JPH01263147A - Composition for composite type vibration-damping material - Google Patents
Composition for composite type vibration-damping materialInfo
- Publication number
- JPH01263147A JPH01263147A JP9124688A JP9124688A JPH01263147A JP H01263147 A JPH01263147 A JP H01263147A JP 9124688 A JP9124688 A JP 9124688A JP 9124688 A JP9124688 A JP 9124688A JP H01263147 A JPH01263147 A JP H01263147A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resins
- composition
- glass transition
- transition temperature
- 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 53
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 230000009477 glass transition Effects 0.000 claims abstract description 17
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 15
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 11
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 11
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 11
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005011 phenolic resin Substances 0.000 claims abstract description 10
- 239000003208 petroleum Substances 0.000 claims abstract description 8
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 8
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 5
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 239000003431 cross linking reagent Substances 0.000 abstract description 12
- -1 polyethylene terephthalate Polymers 0.000 abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 9
- 229920001568 phenolic resin Polymers 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 2
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 description 34
- 229920001225 polyester resin Polymers 0.000 description 34
- 230000001070 adhesive effect Effects 0.000 description 26
- 239000000853 adhesive Substances 0.000 description 25
- 239000011342 resin composition Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000007769 metal material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000010680 novolac-type phenolic resin Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- QYAMPIKBANGIEM-UHFFFAOYSA-N chloroethene;hydrochloride Chemical compound Cl.ClC=C QYAMPIKBANGIEM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、複合型制振材料用組成物に係り、詳しくは車
両、電気部品、機械や構造物の構成部材またはその一部
を構成して、これらの振動を減少させ、騒音を低減させ
ることができる振動吸収性能の高い複合型制振材料を製
造する際に使用される組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a composite vibration damping material composition, and more specifically, it relates to a composite vibration damping material composition that constitutes a component or a part of a vehicle, electrical component, machine or structure. The present invention relates to a composition for use in manufacturing a composite damping material with high vibration absorption performance that can reduce these vibrations and reduce noise.
近年、交通機関の発達や住居の工場への接近に伴なって
騒音や振動の問題が公害として社会問題化するようにな
り、また職場においてもその作業環境の改善を目的とし
て騒音や振動を規制する傾向にある。このような動向に
対応して、騒音源や振動源である金属材料など剛性のあ
る基板に対して制振性能を付与することやその制振性能
の向上を図ることが要請されている。In recent years, with the development of transportation systems and the proximity of residences to factories, noise and vibration problems have become a social problem as pollution, and noise and vibration regulations have also been introduced in workplaces to improve the working environment. There is a tendency to In response to such trends, there is a demand for providing vibration damping performance to rigid substrates such as metal materials that are sources of noise and vibration, and to improve the vibration damping performance.
そこで、従来よりががる制振性能を発揮する材料ノーツ
トシテ、２つの金属材料など剛性のある基板の中間に粘
弾性樹脂からなる粘弾性中間層を挟み込んだ３層構造を
有する複合型制振材料が提案されており、２つの金属層
の中間に粘弾性樹脂を挟み込んだ物として、例えば自動
車のオイルパン、エンジンカバー、ダツシュボードパネ
ル及びフロア−、ホフバーのシュート部、搬送設備のス
トッパー、家電製品、その他金属加工機械の振動低減部
材や振動防止が望まれる精密機械の構造部材等において
検討され採用されている。Therefore, we developed a composite vibration damping material that has a three-layer structure in which a viscoelastic intermediate layer made of viscoelastic resin is sandwiched between two rigid substrates such as metal materials, which exhibits better damping performance than conventional materials. has been proposed, and products in which a viscoelastic resin is sandwiched between two metal layers can be used, for example, in automobile oil pans, engine covers, dash board panels and floors, chute parts of hof bars, stoppers of conveyance equipment, and home appliances. , and other vibration reduction members for metal processing machines and structural members of precision machines where vibration prevention is desired.
この場合、２つの金属層を構成する金属材料としては、
互いに相対面し中間に粘弾性樹脂を挾み込んで制振材料
を構成し得るものであればよく例えば、２枚の金属板、
２本の同心金属管、２本の形鋼、互いに重ね合わせるこ
とができる２枚の成形体、金属成形体と当板、その他の
２層構造を有するものを挙げることができる。そして、
ここに言う金属層を形成する金属としては、特に限定さ
れるものではないが、通常、鉄、アルミニウム、泪、鉛
あるいはこれらを一成分とする合金類、さらには亜夕（
）、錫、クロム等でメツキされた金属材料及びエポキシ
樹脂、メラミン樹脂等で表面処理されたものであっても
よい。In this case, the metal materials constituting the two metal layers are:
For example, two metal plates may be used as long as they face each other and can sandwich a viscoelastic resin between them to form a damping material.
Examples include two concentric metal tubes, two steel sections, two molded bodies that can be stacked on top of each other, a metal molded body and a backing plate, and other two-layered structures. and,
The metal forming the metal layer referred to herein is not particularly limited, but usually includes iron, aluminum, lead, or alloys containing these as one component, and even aluminum (
), metal materials plated with tin, chromium, etc., and surfaces treated with epoxy resin, melamine resin, etc. may be used.
そして、このような複合型制振材料の粘弾性中間層を構
成する粘弾性樹脂としては様々な樹脂系が提案されてい
るが、その中でも金属層との接着性や所望の温度領域に
おいて良好な制振性能が得られるという点からポリエス
テル系樹脂が優れζいる。例えば、飽和ポリエステル樹
脂に架橋剤として有機過酸化物および充填剤を配合した
組成物（特公昭５３−９，７９４号公報）、ポリエステ
ル系樹脂あるいはポリエステル系樹脂とポリオレフィン
系樹脂の樹脂組成物（特開昭６１−８９，８４２号公報
）、ポリアルキレンイソツクレート・テレフタレート共
重合体とポリビニルアセクールとからなる樹脂組成物（
特公昭６２−２，９８２号公報）、ポリエステル系樹脂
と可望剤とからなる樹脂組成物（特開昭６１−２７７、
４３５号公報）、ポリブチレンイソテレフタレートから
なる樹脂組成物（特開昭６２−８０．０３５号公ｆｔｔ
）や、また本発明者等による非晶質ポリエステル、酸無
水物およびエポキシ化合物からなる樹脂組成物（特願昭
６１−２１９，１６０号）や非品性ポリエステル樹脂と
低品性ポリエステル樹脂からなる樹脂組成物（特願昭６
１１８．１６０号）等線々な樹脂系による組成物が提案
されている。Various resin systems have been proposed as the viscoelastic resin that constitutes the viscoelastic intermediate layer of such composite vibration damping materials, but among these resin systems are those that have good adhesion with the metal layer and in the desired temperature range. Polyester resins are superior in terms of their ability to provide vibration damping performance. For example, a composition in which a saturated polyester resin is blended with an organic peroxide and a filler as a crosslinking agent (Japanese Patent Publication No. 53-9,794), a resin composition of a polyester resin or a polyester resin and a polyolefin resin (Japanese Patent Publication No. 53-9,794), JP-A-61-89,842), a resin composition consisting of a polyalkylene isotucrate/terephthalate copolymer and polyvinyl acecool (
Japanese Patent Publication No. 62-2,982), a resin composition comprising a polyester resin and a desensitizer (Japanese Patent Publication No. 61-277,
No. 435), a resin composition consisting of polybutylene isoterephthalate (Japanese Patent Application Laid-open No. 62-80.035 ftt
), resin compositions made by the present inventors consisting of amorphous polyester, acid anhydride, and epoxy compounds (Japanese Patent Application No. 61-219,160), and resin compositions made of non-quality polyester resins and low-grade polyester resins. Resin composition (patent application 1986)
No. 118.160) compositions based on isolinear resin systems have been proposed.
ところで、このような複合型制振材料に要求される特性
としては、第一に制振性能が高いことが挙げられ、これ
は一般に損失係数の大小によって表現される。そして、
第二には複合型制振材料が構造部材としても使用され、
またプレス加工等の二次加工も受けるため粘弾性樹脂で
構成される粘弾性中間層と外側金属層との間の接着強度
、特に剪断接着強度が高いことが挙げられる。さらに、
第三にはプレス加工を受けた複合型制振材料は２００℃
程度まで加熱される焼付塗装工程を経ることがありこの
温度付近で中間層樹脂組成物が流出しないことも要求さ
れる。また、複合型制振材料が実際に使用される際の実
用物性として使用温度領域（室温から８０℃程度）にお
ける耐水性も要求されるものである。By the way, the first characteristic required of such a composite damping material is high damping performance, which is generally expressed by the magnitude of the loss coefficient. and,
Second, composite damping materials are also used as structural members.
Furthermore, since it is subjected to secondary processing such as press processing, the adhesive strength, especially the shear adhesive strength, between the viscoelastic intermediate layer made of a viscoelastic resin and the outer metal layer is high. moreover,
Third, the composite vibration damping material that has undergone press processing is heated to 200℃.
It is also required that the intermediate layer resin composition does not flow out at around this temperature, since the intermediate layer resin composition may be subjected to a baking coating process in which it is heated to a certain temperature. In addition, water resistance in the operating temperature range (room temperature to about 80° C.) is also required as a practical physical property when the composite vibration damping material is actually used.
特に、０〜６０℃の常温域で優れた割振性能を発揮する
制振材料の場合、粘弾性中間層樹脂組成物のガラス転移
領域は常温付近若しくはそれ以下にある必要があり、常
温では弾性率の低い組成物である。一方、プレス加工性
に重要な影響を及ぼす剪断接着強度は一般に高い弾性率
を示す組成物の方が優れている。すなわら、複合型制振
材料に要求される制振性能とプレス加工性に関連する剪
断接着強度とは粘弾性中間層樹脂の弾性率に関して相反
する要求特性となっており、上記従来のポリエステル系
樹脂あるいはポリエステル系樹脂と特定の他系樹脂とを
混合した組成物では金属材料に対して優れた接着性を有
する樹脂組成物であるが、特に常温域で割振性能を発揮
するようなガラス転移温度の低い樹脂の場合、剪断接着
強度はプレス加工に耐えられるほどの高い値は示さず満
足な材料とはいえない。In particular, in the case of a damping material that exhibits excellent vibration distribution performance in the room temperature range of 0 to 60°C, the glass transition region of the viscoelastic intermediate layer resin composition must be near or below room temperature, and the elastic modulus at room temperature is It has a low composition. On the other hand, compositions exhibiting a high elastic modulus are generally superior in terms of shear adhesive strength, which has an important effect on press workability. In other words, the vibration damping performance required for composite vibration damping materials and the shear adhesive strength related to press workability are contradictory requirements regarding the elastic modulus of the viscoelastic intermediate layer resin, and the conventional polyester A resin composition that is a mixture of a polyester resin or a polyester resin with a specific other resin has excellent adhesion to metal materials, but it has a glass transition property that exhibits splitting performance especially in the room temperature range. In the case of a low-temperature resin, the shear adhesive strength does not show a value high enough to withstand press processing, and it cannot be said to be a satisfactory material.
さらに、特公昭５３−９，７９４号公報に開示されてい
るポリエステル樹脂、有機過酸化物架橋剤、充填剤から
なる組成物でも、その剪断接着強度は向上するものの有
機過酸化物等のラジカルを発生する架橋剤はポリエステ
ル樹脂の架橋反応を制御することが困難であり、またラ
ジカル反応はポリエステル樹脂の末端、主鎖あるいは側
鎖いがなるところでも起こり高分子の分子運動を抑制す
るものであり制振性能に悪影古を及ぼずものである。Furthermore, even with the composition disclosed in Japanese Patent Publication No. 53-9,794, which consists of a polyester resin, an organic peroxide crosslinking agent, and a filler, although the shear adhesive strength is improved, radicals such as organic peroxides are It is difficult to control the crosslinking reaction of the polyester resin with the generated crosslinking agent, and radical reactions also occur at the ends, main chain, or side chains of the polyester resin, suppressing the molecular movement of the polymer. It has no negative impact on damping performance.
一方、特願昭６２−１８．１６０号で提案した非品性ポ
リエステル樹脂と低品性ポリエステル樹脂のブレンド物
からなる樹脂組成物は常温域における制振性能及び剪断
接着強度も充分な値を示すが、高温域で極端に流動性が
増大し２００℃程度では外側金属層の口開きが生じる恐
れがある。On the other hand, the resin composition made of a blend of non-quality polyester resin and low-quality polyester resin proposed in Japanese Patent Application No. 62-18.160 shows sufficient vibration damping performance and shear adhesive strength at room temperature. However, the fluidity increases extremely in a high temperature range, and at about 200°C, there is a risk that the outer metal layer may open.
また、特願昭６１−２１９．１６０号で提案した非晶質
ポリエステル樹脂、酸無水物及びエポキシ化合物からな
る組成物の場合、常温域で優れた制振性能を示し、かつ
剪断接着強度もプレス加工に耐え得る値を示すが耐水性
が不足している。この剪断接着強度および耐水性を更に
向上させる為に酸無水物、エポキシ化合物の配合量を多
量とすると樹脂組成物の熱可塑性が損なわれ複合型制振
材料の製造工程において塗料型として鋼板に樹脂組成物
を塗布し貼、り合わせた後に架橋反応を行う必要が生じ
煩雑さが避は難いと共に制振性能（損失係数）の最大値
を示す温度が高温側に移行することは、否めなく、複合
型制振材料としては充分に満足し得るものではなかった
。In addition, in the case of a composition consisting of an amorphous polyester resin, an acid anhydride, and an epoxy compound proposed in Japanese Patent Application No. 61-219.160, it shows excellent vibration damping performance in the room temperature range, and also has excellent shear adhesive strength when pressed. It shows a value that can withstand processing, but water resistance is insufficient. In order to further improve this shear adhesive strength and water resistance, if a large amount of acid anhydride or epoxy compound is blended, the thermoplasticity of the resin composition will be impaired, and the resin will be applied to the steel plate as a paint type in the manufacturing process of composite vibration damping materials. It is necessary to carry out a cross-linking reaction after the composition is applied, pasted and laminated, which inevitably leads to complications, and it is undeniable that the temperature at which the damping performance (loss coefficient) exhibits the maximum value shifts to the higher temperature side. It was not fully satisfactory as a composite vibration damping material.
本発明はかかる観点に鑑みて創案されたもので組成物の
熱可塑性を損なわず、常温域で優れた割振性能を付与し
、金属材料に対して良好な接着性を有し、塗料焼付温度
付近でも流出し難い粘弾性中間層を形成することができ
、さらに耐水性も具備した複合型制振材料を製造するの
に適した組成物を提供することを目的とするものである
。The present invention was devised in view of the above points, and does not impair the thermoplasticity of the composition, provides excellent distribution performance in the room temperature range, has good adhesion to metal materials, and has properties close to the paint baking temperature. The object of the present invention is to provide a composition suitable for producing a composite vibration damping material that can form a viscoelastic intermediate layer that does not easily flow out even when the material is water resistant.
即ち、本発明は一３０〜６０℃のガラス転移温度を有す
ると共にこのガラス転移温度において０．５以上の損失
正接を有する熱可塑性ポリエステル樹脂に、ロジン系樹
脂、クマロン系樹脂、石油系樹脂、ポリビニルアルコー
ル樹脂、フェノール系樹脂、およびフェノキシ樹脂から
なる熱可塑性樹脂群の中から選ばれた軟化点が６０’Ｃ
以上である樹脂を１種以上配合してなる複合型制振材料
用組成物である。That is, the present invention uses a thermoplastic polyester resin having a glass transition temperature of -30 to 60°C and a loss tangent of 0.5 or more at this glass transition temperature, and a rosin resin, a coumaron resin, a petroleum resin, and a polyvinyl resin. A thermoplastic resin with a softening point of 60'C selected from a group of thermoplastic resins consisting of alcohol resins, phenolic resins, and phenoxy resins.
This is a composition for a composite vibration damping material, which is formed by blending one or more of the above resins.
まず、本発明における複合型制振材料とは最初に述べた
ような２つの金属層の中間にこれらの金属層を互いに接
合する粘弾性中間層が挟み込まれたいわゆる３層構造を
有するものである。First, the composite vibration damping material in the present invention has a so-called three-layer structure in which a viscoelastic intermediate layer for bonding these metal layers to each other is sandwiched between two metal layers as described at the beginning. .
この粘弾性樹脂組成物を構成する熱可塑性ポリエステル
樹脂は常温で制振性能を発揮するものであり、−３０〜
６０℃にガラス転移温度を有する粘弾性樹脂組成物であ
る。ガラス転移温度が一３０℃より低い場合、常温より
低い温度領域で割振性能を発揮するものとなり複合型制
振材料用の組成物に通常要求されるガラス転移温度の一
３０〜６０℃にそのガラス転移温度を移行させるために
、高融点固形樹脂、充填剤等を多量に添加する必要が生
じ、また６０℃より高くなると逆に８０℃以上の温度領
域で割振性能を発揮するものとなりガラス転移温度を低
温側に移行させるために多量の可塑剤を添加する必要が
生じる。これら各種添加剤を多量に使用した場合には接
着性が低下したり、高温時に流動し易くなる場合もあり
好ましくない。また、このガラス転移温度における損失
正接（ｔａｎδ）については制振性能の観点から０．５
以上好ましくは０．７以上のものである必要がある。こ
の損失正接（ｔａｎδ）が０．５より小さいと満足し得
る制振性能が発揮されない。The thermoplastic polyester resin constituting this viscoelastic resin composition exhibits vibration damping performance at room temperature, and has a vibration damping performance of -30 to
It is a viscoelastic resin composition having a glass transition temperature of 60°C. If the glass transition temperature is lower than 130°C, it will exhibit its damping performance in a temperature range lower than room temperature, and the glass transition temperature will be 30 to 60°C, which is usually required for compositions for composite vibration damping materials. In order to shift the transition temperature, it is necessary to add large amounts of high-melting point solid resins, fillers, etc., and if the temperature rises above 60°C, the glass transition temperature will conversely exhibit its allocation performance in the temperature range of 80°C or higher. It becomes necessary to add a large amount of plasticizer to move the temperature to the low temperature side. If a large amount of these various additives is used, it is not preferable because the adhesiveness may deteriorate or the adhesive may become more likely to flow at high temperatures. In addition, the loss tangent (tan δ) at this glass transition temperature is 0.5 from the viewpoint of damping performance.
The above value should preferably be 0.7 or more. If this loss tangent (tan δ) is smaller than 0.5, satisfactory damping performance will not be exhibited.
このようなポリエステル樹脂としては、ポリエチレンテ
レフタレート、ボリブチレンチレフタレート等の高結晶
性ポリエステルを高温でエチレングリコールに溶解しト
リエチレングリコール、１゜４−ブタンジオール、ネオ
ペンチルグリコール等の多価アルコールを加え、エステ
ル交換反応によって合成することが可能であり、また多
価カルボン酸と多価アルコールを共重合することによっ
ても合成することができる。後者の合成法で使用する多
価カルボン酸としては、テレフタル酸、イソフタル酸、
フタル酸、２．６−ナフタレンジカルボン酸、ジフェニ
ルジカルボン酸、コハク酸、アジピン酸、アゼライン酸
、セバシン酸、ドデカンジオン酸、無水トリメリット酸
等を挙げることができ、また多価アルコールとしてはエ
チレングリコール、１゜４−ブタンジオール、１．５−
ベンタンジオール、ｌ、６−ヘキサンジオール、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、ネオペンチルグリコール、プロピレング
リコール、１．４−シクロヘキサンジメタツール、ペン
クエリスリトール、トリメチロールプロパン等を挙げる
ことができる。これら単量体の組合せは数多くあり、希
望する融点、ガラス転移ｌＡ度、非品性や結晶性の程度
等により適宜選定して使用される。Such polyester resins are made by dissolving highly crystalline polyesters such as polyethylene terephthalate and polybutylene ethylene phthalate in ethylene glycol at high temperature, and adding polyhydric alcohols such as triethylene glycol, 1°4-butanediol, and neopentyl glycol. , can be synthesized by transesterification reaction, and can also be synthesized by copolymerizing polyhydric carboxylic acid and polyhydric alcohol. Polyvalent carboxylic acids used in the latter synthesis method include terephthalic acid, isophthalic acid,
Phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, trimellitic anhydride, etc. can be mentioned, and polyhydric alcohols include ethylene glycol , 1゜4-butanediol, 1.5-
Bentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, propylene glycol, 1,4-cyclohexane dimetatool, penquerythritol, trimethylolpropane and the like can be mentioned. There are many combinations of these monomers, and they are appropriately selected and used depending on the desired melting point, glass transition degree, degree of purity, degree of crystallinity, etc.
また、使用されるポリエステル樹脂は１種類である必要
はなく２種以上のポリエステル樹脂を混合した組成物で
あってもよい。なお、２種板−ｈ？昆合する場合、それ
らが互いに相溶挙動を示す時は混合物の…失正接が単一
挙動を示しこの損失正接がガラス転移温度において０．
５以上であれば良い。Moreover, the polyester resin used does not need to be one type, and a composition containing two or more types of polyester resins may be used. In addition, the second type board-h? When they are mixed and exhibit mutually compatible behavior, the loss tangent of the mixture exhibits a unitary behavior and this loss tangent is 0.0 at the glass transition temperature.
It is sufficient if it is 5 or more.
また、２種以上のポリエステル樹脂が非相溶挙動を示す
場合は、混合物の…失止接の極大イ直は２つ以上存在す
るがそのうちの−・番大きい極大値が０゜５以上を示せ
ば良い。In addition, when two or more types of polyester resins exhibit incompatible behavior, there are two or more maximum values of discontinuous contact of the mixture, but the largest value among them must be 0°5 or more. Good.
また、選定したポリエステル樹脂の割振材料用組成物と
しての総合的な性能４損なわない範囲で制振性能の改良
あるいは弾性率の向上を計るためにポリエステル樹脂以
外の樹脂を混合して使用してもよい、これらの樹脂とし
ては、例えばポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂、Ｍ
Ｓ樹脂、耐衝撃性ポリスチレン等のスチレン系樹脂、ポ
リメチルアクリレート、ポリメチルメタクリレート、ポ
リエチルメタクリレート、アクリル系共重合体等のアク
リル系樹脂、ポリ塩化ビニル、塩化ビニル・酢酸ビニル
共重合体、塩化ビニル・アクリル酸エステル共重合体等
の塩化ビニル系樹脂、エチレン・α−オレフィン共重合
体、エチレン・酢酸ビニル共重合体、エチレン・アクリ
ル酸共重合体、エチレン・メタクリル酸エステル共重合
体 エチレン・メタクリル酸共重合体の金属架橋物等の
エチレン系樹脂、プロピレン・エチレン共重合体、プロ
ピレン・ブテン共重合体等のプロピレン系樹脂、共重合
ナイロンのような非品性ポリアミド等の熱可塑性樹脂を
例示することができる。また、スチレン・ブタジェンゴ
ム、天然ゴム、ブタジェンゴム、ニトリルゴム、クロロ
ブレンゴム、ブチルゴム、アクリルゴム、エチレン・ア
クリルゴム、ＥＰＤＭ等のガラスＩ・マーも挙げられる
。In addition, resins other than polyester resins may be mixed and used in order to improve damping performance or elastic modulus within a range that does not impair the overall performance of the selected polyester resin as a composition for allocation materials. Examples of these resins include polystyrene, AS resin, ABS resin, M
S resin, styrenic resins such as impact-resistant polystyrene, acrylic resins such as polymethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, acrylic copolymers, polyvinyl chloride, vinyl chloride/vinyl acetate copolymers, chloride Vinyl chloride resins such as vinyl/acrylic acid ester copolymers, ethylene/α-olefin copolymers, ethylene/vinyl acetate copolymers, ethylene/acrylic acid copolymers, ethylene/methacrylic acid ester copolymers, ethylene/ Ethylene resins such as metal crosslinked methacrylic acid copolymers, propylene resins such as propylene/ethylene copolymers, propylene/butene copolymers, and thermoplastic resins such as non-grade polyamides such as copolymerized nylon. I can give an example. Also included are glass I/mers such as styrene-butadiene rubber, natural rubber, butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, acrylic rubber, ethylene-acrylic rubber, and EPDM.
しかし、ポリエステル樹脂のみの組成物およびポリエス
テル樹脂の制振性あるいは弾性率を改良するために上記
の熱可塑性樹脂あるいはエラストマーをポリエステル樹
脂に混合した組成物では、制振性あるいは接着強度に対
しては効果があるものの耐水性が不足している。よって
、組成物の熱可塑性を維持しつつ耐水性を向上させるに
はさらにロジン系樹脂、クマロン系樹脂、石油系樹脂、
ポリビニルアルコール梼脂、フェノール系樹脂およびフ
ェノキシ樹脂からなる熱可塑性樹脂群の中から選ばれた
軟化点が６０’Ｃ以上である樹脂を１種以上添加する必
要がある。However, compositions containing only polyester resin and compositions in which the above-mentioned thermoplastic resin or elastomer is mixed with polyester resin to improve the vibration damping properties or elastic modulus of the polyester resin do not have good vibration damping properties or adhesive strength. Although effective, it lacks water resistance. Therefore, in order to improve the water resistance while maintaining the thermoplasticity of the composition, rosin-based resins, coumaron-based resins, petroleum-based resins,
It is necessary to add one or more resins having a softening point of 60'C or more selected from the thermoplastic resin group consisting of polyvinyl alcohol resin, phenolic resins, and phenoxy resins.
一方、これらの熱可塑性樹脂の軟化点が６０’Ｃより低
い半固体状あるいは液状のものを用いると常温での接着
強度は向上するものの高温では組成物が流動し易くなり
高温接着強度も低下し好ましいものではない。On the other hand, if a semi-solid or liquid thermoplastic resin with a softening point lower than 60'C is used, the adhesive strength at room temperature will improve, but at high temperatures the composition will tend to flow and the high temperature adhesive strength will decrease. Not desirable.
御所にロジン系樹脂、クマロン系樹脂、石油系樹脂は粘
着性付与剤として知られており、ポリビニルアルコール
樹脂、フェノール系樹脂およびフェノキシ樹脂は塗料の
下地処理を行う際の有効成分として知られている。これ
らの粘着性付与剤および下地処理有効成分は金属材料へ
の密着性の向上が期待できるものである。Rosin-based resins, coumaron-based resins, and petroleum-based resins are known as tackifiers, and polyvinyl alcohol resins, phenolic resins, and phenoxy resins are known as active ingredients when performing base treatment for paints. . These tackifiers and base treatment active ingredients are expected to improve adhesion to metal materials.
軟化点が６０℃以上の上記熱可塑性樹脂としては、例え
ばロジン、ロジンエステル、水添ロジンエステル等のロ
ジン系樹脂、クマロン・インデン樹脂、フェノール変性
クマロン樹脂等のクマロン系樹脂、脂肪族系石油樹脂、
芳香族系石油樹脂、ポリジシクロペンタジェン等の石油
系樹脂、ポリビニルアルコール樹脂、ノボラック型フェ
ノール樹脂、アルキルフェ、ノール樹脂、テルペンフェ
ノール樹脂等のフェノール系樹脂あるいはフェノキシ樹
脂等を挙げることができる。これらの熱可塑性樹脂の添
加量は選定した樹脂の種類によって異なるがポリエステ
ル系樹脂１００重吋部に対して１〜５０重吋部、好まし
くは５〜３０重量部である。添加量が１重世部より少な
いと期待する効果が得られない。Examples of the thermoplastic resins having a softening point of 60° C. or higher include rosin resins such as rosin, rosin ester, and hydrogenated rosin ester, coumaron resins such as coumaron-indene resins and phenol-modified coumaron resins, and aliphatic petroleum resins. ,
Examples include petroleum resins such as aromatic petroleum resins and polydicyclopentadiene, phenolic resins such as polyvinyl alcohol resins, novolac type phenolic resins, alkylphene resins, nol resins, and terpene phenol resins, and phenoxy resins. The amount of these thermoplastic resins added varies depending on the type of resin selected, but is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the polyester resin. If the amount added is less than 1 part, the expected effect will not be obtained.
また、添加量が５０重量部より多くなるとポリエステル
系樹脂により発現する割振性能が発揮される温度領域が
高温側にずれるため好ましくない。Furthermore, if the amount added exceeds 50 parts by weight, the temperature range in which the distribution performance exhibited by the polyester resin is shifted to the high temperature side, which is not preferable.
また、得られた制振材料のプレス加工性に影Ｃを及ぼす
剪断接着強度を向上させ、更に塗料焼付温度付近での流
出性を抑えた組成物とするために架橋剤を添加しても良
い。このような架橋剤としては、例えばイソシアネート
化合物、エポキシ化合物、酸無水物、アミン化合物、ア
ジリジル化合物、オキサプリン化合物あるいは有機金属
化合物等が例示される。これらの架橋剤の中で特に好ま
しいものとしてはポリエステル系樹脂末端の水酸基との
反応性が高いイソシアネート化合物あるいはエポキシ化
合物、酸無水物が挙げられる。またこれらの架橋剤は単
独でももしくは２種以上混合して使用してもかまわない
。さらに、必要に応じて官能基間の反応を促進あるいは
遅延させるために各種の触媒を使用することもできる。In addition, a crosslinking agent may be added to improve the shear adhesive strength, which affects the press workability of the obtained damping material, and to create a composition that suppresses run-off near the paint baking temperature. . Examples of such crosslinking agents include isocyanate compounds, epoxy compounds, acid anhydrides, amine compounds, aziridyl compounds, oxapurine compounds, and organometallic compounds. Among these crosslinking agents, particularly preferred are isocyanate compounds, epoxy compounds, and acid anhydrides that are highly reactive with the hydroxyl group at the end of the polyester resin. Further, these crosslinking agents may be used alone or in combination of two or more. Furthermore, various catalysts can be used to promote or delay the reaction between functional groups as required.
これらの架橋剤の添加量は選定した架橋剤の種類によっ
て異なるがポリエステル系樹脂１００重量部に対して５
０重量部以下の使用が好ましい。５０重量部より多くな
るとポリエステル樹脂の熱可塑性が損なわれると共に制
振性が発揮される頭載が高温側に移行し好ましくない。The amount of these crosslinking agents added varies depending on the type of crosslinking agent selected, but it is 5 parts by weight per 100 parts by weight of the polyester resin.
It is preferred to use 0 parts by weight or less. If the amount exceeds 50 parts by weight, the thermoplasticity of the polyester resin will be impaired, and the head position where vibration damping properties are exhibited will shift to the high temperature side, which is not preferable.
また、本発明の組成物の剪断接着強度をより向上させる
ためにさらに無機フィラーを充填してもよい。このよう
な無機フィラーとしては２００℃程度まで加熱しても熱
分解しないものである必要があり、カーボンブランク、
シリカ、アルミナ、クレー、酸化チタン、亜鉛華、マイ
カ、黒鉛等が挙げられるが、特に高温時の剪断接着強度
を向上させる効果が大きい点からカーボンブランク、シ
リカあるいはクレーの１種以上を用いることが望ましく
、その添加量についてはポリエステル系樹脂１００重量
部に対して１〜１００重量部、特に５〜５０重量部が好
ましい。Further, in order to further improve the shear adhesive strength of the composition of the present invention, an inorganic filler may be added. Such inorganic fillers must not be thermally decomposed even when heated to about 200℃, and carbon blanks,
Examples include silica, alumina, clay, titanium oxide, zinc white, mica, graphite, etc., but it is recommended to use one or more of carbon blank, silica, or clay because it is particularly effective in improving shear adhesive strength at high temperatures. Desirably, the amount added is 1 to 100 parts by weight, particularly preferably 5 to 50 parts by weight, per 100 parts by weight of the polyester resin.
また、樹脂組成物のガラス転移温度を所望の値に移行す
るために可塑剤を添加してもよい。この目的で使用され
る可塑剤としては、例えばポリエステル系可塑剤、ポリ
エーテルエステル系可塑剤、リン酸エステル類、エポキ
シ系可塑剤、フタル酸ジエステル、セバシン酸ジエステ
ル等のエステル系可塑剤、トリメリット酸系可塑剤、塩
素化パラフィン等を挙げることができ、使用するポリエ
ステル樹脂により適宜選定して使用する。Furthermore, a plasticizer may be added in order to shift the glass transition temperature of the resin composition to a desired value. Plasticizers used for this purpose include, for example, polyester plasticizers, polyether ester plasticizers, phosphoric acid esters, epoxy plasticizers, ester plasticizers such as phthalic acid diesters, sebacic acid diesters, etc. Examples include acid plasticizers and chlorinated paraffins, which are appropriately selected and used depending on the polyester resin used.
また、上記粘弾性組成物に充填剤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、得られた制振材
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、錫、銅、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
物質を挙げることができる。これらの導電性物質は単独
で使用できるほか、２種以上を組合わせて使用すること
もできる。この導電性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の
厚さを、さらにファイバー状である場合にはその最大直
径をそれぞれの代表長さ（Ｌ）としたとき、より良好な
スポット溶接性を得るにはこの代表長さ（Ｌ）と複合制
振材料の中間樹脂層の厚さ（Ｔ）との比（Ｌ／Ｔ）を０
．５以上、好ましくは０．８以上、より好ましくは１．
０以上にするのがよい。Furthermore, conductivity can be imparted to the viscoelastic composition by blending it with a conductive solid substance as a filler, and the resulting damping material can be made into a material that can be spot welded. Conductive substances used for this purpose include metal materials such as stainless steel, zinc, tin, copper, brass, and nickel processed into powder, flake, fiber, wire, etc. . These conductive substances can be used alone or in combination of two or more. If this conductive substance is in powder form, its maximum particle size, if it is in flake form, its maximum thickness, and if it is in fiber form, its maximum diameter is determined by its representative length. (L), in order to obtain better spot weldability, the ratio (L/T) between this representative length (L) and the thickness (T) of the intermediate resin layer of the composite damping material is 0.
．． 5 or more, preferably 0.8 or more, more preferably 1.
It is better to set it to 0 or more.
本発明の組成物層の厚さは要求される制振性能等から適
宜選定されるものであるが、割振性能の観点から１０μ
翔以上、特に２０μｍ以上が好ましく、複合制振材料の
プレス加工性等の観点から３００μ−以下、特に２００
μ鋼以下が好ましい。The thickness of the composition layer of the present invention is appropriately selected depending on the required vibration damping performance, etc., but from the viewpoint of vibration allocation performance, the thickness is 10 μm.
The thickness is preferably 20 μm or more, especially 20 μm or more, and 300 μm or less, especially 200 μm or less from the viewpoint of press workability of the composite vibration damping material.
μ steel or less is preferable.
本発明の組成物を使用して複合型制振材料を製造する方
法については、特に制限されるものではなく、切板を使
用するバッチ法、コイルを使用する連続性等任意の方法
をとることができる。一方、粘弾性樹脂と金属材料とを
複合化し複合型制振材料を製造する方法としては、粘弾
性樹脂を溶剤に溶解させた塗料状のものを金属材料に塗
布して貼り合わせる方法、Ｔ−ダイ押出機等で金属材料
上に粘弾性樹脂の中間層を形成する方法、オフラインで
製造したフィルム状の粘弾性樹脂を中間層として金属材
料の間に挟み込みホットメルト接着する方法等が挙げら
れ、樹脂組成物の性状あるいは得られる複合型制振材料
の種類等の目的に合わせ任意の方法を採用する、：とが
できる。There are no particular restrictions on the method for producing the composite damping material using the composition of the present invention, and any method may be used, such as a batch method using a cut plate or a continuous method using a coil. I can do it. On the other hand, methods for manufacturing a composite vibration damping material by compounding a viscoelastic resin and a metal material include a method in which a paint-like material in which a viscoelastic resin is dissolved in a solvent is applied to a metal material and bonded together; Examples include a method of forming an intermediate layer of a viscoelastic resin on a metal material using a die extruder, etc., a method of sandwiching a film-like viscoelastic resin produced off-line as an intermediate layer between metal materials and hot melt bonding, etc. Any method can be adopted depending on the purpose, such as the properties of the resin composition or the type of composite vibration damping material to be obtained.
以下、実施例及び比較例に基づいて本発明を説明する。 The present invention will be described below based on Examples and Comparative Examples.
これらの実施例及び填較例において試験に供するフィル
ムは次に述べる方法で作製した。The films to be tested in these Examples and Comparative Examples were prepared by the method described below.
第１表に示すポリエステル樹脂を加圧型ニーグーに投入
し、ここに第１表に示す架橋剤、熱可塑性樹脂を添加し
１００℃〜１８０℃で混練して組成物を得た。この混練
物を１２０℃〜１７０℃のダイス温度でＴ−グイ押出し
し離型紙上に厚さ７０μｍのフィルムとして作製した。The polyester resins shown in Table 1 were put into a pressurized Ni-Goo, and the crosslinking agents and thermoplastic resins shown in Table 1 were added thereto and kneaded at 100°C to 180°C to obtain a composition. This kneaded product was extruded through T-guidry at a die temperature of 120° C. to 170° C. to form a film with a thickness of 70 μm on release paper.
なお、ポリエステル樹脂に添加した熱可塑性樹脂はクマ
ロン樹脂（軟化点：１２０℃）、ロジンエステル樹脂（
軟化点： １００ ’Ｃ） 、フェノキシ樹脂（軟化点
二６５℃）、およびノボラック型フェノール樹脂（軟化
点ニア０℃）である。The thermoplastic resins added to the polyester resin include Coumaron resin (softening point: 120°C), Rosin ester resin (
Softening point: 100'C), phenoxy resin (softening point: 265°C), and novolac type phenolic resin (softening point: 0°C).
上記フィルムを２枚の０．８ｍｍ１’Ｘの冷延鋼板間に
挟み込み２００℃で１分間加熱圧着し厚さ７０μ鋼の粘
弾性樹脂中間層を有する複合制振材料を得た。The above film was sandwiched between two 0.8 mm 1'X cold rolled steel plates and heated and pressed at 200° C. for 1 minute to obtain a composite damping material having a viscoelastic resin intermediate layer of 70 μm thick steel.
Ｔ剥離接着強度はＪ Ｉｓ−に−６８５４試験法に基づ
く５０ｍｍ／ｗｉｎの引張速度で評価し、剪断接着強度
はＪＩＳ−に−６８５０試験法に基づいて５ｍｍ／ｗｉ
ｎの引張速度で評価、耐水性試験は沸騰水中で３時間処
理した後の剪断接着強度の保持率を測定した。また割振
性能は機械インピーダンス法５００Ｈｚで振動吸収能を
表すＩ置火係数（η）を測定しηの最大値（η１．。）
及びこのη□８を示すときの温度（Ｔ、）を測定して評
価した。さらに、粘弾性物質の動的力学的性質は、非共
振強制振動型の動的粘弾性測定装置により、３１ｍ１１
１×３１１ＩＩ１１×厚さ１ｍ＋ｗの試料を２枚使用し
、剪断モードで周波数１０１１ｚ、昇温温度２℃／ｍｉ
ｎでの温度分散試験により測定した。T-peel adhesive strength was evaluated at a tensile rate of 50 mm/win based on JIS-6854 test method, and shear adhesive strength was evaluated at 5 mm/win based on JIS-6850 test method.
The water resistance test was performed by measuring the retention rate of shear adhesive strength after being treated in boiling water for 3 hours. In addition, the allocation performance was measured by the mechanical impedance method at 500 Hz, and the I firing coefficient (η), which represents vibration absorption ability, was measured and the maximum value of η (η1..)
The temperature (T, ) at which this value of η□8 was measured was evaluated. Furthermore, the dynamic mechanical properties of the viscoelastic material were measured using a non-resonant forced vibration type dynamic viscoelasticity measuring device.
Using two samples of 1 x 311 II 11 x thickness 1 m + w, frequency 1011z in shear mode, heating temperature 2 ° C / mi
Measured by temperature dispersion test at n.
これらのフィルムを鋼板に挟み込んで試験した結果を第
１表に示す。Table 1 shows the results of tests conducted by sandwiching these films between steel plates.
ポリエステルＡのみでは剪断接着強度５５ｋｇｆ／ｃａ
ｔ。Shear adhesive strength of polyester A alone is 55 kgf/ca
t.
耐水性１０％と低いものであり（比較例１）、架橋剤と
して酸無水物、エポキシ化合物を添加した比較例２にお
いても剪断接着強度が８５ｋｇｆ／ｃｄ、耐水性６０％
と向上するがまだ満足のゆくものではない。The water resistance was low at 10% (Comparative Example 1), and even in Comparative Example 2 in which an acid anhydride and an epoxy compound were added as a crosslinking agent, the shear adhesive strength was 85 kgf/cd and the water resistance was 60%.
However, it is still not satisfactory.
それに対してこの組成物に熱可塑性樹脂としてクマロン
樹脂、ロジン樹脂、フェノキシ樹脂およびフェノール樹
脂を１０ ｐｈｒずつ１種あるいは２種配合した実施例
１〜５では剪断接着強度が９５〜１５５ｋｇｆ／ａｊ、
耐水性が８０〜９５％と著しく向上した。この際の割振
性能は熱可塑性樹脂を上記範囲内添加しても無添加の比
較例２に比べ損失係数の最大値（η１．Ｘ）は低下する
ことなくこの損失係数の最大値を与える温度（Ｔ２）も
３℃上昇するのみである。しかし、常温で液状のフェノ
ール樹脂を１０ｐｈｒ添加した比較例３においては常温
での剪断接着強度が９０ｋｇｆ／−とフェノール樹脂無
添加の比較例２の値より向上するが耐水性が４５％と低
下しており常温用の複合型制振材料としては不適なもの
である。On the other hand, in Examples 1 to 5, in which one or two types of thermoplastic resins such as coumaron resin, rosin resin, phenoxy resin, and phenol resin were blended at 10 phr each, the shear adhesive strength was 95 to 155 kgf/aj,
Water resistance was significantly improved to 80-95%. The allocation performance in this case is that even if the thermoplastic resin is added within the above range, the maximum value of the loss coefficient (η1. T2) also increases by only 3°C. However, in Comparative Example 3, in which 10 phr of phenolic resin, which is liquid at room temperature, was added, the shear adhesive strength at room temperature was 90 kgf/-, which was improved compared to the value of Comparative Example 2, which did not contain phenolic resin, but the water resistance decreased to 45%. Therefore, it is unsuitable as a composite vibration damping material for room temperature use.
また、ポリエステル樹脂を２種類混合使用した（混合物
のｔａｎδ１．３５）実施例６においても剪断接着強度
が７５ｋｇｆ／ｃ＋Ｊ、耐水性８０％と熱可塑性樹脂無
添加の比較例４の剪断接着強度が５５１ｇｆ／ｃ＋Ｊ、
耐水性３０％に比べ著しく上昇しており、割振性能につ
いては損失係数の最大値（η１□）が低下せず、損失係
数の最大値を与える温度（Ｔ、）も僅かの上昇しかない
。Also, in Example 6, in which two types of polyester resins were mixed (tan δ 1.35 of the mixture), the shear adhesive strength was 75 kgf/c+J, and the shear adhesive strength of Comparative Example 4, which had a water resistance of 80% and no thermoplastic resin was added, was 551 gf. /c+J,
The water resistance is significantly increased compared to 30%, and regarding the allocation performance, the maximum value of the loss coefficient (η1□) does not decrease, and the temperature (T, ) that gives the maximum value of the loss coefficient only increases slightly.
本発明の組成物は２つの金属材料に挟み込まれ、得られ
た複合型制振材料が優れた接着性を有すると共に常温付
近において優れた制振性能を発揮するものであり、産業
上極めて有用である。The composition of the present invention is sandwiched between two metal materials, and the resulting composite vibration damping material has excellent adhesive properties and exhibits excellent vibration damping performance at around room temperature, making it extremely useful industrially. be.
Claims (1)
ラス転移温度において０．５以上の損失正接を有する熱
可塑性ポリエステル樹脂に、ロジン系樹脂、クマロン系
樹脂、石油系樹脂、ポリビニルアルコール樹脂、フェノ
ール系樹脂、およびフェノキシ樹脂からなる熱可塑性樹
脂群の中から選ばれた軟化点が６０℃以上である樹脂を
１種以上配合してなる複合型制振材料用組成物。A thermoplastic polyester resin having a glass transition temperature of -30 to 60°C and a loss tangent of 0.5 or more at this glass transition temperature, rosin resin, coumaron resin, petroleum resin, polyvinyl alcohol resin, phenol resin A composite vibration damping material composition comprising a resin and one or more resins having a softening point of 60° C. or higher selected from a thermoplastic resin group consisting of phenoxy resins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9124688A JPH01263147A (en) | 1988-04-15 | 1988-04-15 | Composition for composite type vibration-damping material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9124688A JPH01263147A (en) | 1988-04-15 | 1988-04-15 | Composition for composite type vibration-damping material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01263147A true JPH01263147A (en) | 1989-10-19 |
Family
ID=14021062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9124688A Pending JPH01263147A (en) | 1988-04-15 | 1988-04-15 | Composition for composite type vibration-damping material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01263147A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015083626A1 (en) * | 2013-12-02 | 2015-06-11 | ユニチカ株式会社 | Polyester resin composition, and adhesive containing same |
| JP2021523031A (en) * | 2018-05-01 | 2021-09-02 | ユナイテッド・ステイツ・ジプサム・カンパニー | Methods for making high sound transmission class gypsum boards and gypsum boards made by those methods |
-
1988
- 1988-04-15 JP JP9124688A patent/JPH01263147A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015083626A1 (en) * | 2013-12-02 | 2015-06-11 | ユニチカ株式会社 | Polyester resin composition, and adhesive containing same |
| JPWO2015083626A1 (en) * | 2013-12-02 | 2017-03-16 | ユニチカ株式会社 | Polyester resin composition and adhesive containing the same |
| JP2021523031A (en) * | 2018-05-01 | 2021-09-02 | ユナイテッド・ステイツ・ジプサム・カンパニー | Methods for making high sound transmission class gypsum boards and gypsum boards made by those methods |
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