 同様に接着部分を２５ｍｍＸ２５ｍｍの面積に
裁断し引張剪断強度を引張速度１０ｍｍ／分、室温２３
℃で測定した．
■戊形性能
同様に上記で積層接着したものを２ ５ｍｍ巾Ｘ１００
ｍｍ長に裁断し、４ｍｍφに折り曲げ加工し、曲げ部に
うきのあるものを×、変化のないものを○で表示した。(2) Adhesion performance The steel plates laminated and bonded above were cut into 25 mm width pieces, and the T-peel strength was measured. The tensile speed was measured at 200 mm/min. Similarly, the adhesive part was cut into an area of 25 mm x 25 mm, and the tensile shear strength was measured at a tensile speed of 10 mm/min and at room temperature of 23 mm.
Measured at °C. ■Shaping performance: 25mm wide x 100 pieces laminated and bonded as above.
It was cut into lengths of mm and bent into 4 mm diameter. Those with ridges at the bent portions were marked with an x, and those with no change were marked with an ○.
沸水中に２４時間浸漬したものまたは１５０℃のオー
ブン中に２４時間置いたものを取り出し、うきが生じた
ものを×、変化のないものを○で表示した。Those that had been immersed in boiling water for 24 hours or those that had been placed in an oven at 150°C for 24 hours were taken out, and those with swelling were marked with an x, and those with no change were marked with an ○.
■制振性能
制振性能の評価として、積層接着品の損失係数（η）を
機械インピーダンス法により測定し、１０００Ｈｚにお
ける損失係数の温度依存性を表示した．
［相］熱安定性
熱安定性の評価として、積層接着品を２５ｍｍ巾に裁断
したもの、および２５ｍｍＸ２５ｍｍの面積に裁断した
ものをそれぞれ１８０℃、２００℃、２２０℃の熱風循
環式オーブン中１ｖｆ間放置したものを取り出し，■と
同様の方法で接着強度を測定した。■Vibration damping performance As an evaluation of vibration damping performance, the loss coefficient (η) of the laminated adhesive product was measured using the mechanical impedance method, and the temperature dependence of the loss coefficient at 1000 Hz was displayed. [Phase] Thermal stability To evaluate thermal stability, the laminated adhesive product was cut to a width of 25 mm and cut to an area of 25 mm x 25 mm, respectively, for 1 Vf in a hot air circulation oven at 180°C, 200°C, and 220°C The left sample was taken out and the adhesive strength was measured in the same manner as in ■.
■スポット溶接性
加圧力２００ｋｇｆ、電流８ＫＡ、通電８サイクル、チ
ップ８Ｒ球形状でダイレクトスポット溶接を行ない、溶
接できたものを良好とし、未通電のものを不良とした（
表３）。■Spot welding Direct spot welding was performed with a pressure of 200 kgf, a current of 8 KA, 8 cycles of energization, and an 8R spherical tip.Those that could be welded were considered good, and those that were not energized were judged as defective.
Table 3).
（実施例１）
テレフタル酸残基８０モル、アジビン酸残基２０モル、
エチレングリコール残基４５モル、１．６−ヘキサンジ
オール残基５５モルの当量比よりなり、重量平均分子量
が２３０００、軟化点が１２０℃、ガラス転移点が−１
０℃のポリエステルを常法により合成した。 このポリ
エステルをトルエン％ＭＥＫ重量比１／１の溶剤に固形
分３０％になるように溶解し、重合ポリイソシアナート
としてコロネート２０３０（ＮＶ ： ５０％、ＮＣＯ
％：７．９、日本ポリウレタン■製）をポリエステル１
００重量部に対し８重量部添加混合し、鋼板に塗布乾燥
後、二枚の鋼板を重ね、熱プレスにより積層接着した．
この時イソシアナート当量はポリエステルの末端水酸
基１当量に対し、１．７当量部数であった。 この積層
した鋼板の接着性能、成形性、周波数１０００Ｈｚでの
損失係数を測定した結果を表１及び第１図に、又、熱安
定性の結果を表２に示す。 制振鋼板としていずれも優
れた性能のものが得られた。 同様にして、所定のポリ
エステルと重合ポリイソシアナートよりなる発明例２〜
６の結果を表１、２に、・発明例４、５の損失係数の値
を第１図に示す。(Example 1) 80 mol of terephthalic acid residue, 20 mol of adivic acid residue,
Consisting of an equivalent ratio of 45 moles of ethylene glycol residue and 55 moles of 1.6-hexanediol residue, weight average molecular weight is 23,000, softening point is 120°C, and glass transition point is -1.
Polyester at 0°C was synthesized by a conventional method. This polyester was dissolved in a solvent with a weight ratio of toluene% MEK 1/1 to a solid content of 30%, and Coronate 2030 (NV: 50%, NCO
%: 7.9, made by Japan Polyurethane) to polyester 1
8 parts by weight to 00 parts by weight were added and mixed, coated on a steel plate and dried, then two steel plates were stacked and laminated and bonded by hot pressing.
At this time, the isocyanate equivalent was 1.7 parts per equivalent of the terminal hydroxyl group of the polyester. The results of measuring the adhesion performance, formability, and loss coefficient at a frequency of 1000 Hz of this laminated steel plate are shown in Table 1 and FIG. 1, and the results of thermal stability are shown in Table 2. All of the vibration damping steel plates had excellent performance. Similarly, invention examples 2-
The results of Example 6 are shown in Tables 1 and 2, and the loss coefficient values of Invention Examples 4 and 5 are shown in FIG.
この時ポリエチレングリコールは数平均分子量２００の
ものを用いた。At this time, polyethylene glycol having a number average molecular weight of 200 was used.
比較例ｌ、２に発明例１で用いたポリエステルとイソシ
アナート化合物としてＭＤＩ（ミリオネートＭＴ，ＮＣ
Ｏ％：３０、日本ポリウレタン■製）及びコロネートＬ
（ＮＶ：７５％、ＮＣＯ％：１３．２、日本ポリウレタ
ン■製）を使用した例を示したが、表２に示すように２
００℃前後の高温に曝した後の接着強度の低下が大きく
耐熱性に欠ける。 比較例３は分子量の低いポリエステ
ルにイソシアナートとしてコロネート２０３０を使用し
た場合であるが、積層接着時に樹脂の流れだしがあり、
接着性能、戊形性とも満足できる性能が得られなかった
。 このように本発明の組み合わせにおいてのみ、制振
鋼板として良好な性能が得られることがわかる。In Comparative Examples 1 and 2, MDI (Millionate MT, NC) was used as the polyester and isocyanate compound used in Invention Example 1.
O%: 30, made by Japan Polyurethane) and Coronate L
(NV: 75%, NCO%: 13.2, manufactured by Nippon Polyurethane) was shown, but as shown in Table 2,
After exposure to high temperatures of around 00°C, the adhesive strength decreases significantly and heat resistance is lacking. Comparative Example 3 is a case where Coronate 2030 is used as an isocyanate for polyester with a low molecular weight, but the resin flows out during lamination and adhesion.
Satisfactory performance was not obtained in terms of adhesive performance and formability. Thus, it can be seen that good performance as a damping steel plate can be obtained only in the combination of the present invention.
表３には、発明例ｌで用いた樹脂組成物と導電性物質と
してニッケル粉末を用いた時のスポット溶接性能及び接
着性能に及ぼす導電性物質の充填量を示した． ０．５
％未満ではスポット溶接性能が達成されず、又、１０％
超では接着性能が低下した。Table 3 shows the filling amount of the conductive material on the spot welding performance and adhesion performance when the resin composition used in Invention Example 1 and nickel powder were used as the conductive material. 0.5
If the spot welding performance is less than 10%, spot welding performance cannot be achieved.
Adhesive performance deteriorated at ultra-low temperature.
表
３
用が困難であった用途にも使用できるなど、極めて優れ
た性能を有する制振材料が可能となり、自動車業界、土
木建築業界、電機業界において巾広く使用できる割振材
料を提供できるものであり、それらの業界に与える効果
は非常に大きなものである．
く発明の効果〉
以上のように、本発明は制振作用を発揮させるための中
間樹脂層として特定の飽和共重合ポリエステルと重合ポ
リイソシアナートを併用することにより、常温付近、具
体的にはＯ℃〜５０℃の割振性に優れ、かつ成形性に耐
えつる接着性能を有するとともに、２００℃前後の高温
に曝した後の耐熱耐久−性を有するため、成形性を必要
としない平板に近い状態で用いる建材用途は勿論、自動
車ボディー回りのダッシュパネル、フロアーパネル、ル
ーフパネル等従来使Table 3 It has become possible to create a vibration damping material with extremely excellent performance that can be used in applications where it was previously difficult to use, and to provide a vibration damping material that can be widely used in the automobile, civil engineering and construction, and electrical industries. , the effects on these industries are enormous. Effects of the Invention> As described above, the present invention uses a specific saturated copolymerized polyester and a polymerized polyisocyanate together as an intermediate resin layer for exhibiting a vibration damping effect, so that the temperature at around room temperature, specifically O It has excellent distribution properties from °C to 50 °C, has adhesive performance that can withstand moldability, and has heat resistance and durability after being exposed to high temperatures of around 200 °C, so it is close to a flat plate that does not require moldability. Not only can it be used as a building material for automobile bodies, but it can also be used for conventional uses such as dash panels, floor panels, and roof panels around automobile bodies.
第１図は本発明の樹脂を用いて作られた制振鋼板の周波
数１０００Ｈｚにおける損失係数の測定結果を示す図で
あり、イ、ロ、ハはそれぞれ発明例１，４及び５で得ら
れた割振鋼板の損失係数の測定結果を示すものである。Figure 1 is a diagram showing the measurement results of the loss coefficient at a frequency of 1000 Hz of a damping steel plate made using the resin of the present invention, where A, B, and C were obtained in Invention Examples 1, 4, and 5, respectively. This figure shows the measurement results of the loss coefficient of the divided steel plate.
Claims (6)
℃以上１５０℃以下の飽和ポリエステルおよび架橋剤と
しての重合ポリイソシアナート化合物を含有することを
特徴とする複合型制振材料用樹脂組成物。(1) Weight average molecular weight of 10,000 or more and softening point of 50
A resin composition for a composite vibration damping material, comprising a saturated polyester having a temperature of 150°C or higher and a polymerized polyisocyanate compound as a crosslinking agent.
℃以上１５０℃以下の飽和ポリエステルおよび架橋剤と
しての重合ポリイソシアナート化合物を含有し、さらに
導電性物質を０．５〜１０ｖｏｌ％含有することを特徴
とする複合型制振材料用樹脂組成物。(2) Weight average molecular weight of 10,000 or more and softening point of 50
A resin composition for a composite vibration damping material, comprising a saturated polyester having a temperature of 150°C or higher and a polymerized polyisocyanate compound as a crosslinking agent, and further containing 0.5 to 10 vol% of a conductive substance.
℃以上１５０℃以下の飽和ポリエステルおよび架橋剤と
しての重合ポリイソシアナート化合物を含有する組成物
を中間層として有することを特徴とする複合型制振材料
。(3) Weight average molecular weight of 10,000 or more and softening point of 50
A composite vibration damping material comprising, as an intermediate layer, a composition containing a saturated polyester having a temperature of 150°C or higher and a polymerized polyisocyanate compound as a crosslinking agent.
℃以上１５０℃以下の飽和ポリエステルおよび架橋剤と
しての重合ポリイソシアナート化合物を含有する組成物
に対し、樹脂厚の０．５倍以上の径を有する導電性物質
を０．５〜１０ｖｏｌ％混合してなる中間層を有するこ
とを特徴とするスポット溶接可能な複合型制振材料。(4) Weight average molecular weight of 10,000 or more and softening point of 50
0.5 to 10 vol% of a conductive substance having a diameter of 0.5 times or more the thickness of the resin is mixed into a composition containing a saturated polyester having a temperature of 150°C or higher and a polymerized polyisocyanate compound as a crosslinking agent. A spot-weldable composite vibration damping material characterized by having an intermediate layer consisting of:
℃以上１５０℃以下の飽和ポリエステルと重合ポリイソ
シアナート化合物を混合して得た混合物を金属板間に介
在させることを特徴とする複合型制振材料の製造方法。(5) Weight average molecular weight of 10,000 or more and softening point of 50
1. A method for producing a composite vibration damping material, comprising interposing a mixture obtained by mixing a saturated polyester and a polymerized polyisocyanate compound at a temperature of 150° C. or higher between metal plates.
℃以上１５０℃以下の飽和ポリエステルと重合ポリイソ
シアナート化合物と導電性物質を０．５〜１０ｖｏｌ％
混合して得た混合物を金属板間に介在させることを特徴
とする複合型制振材料の製造方法。(6) Weight average molecular weight of 10,000 or more and softening point of 50
0.5 to 10 vol% of saturated polyester, polymerized polyisocyanate compound, and conductive substance at a temperature of ℃ to 150℃
A method for manufacturing a composite vibration damping material, characterized in that a mixture obtained by mixing is interposed between metal plates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2041509A JPH0320321A (en) | 1989-02-22 | 1990-02-22 | Resin composition for composite vibration-damping mateiral, composite vibration-damping material produced therefrom, and its production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4229689 | 1989-02-22 | ||
| JP1-42296 | 1989-02-22 | ||
| JP2041509A JPH0320321A (en) | 1989-02-22 | 1990-02-22 | Resin composition for composite vibration-damping mateiral, composite vibration-damping material produced therefrom, and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0320321A true JPH0320321A (en) | 1991-01-29 |
Family
ID=26381149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2041509A Pending JPH0320321A (en) | 1989-02-22 | 1990-02-22 | Resin composition for composite vibration-damping mateiral, composite vibration-damping material produced therefrom, and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0320321A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014193962A (en) * | 2013-03-29 | 2014-10-09 | Unitika Ltd | Copolyester resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63207809A (en) * | 1987-02-23 | 1988-08-29 | Nippon Steel Corp | Viscoelastic resin for vibration-damping material |
| JPS6448813A (en) * | 1987-08-19 | 1989-02-23 | Kawasaki Steel Co | Resin composition for composite damping steel sheet |
| JPS6469685A (en) * | 1987-09-10 | 1989-03-15 | Nippon Steel Chemical Co | Composition for composite vibration-damping material |
-
1990
- 1990-02-22 JP JP2041509A patent/JPH0320321A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63207809A (en) * | 1987-02-23 | 1988-08-29 | Nippon Steel Corp | Viscoelastic resin for vibration-damping material |
| JPS6448813A (en) * | 1987-08-19 | 1989-02-23 | Kawasaki Steel Co | Resin composition for composite damping steel sheet |
| JPS6469685A (en) * | 1987-09-10 | 1989-03-15 | Nippon Steel Chemical Co | Composition for composite vibration-damping material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014193962A (en) * | 2013-03-29 | 2014-10-09 | Unitika Ltd | Copolyester resin composition |
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