JPS63202446A - Composite type vibration-damping laminate and manufacture thereof - Google Patents
Composite type vibration-damping laminate and manufacture thereofInfo
- Publication number
- JPS63202446A JPS63202446A JP3537687A JP3537687A JPS63202446A JP S63202446 A JPS63202446 A JP S63202446A JP 3537687 A JP3537687 A JP 3537687A JP 3537687 A JP3537687 A JP 3537687A JP S63202446 A JPS63202446 A JP S63202446A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- molecular weight
- mixture
- high molecular
- weight
- 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 description 66
- 239000002131 composite material Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920005989 resin Polymers 0.000 claims description 101
- 239000011347 resin Substances 0.000 claims description 101
- 239000000203 mixture Substances 0.000 claims description 39
- 229920006395 saturated elastomer Polymers 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 33
- 229920001225 polyester resin Polymers 0.000 claims description 29
- 239000004645 polyester resin Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 238000004132 cross linking Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 230000009477 glass transition Effects 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 description 60
- 239000010959 steel Substances 0.000 description 60
- 239000000853 adhesive Substances 0.000 description 40
- 230000001070 adhesive effect Effects 0.000 description 40
- 229920000728 polyester Polymers 0.000 description 20
- 239000007788 liquid Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000011162 core material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000010960 cold rolled steel Substances 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 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
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 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 2
- 238000007731 hot pressing Methods 0.000 description 2
- -1 isocyanate compound Chemical class 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
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003973 paint 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids 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
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 229920003180 amino resin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 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
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- 229920002554 vinyl polymer Polymers 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
Landscapes
- Vibration Prevention Devices (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、制振効果のある樹脂層とそれを両側からはさ
む金属層とからなる３層構造の複合型制振積層体に関す
る。特に、芯材樹脂層に熱可塑性ポリエステル含有樹脂
混合物を使用し、比較的低温での割振性能に優れ、かつ
加工性にも優れるといった、従来技術では達成できなか
った性能を示す複合型制振積層体に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a composite vibration damping laminate having a three-layer structure consisting of a resin layer having a damping effect and metal layers sandwiching the resin layer from both sides. In particular, a composite vibration-damping laminate that uses a thermoplastic polyester-containing resin mixture for the core resin layer has excellent vibration distribution performance at relatively low temperatures and excellent workability, which is unattainable with conventional technology. Regarding the body.
（従来の技術）
近年、産業機械や家電用品の発達により、各種機械装置
より発生する騒音、振動が保健衛生あるいは環境保全の
面から問題とされるようになってきた。特に、輸送期間
の発達、自動車の普及率の上昇は著しく、それに伴う騒
音が社会問題として取上げられ、騒音防止対策が要望さ
れている。(Prior Art) In recent years, with the development of industrial machinery and home appliances, noise and vibration generated by various mechanical devices have become a problem from the viewpoint of health and hygiene and environmental conservation. In particular, the development of transportation periods and the rise in the prevalence of automobiles have been remarkable, and the accompanying noise has been raised as a social problem, and noise prevention measures have been demanded.
特に、自動車のエンジン廻り部品（オイルパンやエンジ
ンカバー）、ボディー（ダッシュパネル、ドア、フード
、フロア−など）、”家電機器、金属加工機械、ダクト
、建材（屋根、塀、壁、床など）等における騒音低減が
強（要望されている。In particular, automobile engine parts (oil pans and engine covers), bodies (dash panels, doors, hoods, floors, etc.), home appliances, metal processing machines, ducts, building materials (roofs, fences, walls, floors, etc.) Strong noise reduction (desired).
かかる対策の１つとして、制振鋼板などの制振金属板の
使用があり、防振合金を利用する方法、金属に割振材料
を貼合わせた２層型（非拘束型）の割振鋼板を使用する
方法、さらには金属と金属との間に芯材樹脂層を挟み込
んだ複合型（拘束型）割振鋼板を使用する方法が開発さ
れ、広範囲の分野で採用され始めている。特に複合拘束
型制振ｔｌｉｌＦｉ、（以下、単に制振鋼板という）は
、中間層の粘弾性物質の剪断変形による内部摩擦を利用
して振動を減衰させるものであり、上記の中でも最も割
振性能に優れている。しかも、かかる複合型制 、振鋼
板は、そのままでプレス加工などの二次加工が可能で、
通常の鋼板と同様に取扱うことができるという利点があ
る。One such countermeasure is the use of vibration-damping metal plates such as vibration-damping steel plates, methods that utilize vibration-proof alloys, and the use of two-layer type (non-constraint type) distributed steel plates in which a vibration-damping material is laminated to metal. A method using a composite type (restricted type) split steel plate in which a core resin layer is sandwiched between two metals has been developed and is beginning to be adopted in a wide range of fields. In particular, composite restraint type vibration damping tlilFi (hereinafter simply referred to as vibration damping steel plate) uses internal friction caused by shear deformation of the viscoelastic material in the intermediate layer to damp vibration, and has the highest vibration allocation performance among the above. Are better. Moreover, such composite die and shaken steel plates can be subjected to secondary processing such as press working as they are.
It has the advantage that it can be handled in the same way as ordinary steel plates.
制振鋼板は、その樹脂層と金属層との剪断接着強度が大
きい方が一般に加工性も良好となることが知られている
。また、この剪断接着強度は、中間層樹脂の硬さと相関
関係があり、硬いほど良好となる。一方、割振鋼板の制
振性能は、中間層樹脂がある程度柔らかい場合に良好で
ある。It is known that the workability of a damping steel plate is generally better when the shear adhesive strength between the resin layer and the metal layer is greater. Moreover, this shear adhesive strength has a correlation with the hardness of the intermediate layer resin, and the harder it is, the better it is. On the other hand, the vibration damping performance of the distributed steel plate is good when the intermediate layer resin is soft to some extent.
したがって、自動車エンジンオイルパンなどのように比
較的高温での割振性が要求される場合には、中間層樹脂
として常温（プレス加工時の温度）では硬く、高温（使
用温度）では適当な柔らかさになる樹脂を選択すること
によって、加工性と制振性とが両立した割振鋼板を提供
することが可能である。Therefore, in cases where distribution performance at relatively high temperatures is required, such as in automobile engine oil pans, the intermediate layer resin should be hard at room temperature (temperature during press processing) and suitably soft at high temperatures (usage temperature). By selecting a resin that has the following properties, it is possible to provide a distributed steel plate that has both workability and vibration damping properties.
一方、常温で割振性能を発揮させたい場合、必然的に常
温で柔らかい樹脂を使用する必要があるが、その鋼板と
の剪断接着強度は小さいので加工性が十分でな（、常温
での制振鋼板の用途は比較的単純な形状のものに限定さ
れているのが現状であった。On the other hand, if you want to exhibit vibration damping performance at room temperature, it is necessary to use a resin that is soft at room temperature, but its shear adhesive strength with the steel plate is low, so it is not easy to work with. Currently, the uses of steel plates are limited to those with relatively simple shapes.
したがって、常温で使用する複雑な形状の物品に制振鋼
板を適用するために、常温での剪断接着強度と柔らかさ
とを両立させるという、矛盾した特性を有する中間層樹
脂の開発が求められている。Therefore, in order to apply damping steel plates to products with complex shapes that are used at room temperature, there is a need to develop an intermediate layer resin that has the contradictory properties of achieving both shear adhesive strength and softness at room temperature. .
常温用制振鋼板としては、アクリル系、ポリエステル系
の粘着性樹脂や、ブタジェンゴムなどのゴム系材料がそ
の中間層樹脂として用いられてきた。これらの比較的柔
らかい樹脂を中間層として用いた割振鋼板は、常温での
割振性には優れるが、鋼板との剪断接着強度が低いとい
う固有の欠点を有している。ポリビニルブチラール樹脂
などのビニルアセクール重合体を主成分とする粘着性樹
脂からなる割振鋼板が、特公昭５５−２７９７５号およ
び特開昭５９−１２４８４７号公報に開示されているが
、やはり常温割振性と剪断接着強度とは両立していない
。For normal temperature damping steel plates, adhesive resins such as acrylic and polyester, and rubber materials such as butadiene rubber have been used as intermediate layer resins. Distributed steel plates using these relatively soft resins as an intermediate layer have excellent distributability at room temperature, but have an inherent drawback of low shear adhesive strength with the steel plate. Distributable steel sheets made of adhesive resins mainly composed of vinyl acecool polymers such as polyvinyl butyral resins are disclosed in Japanese Patent Publication No. 55-27975 and Japanese Patent Application Laid-open No. 59-124847, but they also have poor room temperature dissociation properties. and shear adhesive strength are not compatible.
この欠点を克服するため、樹脂の硬さの温度依存性を利
用し、割振鋼板を常温よりかなり低温に冷却して樹脂層
を硬くした状態でプレス加工する方法も提案されている
が、実際的な方法ではない。In order to overcome this drawback, a method has been proposed that takes advantage of the temperature dependence of the hardness of resin and cools the split steel plate to a temperature much lower than room temperature to harden the resin layer and then press it, but it is not practical. Not in a good way.
割振鋼板の制振性もしくは接着強度を改善する別の方法
として、中間層の熱可塑性樹脂を架橋させるか、あるい
は２種以上のモノマーの共重合体もしくは２１１以上の
樹脂の混合物を中間層に利用する方法が提案されている
。Another method for improving the damping properties or adhesive strength of a split steel plate is to crosslink the thermoplastic resin in the intermediate layer, or to use a copolymer of two or more monomers or a mixture of 211 or more resins in the intermediate layer. A method has been proposed.
たとえば、特公昭５３−９７９４号公報に記載の割振鋼
板では、飽和ポリエステル樹脂に有機過酸化物系架橋剤
および充填剤を配合し、加熱により架橋させた架橋ポリ
エステル系の中間樹脂層が使用されている。この公報は
、また従来技術として熱可塑性ポリエステルをエポキシ
化合物やイソシアネート化合物で三次元架橋させる方法
、メラミンなどの熱硬化性成分と硬化剤を配合する方法
、ポリエステルの重合中にエステル形成性官能基を３個
以上含有する化合物を配合することによりポリエステル
を分岐架橋させる方法が公知であることも開示している
。しかし、これらの方法でも良好な剪断接着強度は得ら
れず、たとえばこの公報記載の実施例で得られた最高の
剪断接着強度でも約１８ｋｇ／−であり、十分な値とは
いえない。For example, in the distributed steel sheet described in Japanese Patent Publication No. 53-9794, a crosslinked polyester intermediate resin layer is used, which is a mixture of a saturated polyester resin, an organic peroxide crosslinking agent and a filler, and crosslinking by heating. There is. This publication also describes a method of three-dimensionally crosslinking thermoplastic polyester with an epoxy compound or an isocyanate compound, a method of blending a thermosetting component such as melamine with a curing agent, and a method of adding an ester-forming functional group during polymerization of polyester. It is also disclosed that a method of branching and crosslinking polyester by blending a compound containing three or more compounds is known. However, even with these methods, good shear adhesive strength cannot be obtained; for example, even the highest shear adhesive strength obtained in the example described in this publication is about 18 kg/-, which is not a sufficient value.
また、２種以上のモノマーの共重合体を樹脂層に用いた
制振鋼板としては、酢酸ビニルにエチレン、不飽和ジカ
ルボン酸もしくはそのエステルなどの１種以上を共重合
させた共重合体を始めとして各種の共重合体樹脂が提案
されている（例、特公昭４５−３５６６４号、同４５−
３６８２３号、および同４６−１７０６４号公報）、こ
れらも、常温での制振性または加工性の少な（ともいず
れかが十分でない。In addition, vibration-damping steel sheets using copolymers of two or more monomers in the resin layer include copolymers made by copolymerizing vinyl acetate with one or more of ethylene, unsaturated dicarboxylic acids, or their esters, etc. Various copolymer resins have been proposed as
No. 36823 and No. 46-17064), these also have insufficient vibration damping properties or poor workability at room temperature (either of which is insufficient).
特公昭３９−１２４５１号公報は、ホモポリマー〇ガラ
ス転移温度が互いに２０℃以上異なる２種類の七ツマ−
の不均質な共重合体を中間層樹脂として使用することに
より、広範囲の温度で割振性能を発揮させる方法が記載
されている。しかし、この方法は、常温付近でも制振性
が得られるものの、剪断接着強度の改善は図られていな
い。Japanese Patent Publication No. 39-12451 describes two types of homopolymers whose glass transition temperatures differ by 20°C or more from each other.
A method is described in which a heterogeneous copolymer of 100% is used as an intermediate layer resin to exhibit splitting performance over a wide range of temperatures. However, although this method provides vibration damping properties even at room temperature, it does not improve shear adhesive strength.
２種以上の樹脂の混合物を中間層に使用した割振鋼板と
して、たとえば特公昭５５−２３１号および特開昭６０
−２４５５５０号公報に、アクリロニトリル−ブタジェ
ン系共重合体ゴムとエポキシ樹脂とを含有する樹脂混合
物を架橋させた硬化樹脂を中間層とする割振鋼板が開示
されている。かかる系もやはり、大きな剪断接着強度を
有するものは割振性を発揮する温度が高く、常温付近で
割振性に優れるものは剪断接着強度が低い。For example, Japanese Patent Publication No. 55-231 and Japanese Patent Application Laid-Open No. 60-1980 disclose a split steel plate using a mixture of two or more resins in the intermediate layer.
Japanese Patent No. 245,550 discloses a split steel plate having an intermediate layer made of a cured resin obtained by crosslinking a resin mixture containing an acrylonitrile-butadiene copolymer rubber and an epoxy resin. As for such systems, those having a high shear adhesive strength exhibit their splitting properties at a high temperature, and those exhibiting excellent splitting properties at around room temperature have a low shearing adhesive strength.
特開昭６１−８９８４１号および同６１−８９８４２号
公報には、飽和ポリエステル樹脂と他の樹脂との混合物
あるいは層状積層体を中間層樹脂として使用した例が示
されているが、この例でも接着強度が高いと同時に制振
性を発揮する温度もまた高く、常温用の割振鋼板には不
向きである。JP-A-61-89841 and JP-A No. 61-89842 show examples in which a mixture or layered laminate of saturated polyester resin and other resins is used as the intermediate layer resin. Although it has high strength, the temperature at which it exhibits vibration damping properties is also high, making it unsuitable for use as a damping steel plate for room temperature use.
特公昭５４−３０２８号公報には、３層以上の多層金属
板の中間層として、互いにガラス転移温度が異なる異種
の樹脂を使用した、広範囲の温度で割振性を発揮できる
制振鋼板が開示されている。しかし、この割振鋼板も、
広範囲の温度で割振性を発揮するものの、剪断接着強度
は改善されず、しかも３層以上の金属板を必要とするた
め必然的に厚くなり、加工性が劣化する上に用途が限定
され、また価格的にも不利である。Japanese Patent Publication No. 54-3028 discloses a damping steel plate that uses different types of resins with different glass transition temperatures as the intermediate layer of a multilayer metal plate of three or more layers, and can exhibit vibration damping properties over a wide range of temperatures. ing. However, this divided steel plate also
Although it exhibits dispersion properties over a wide range of temperatures, it does not improve shear adhesive strength, and because it requires three or more layers of metal plates, it is inevitably thicker, resulting in poor workability and limited applications. It is also disadvantageous in terms of price.
（発明が解決しようとする問題点）
本発明の目的は、以上に概説したように、従来技術では
達成できなかった常温付近の比較的低温で優れた割振性
能を発揮し、しかも剪断接着強度すなわち加工性も良好
な制振鋼板などの複合型制振積層体およびその製造方法
を提供することである。(Problems to be Solved by the Invention) As outlined above, the purpose of the present invention is to exhibit excellent allocation performance at relatively low temperatures near room temperature, which could not be achieved with conventional techniques, and to exhibit shear adhesive strength or It is an object of the present invention to provide a composite vibration damping laminate such as a damping steel plate having good workability and a method for manufacturing the same.
（問題点を解決するための手段）
本発明者らは研究の結果、ガラス転移温度の異なる２種
類の高分子量線状飽和ポリエステル樹脂の混合物を架橋
させて得た樹脂を制振鋼板の中間層として用いることに
より、比較的低温での高制振性と高剪断接着強度とを両
立させるという技術的困難が解決できること、およびガ
ラス転移温度の高い方のポリエステル樹脂は、高分子量
エポキシ樹脂で代替しても同様の好結果が得られること
を知り、本発明を完成させた。(Means for Solving the Problems) As a result of research, the present inventors found that a resin obtained by crosslinking a mixture of two types of high molecular weight linear saturated polyester resins with different glass transition temperatures was used as an intermediate layer of a damping steel plate. The technical difficulty of achieving both high vibration damping properties and high shear adhesive strength at relatively low temperatures can be solved by using the resin as a material, and the polyester resin with a higher glass transition temperature can be replaced with a high molecular weight epoxy resin. The present invention was completed based on the knowledge that similar good results could be obtained using the same method.
ここに、本発明は、２枚の金属板の間に樹脂層を挟んで
なる複合型制振積層体において、前記樹脂層が、（Ａ）
および（Ｂ）の合計重量に基づいて、（Ａ）ガラス転移
温度θ℃以下の線状高分子！飽和ポリエステル樹脂５〜
９５重量％と、（Ｂ）゛ガラス転移温度１０℃以上の線
状高分子Ｉ！和ポリエステル樹脂、高分子量エポキシ樹
脂、またはこれら−の混合物５〜９５重量％とを含有す
る樹脂混合物を架橋して得た樹脂から構成されることを
特徴とする、複合型制振積層体である。Here, the present invention provides a composite vibration damping laminate in which a resin layer is sandwiched between two metal plates, wherein the resin layer comprises (A)
Based on the total weight of and (B), (A) a linear polymer with a glass transition temperature of θ°C or lower! Saturated polyester resin 5~
95% by weight and (B) linear polymer I with a glass transition temperature of 10°C or higher! A composite vibration damping laminate characterized in that it is composed of a resin obtained by crosslinking a resin mixture containing 5 to 95% by weight of a Japanese polyester resin, a high molecular weight epoxy resin, or a mixture thereof. .
本発明によれば、かかる割振積層体の製造方法も提供さ
れ、この方法は、（Ａ）とＣＢ）の合計１ｉｆに基づい
て、（Ａ）ガラス転移温度θ℃以下の線状高分子！飽和
ポリエステル樹脂５〜９５重量％と、（Ｂ）ガラス転移
温度１０℃以上の線状高分子Ｎ飽和ポリエステル樹脂、
高分子量エポキシ樹脂、またはこれらの混合物５〜９５
重量％とを含有する樹脂混合物を前記金属板の少なくと
も一方の片面に塗装し、得られた塗膜を焼付けて上記樹
脂混合物を架橋させ、この架橋塗膜を内側にして前記２
枚の金属板を重ね合わせ、熱圧着させて積層体を得るこ
とからなる。According to the present invention, there is also provided a method for manufacturing such an allocated laminate, and this method is based on the sum of 1if of (A) and CB), and is based on (A) a linear polymer having a glass transition temperature of θ° C. or less! 5 to 95% by weight of a saturated polyester resin; (B) a linear polymer N saturated polyester resin with a glass transition temperature of 10°C or higher;
High molecular weight epoxy resin or mixture thereof 5-95
% by weight is applied to at least one side of the metal plate, the resulting coating film is baked to crosslink the resin mixture, and the crosslinked coating film is placed inside to form the above-mentioned 2.
It consists of stacking two metal plates and bonding them under heat to obtain a laminate.
（作用）
このように、本発明によれば、ガラス転移温度が異なる
２種類の特定の樹脂を中間層に使用するが、これを特公
昭３９−１２４５１号公報に記載のように共重合体化し
たり、また特公昭５４−３０２４号公報に記載のように
別の樹脂層として存在させたり、あるいは２種以上の樹
脂を単なる混合物として使用するのではなく、両者の混
合物を架橋させて使用することに特徴がある。(Function) As described above, according to the present invention, two types of specific resins having different glass transition temperatures are used in the intermediate layer, and these are copolymerized as described in Japanese Patent Publication No. 39-12451. Alternatively, as described in Japanese Patent Publication No. 54-3024, it may be present as a separate resin layer, or rather than using two or more resins as a mere mixture, a mixture of both may be crosslinked. There are characteristics.
本発明の制振積層体の中間層、すなわち芯材樹脂層に用
いる２種類の樹脂の一方は、ガラス転移温度（Ｔｇ）が
０℃以下の線状高分子量飽和ポリエステル（以下、樹脂
Ａという）である、この樹脂は、比較的低温で良好な制
振性を発揮するが、この樹脂単独では剪断接着強度が非
常に低く、積層体の加工性は極度に悪化する。樹脂Ａは
、混合物のＴｇが０℃以下となる限り、２種以上の線状
高分子量飽和ポリエステルの混合物であってもよい、ポ
リエステル樹脂Ａの好ましいガラス転移温度は、−３０
〜θ℃である。One of the two types of resin used for the intermediate layer, that is, the core resin layer, of the vibration damping laminate of the present invention is a linear high molecular weight saturated polyester (hereinafter referred to as resin A) having a glass transition temperature (Tg) of 0°C or less. Although this resin exhibits good vibration damping properties at relatively low temperatures, the shear adhesive strength of this resin alone is extremely low, and the workability of the laminate is extremely poor. Resin A may be a mixture of two or more types of linear high molecular weight saturated polyesters as long as the Tg of the mixture is 0°C or less. The preferred glass transition temperature of polyester resin A is -30
~θ°C.
もう一方の樹脂は、Ｔｇが１０℃以上の線状高分子量飽
和ポリエステル樹脂であるか、高分子量エポキシ樹脂で
あるか、またはこの両者の混合物（以下、樹脂Ｂという
）である、この樹脂Ｂは、制振積層体の中間層とした場
合に、非常に優れた剪断接着強度を与えるが、常温付近
では制振性を発揮できない、樹脂Ｂがポリエステルであ
る場合、混合物のＴｇが１０℃以上となる限り、２種以
上の線状高分子量飽和ポリエステル樹脂の混合物を使用
することができ、また２種以上の高分子量エポキシ樹脂
、あるいはポリエステル樹脂とエポキシ樹脂の混合物を
使用することもできる。樹脂Ｂとして使用するポリエス
テル樹脂の好ましいガラス転移温度は、１０〜１００℃
である。The other resin is a linear high molecular weight saturated polyester resin with a Tg of 10°C or higher, a high molecular weight epoxy resin, or a mixture of both (hereinafter referred to as resin B). When resin B is polyester, it provides very excellent shear adhesive strength when used as an intermediate layer of a vibration damping laminate, but cannot exhibit vibration damping properties near room temperature. As far as possible, mixtures of two or more linear high molecular weight saturated polyester resins can be used, and also mixtures of two or more high molecular weight epoxy resins or of polyester resins and epoxy resins. The preferable glass transition temperature of the polyester resin used as resin B is 10 to 100°C.
It is.
本明細書において、「高分子量」とは、重合体の数平均
分子量が少なくとも３，０００であるものをいう、飽和
ポリエステルもしくはエポキシ樹脂の分子量が３，００
０未満であると、架橋した際に脆くなってしまう、一方
、これらの樹脂の分子量があまりに大きすぎると、後述
するように塗料化する場合やフィルム成形する場合、粘
度が著しく大となり、実用的でない、好ましい分子量の
上限は、飽和ポリエステル樹脂については３０，０００
．エポキシ樹脂については５０，０００である。As used herein, "high molecular weight" refers to a polymer having a number average molecular weight of at least 3,000, and a saturated polyester or epoxy resin having a molecular weight of at least 3,000.
If it is less than 0, it will become brittle when cross-linked. On the other hand, if the molecular weight of these resins is too large, the viscosity will be extremely high when making it into a paint or forming a film as described later, making it impractical for practical use. The preferred upper molecular weight limit is 30,000 for saturated polyester resins.
．． 50,000 for epoxy resin.
樹脂ＡおよびＢの混合物における各樹脂の量は、樹脂Ａ
５〜９５重量％、好ましくは３０〜７０重量％、樹脂８
５〜９５重量％、好ましくは３０〜７０重量％の範囲内
である。樹脂入が多すぎると、剪断接着強度が十分でな
くなり、樹脂Ｂが多すぎると常温付近で満足すべき制振
性を得ることが困難となる。The amount of each resin in the mixture of resins A and B is
5-95% by weight, preferably 30-70% by weight, resin 8
It is within the range of 5 to 95% by weight, preferably 30 to 70% by weight. If the amount of resin B is too large, the shear adhesive strength will not be sufficient, and if the amount of resin B is too large, it will be difficult to obtain satisfactory damping properties at around room temperature.
本発明で使用する線状飽和ポリエステル樹脂は、脂肪族
、脂環式もしくは芳香族の飽和多価カルボン酸と飽和多
価アルコールとから誘導された重合体であり、「飽和」
とは重合性の不飽和結合を有しない意味である。The linear saturated polyester resin used in the present invention is a polymer derived from an aliphatic, alicyclic, or aromatic saturated polycarboxylic acid and a saturated polyhydric alcohol, and is a "saturated"
This means that it does not have a polymerizable unsaturated bond.
飽和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、１．４−シク
ロヘキサンジカルボン酸、無水トリメリット酸などが挙
げられる。Examples of saturated polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2.6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 1.4-cyclohexane. Examples include dicarboxylic acid and trimellitic anhydride.
飽和多価アルコールの例には、エチレングリコ−／し、
１．４−ブタンジオール、ｌ、５−ベンタンジオール、
１，６−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、ポリ
テトラメチレングリコール、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、ハイドロキノン、スチレングリコールなどがある。Examples of saturated polyhydric alcohols include ethylene glycol,
1.4-butanediol, l,5-bentanediol,
1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, neopentyl glycol,
Examples include propylene glycol, 1,4-cyclohexane dimetatool, penquerythritol, trimethylolpropane, hydroquinone, and styrene glycol.
熱可塑性飽和ポリエステル樹脂は、周知のように、その
構成要素である多価カルボン酸および多価アルコールの
種類やその使用割合、および重合度によって各種のＴｇ
を有する重合物を得ることできる。As is well known, thermoplastic saturated polyester resins have various Tg values depending on the types and proportions of their constituent polyhydric carboxylic acids and polyhydric alcohols, and the degree of polymerization.
It is possible to obtain a polymer having the following.
本発明で用いる線状高分子量ポリエステルは、樹脂Ａお
よびＢのいずれに該当するものであっても、一般に水酸
基価が１〜５０の範囲内のものが望ましい。水酸基価は
、単位重量当たりの架橋点の多寡を示し、水酸基が低す
ぎると実質的に架橋点が少なくなり、架橋後に優れた接
着強度が得られない。また、水酸基価が高すぎると、架
橋密度が大きくなりすぎて、制振性が低下したり、また
延性が低下して加工性の劣化を生じたりする。Regardless of whether the linear high molecular weight polyester used in the present invention falls under either resin A or B, it is generally desirable that the hydroxyl value is within the range of 1 to 50. The hydroxyl value indicates the number of crosslinking points per unit weight, and if the hydroxyl group value is too low, the number of crosslinking points will substantially decrease, making it impossible to obtain excellent adhesive strength after crosslinking. On the other hand, if the hydroxyl value is too high, the crosslinking density becomes too large, resulting in a decrease in vibration damping properties and a decrease in ductility, resulting in deterioration in workability.
本発明で樹脂Ｂとして使用しうる高分子量エポキシ樹脂
は、ビスフェノールＡ系、ノボラック系、レゾルシン系
などのエポキシ樹脂゛でよく、分子量は上記のように３
．０００以上、好ましくは５０．０００以下の範囲内で
ある。The high molecular weight epoxy resin that can be used as resin B in the present invention may be a bisphenol A-based, novolac-based, resorcinol-based epoxy resin, etc., and the molecular weight is 3 as described above.
．． 000 or more, preferably 50,000 or less.
樹脂Ａと樹脂Ｂは有機溶媒にとかして溶液状で混合する
と、得られた樹脂ＡおよびＢを含有する溶液をそのまま
塗布液として利用できるので、割振積層体の形成に有利
である。When resin A and resin B are dissolved in an organic solvent and mixed in the form of a solution, the resulting solution containing resins A and B can be used as is as a coating liquid, which is advantageous for forming a distributed laminate.
本発明によれば、上述したように、芯材樹脂として２種
類の樹脂ＡおよびＢを単に混合物として用いるのではな
く、これを熱あるいはその他のエネルギーで相互に架橋
させて用いることにより、割振性を低下″させずに剪断
接着強度のみを著しく増加させることが予想外にも可能
であり、その結果、常温付近での制振性と剪断接着強度
に優れた割振積層体が得られるのである。According to the present invention, as described above, the two types of resins A and B are not simply used as a mixture as the core material resin, but are crosslinked with each other using heat or other energy, thereby improving the allocation property. It is unexpectedly possible to significantly increase only the shear adhesive strength without decreasing the oscillation rate, and as a result, a split laminate with excellent vibration damping properties and shear adhesive strength near room temperature can be obtained.
本発明において前記樹脂混合物の架橋は、熱エネルギー
により行うのが簡便であるが、紫外線、電子線などの他
のエネルギーを利用した方法も可能である。アミノ樹脂
、ポリイソシアネートなどの適当な多官能性物質を架橋
剤として配合すると、架橋時間の短縮が図れ、有利であ
る。樹脂Ｂにエポキシ樹脂を使用する場合には、エポキ
シ樹脂が架橋剤の作用を果たすので、別に架橋剤を添加
せずに線状飽和ポリエステルとエポキシ樹脂との架橋を
利用することもできるが、樹脂Ｂが飽和ポリエステル樹
脂のみの場合には、架橋剤を配合して架橋させる必要が
ある。エポキシ樹脂を使用する場合でも、架橋剤を配合
すると架橋時間の短縮が図られるので有利である。架橋
剤の使用量は、樹脂ＡおよびＢの合計１００重量部に対
して約５〜４０重量部の範囲内が好ましい。さらに、架
橋促進剤として酸触媒などを少量、たとえば樹脂混合物
合計１００重量部に対して０．５重量部以下の量で用い
てもよい。In the present invention, it is convenient to crosslink the resin mixture using thermal energy, but methods using other energies such as ultraviolet rays and electron beams are also possible. It is advantageous to incorporate a suitable polyfunctional substance such as an amino resin or polyisocyanate as a crosslinking agent, since the crosslinking time can be shortened. When using an epoxy resin as resin B, the epoxy resin acts as a crosslinking agent, so crosslinking between the linear saturated polyester and the epoxy resin can be used without adding a separate crosslinking agent. When B is only a saturated polyester resin, it is necessary to mix a crosslinking agent to effect crosslinking. Even when using an epoxy resin, it is advantageous to incorporate a crosslinking agent because the crosslinking time can be shortened. The amount of crosslinking agent used is preferably within the range of about 5 to 40 parts by weight based on the total of 100 parts by weight of resins A and B. Furthermore, an acid catalyst or the like may be used as a crosslinking promoter in a small amount, for example, in an amount of 0.5 parts by weight or less based on 100 parts by weight of the resin mixture in total.
本発明の制振積層体の樹脂層は、樹脂ＡおよびＢと、必
要により加えた架橋剤のみからなる架橋樹脂からなるこ
とが好ましいが、場合により、充填剤や熱劣化防止剤な
どの添加剤を中間樹脂層に少量存在させることもできる
。The resin layer of the damping laminate of the present invention is preferably made of a crosslinked resin consisting only of resins A and B and a crosslinking agent added as necessary, but in some cases, additives such as fillers and thermal deterioration inhibitors may be added. can also be present in a small amount in the intermediate resin layer.
本発明の複合型制振積層体は、たとえば次のようにして
製造することができる。まず、ガラス転移温度０℃以下
の線状飽和ポリエステル樹Ｄｉ！Ａと、ガラス転移温度
３０℃以上の線状飽和ポリエステル樹脂、高分子量エポ
キシ樹脂およびこれらの混合物から選んだ樹脂Ｂとを混
合して塗布液を形成する。樹脂の分子量がいずれも比較
的低い場合には、溶剤を使用せずに塗布に適した粘度の
混合物が得られることもあるが、通常は樹脂を溶剤で希
釈した溶液状で混合することが、塗装性および混合の容
易さの観点から好ましい。この場合、たとえば各樹脂を
別々に同じ溶剤あるいは混和性の異種溶剤に溶解させ、
得られた溶液を混合することによって塗布液を形成して
もよく、または樹脂ＡおよびＢを一緒に適当な溶剤に溶
解してもよい、好ましくは、この溶液に適当な架橋剤を
配合する。使用する溶剤および塗布液の濃度は、樹脂層
、塗膜厚みなどにより適宜決定する。The composite damping laminate of the present invention can be manufactured, for example, as follows. First, a linear saturated polyester tree Di! with a glass transition temperature of 0°C or less! A and a resin B selected from a linear saturated polyester resin having a glass transition temperature of 30° C. or higher, a high molecular weight epoxy resin, and a mixture thereof are mixed to form a coating liquid. If the molecular weights of the resins are all relatively low, a mixture with a viscosity suitable for coating may be obtained without using a solvent, but usually it is better to mix the resins in the form of a solution diluted with a solvent. Preferred from the viewpoint of paintability and ease of mixing. In this case, for example, each resin is dissolved separately in the same solvent or in different miscible solvents,
A coating solution may be formed by mixing the resulting solutions, or resins A and B may be dissolved together in a suitable solvent, preferably a suitable crosslinking agent is incorporated into this solution. The concentration of the solvent and coating liquid to be used is appropriately determined depending on the resin layer, coating thickness, etc.
所望により適宜の下地処理を施し、表面を清浄化した鋼
板などの金属板の片面に、上で得られた塗布液を塗装す
る。この塗装は、ロールコータ−、カーテンフローコー
ターなどの塗装機により行うのが簡便であるが、その他
の塗装方法も採用できる０次いで、金属板を焼付けて塗
布した樹脂混合物を架橋させる。塗布液が溶剤で希釈さ
れたものである場合には、溶剤の連敗と樹脂の焼付架橋
を同時に行うことが望ましい、焼付条件は、樹脂層や架
橋剤により異なるが、一般に約１００〜３００℃で３０
秒〜１時間程度である。The coating liquid obtained above is applied to one side of a metal plate, such as a steel plate, which has been subjected to an appropriate surface treatment if desired and whose surface has been cleaned. This coating is conveniently carried out using a coating machine such as a roll coater or a curtain flow coater, but other coating methods can also be used.Next, the metal plate is baked and the applied resin mixture is crosslinked. If the coating solution is diluted with a solvent, it is desirable to simultaneously carry out continuous failure of the solvent and baking and crosslinking of the resin. Baking conditions vary depending on the resin layer and crosslinking agent, but are generally about 100 to 300°C. 30
It is about seconds to 1 hour.
焼付架橋後、もう一枚の金属板（これは、塗膜を有しな
いものでも、あるいは上記方法により片面に樹脂混合物
の架橋塗膜を形成した金属板でもよい）を供給し、樹脂
塗膜面が内側になるように２枚の金属板を重ね合わせて
熱圧着することによ２す、強固に接着した割振積層体が
得られる。上下の金属板の両方に上記樹脂混合物を塗布
し、焼付架橋させる方が、より良好な剪断接着強度が得
られる傾向がある。もちろん、焼付架橋した際の予熱を
利用して熱圧着すると、製造コストの低減に有利なこと
はいうまでもない、熱圧着の温度は、一般に約１００〜
３００℃である。場合によっては、上記の焼付架橋と熱
圧着とを岡崎に、たとえば熱プレスのみで行うこともで
きる。After crosslinking by baking, another metal plate (this may be a metal plate without a coating film or a metal plate with a crosslinked coating film of a resin mixture formed on one side by the above method) is supplied, and the resin coating surface is By superimposing two metal plates so that the metal plates are on the inside and bonding them under heat, a strongly bonded divided laminate can be obtained. Better shear adhesive strength tends to be obtained when the resin mixture is applied to both the upper and lower metal plates and crosslinked by baking. Of course, it goes without saying that thermocompression bonding using preheating during baking crosslinking is advantageous in reducing manufacturing costs.
The temperature is 300°C. In some cases, the baking crosslinking and thermocompression bonding described above may be performed using Okazaki, for example, only by hot pressing.
本発明の制振積層体において、外側の金属板としては、
冷延鋼板、亜鉛系めっき調板、アルミニウム系めっき鋼
板、ステンレス鋼板などの綱板が主に用いられるが、他
の金属板、たとえばアルミニウム板なども用途により使
用できる。また、鋼板の下地処理としては、コロイダル
シリカを含有する塗布型クロメート処理を施すことが望
ましい。In the vibration damping laminate of the present invention, as the outer metal plate,
Steel plates such as cold-rolled steel plates, zinc-plated conditioned plates, aluminum-plated steel plates, and stainless steel plates are mainly used, but other metal plates such as aluminum plates can also be used depending on the purpose. Furthermore, as a surface treatment for the steel sheet, it is desirable to perform a coating type chromate treatment containing colloidal silica.
特に、使用鋼板が亜鉛系めっき鋼板である場合、塗布型
クロメート処理を施すことにより、割振性、接着強度が
共に向上する。所望により、他の下地処理を通用しても
よい、 ゛
以下、実施例により、本発明をさらに詳しく説明する。Particularly, when the steel sheet used is a zinc-based plated steel sheet, applying the coating type chromate treatment improves both the splitting property and the adhesive strength. If desired, other surface treatments may be used. The present invention will be explained in more detail below with reference to Examples.
′ １および・ １〜２
東洋紡■製の線状高分子量飽和ポリエステル、バイロン
１０３Ｎ （Ｔ ｇ ４７℃、分子量約２万、水酸基価
５）をトルエン／メチルエチルケトン（ＭＥＫ）（４：
１）混合溶媒にとかして得た２０重量％溶液と、同社製
の同様の線状飽和ポリエステル、バイロンＲＶ５５０
（Ｔ ｇ−１５℃、分子量約２万、水酸基価５）をトル
エン／ＭＥＫ （４：１）混合溶媒にとかして得た２０
重量％溶液とを同量づつ混合して、塗布液（以下、Ａ液
という）を形成した。1 and 1-2 A linear high molecular weight saturated polyester manufactured by Toyobo ■, Vylon 103N (T g 47°C, molecular weight approximately 20,000, hydroxyl value 5) was mixed with toluene/methyl ethyl ketone (MEK) (4:
1) A 20% by weight solution obtained by dissolving in a mixed solvent and a similar linear saturated polyester manufactured by the same company, Vylon RV550.
(Tg-15℃, molecular weight approximately 20,000, hydroxyl value 5) was dissolved in a toluene/MEK (4:1) mixed solvent.
A coating solution (hereinafter referred to as "Liquid A") was formed by mixing the same amount of the solution by weight.
このＡ液に、架橋剤として住友化学工業■製のメラミン
樹脂、スミマール４０Ｓを、Ａ液中の線状飽和ポリエス
テル合計１００重量部に対して２４重量部となるように
混合した塗布液（Ｂ液）、およびＡ液に別の架橋剤とし
て日本ポリウレタン■製のプロンクトイソシアネート、
コロネート２５１３を、Ａ液中の線状飽和ポリエステル
合計１００！１．１部に対して８重量部となるように混
合した塗布液（Ｃ液）をそれぞれ準備した。A coating liquid (liquid B) was mixed with Sumimaru 40S, a melamine resin manufactured by Sumitomo Chemical Co., as a crosslinking agent, in an amount of 24 parts by weight based on a total of 100 parts by weight of the linear saturated polyester in liquid A. ), and Pronctoisocyanate manufactured by Nippon Polyurethane ■ as another crosslinking agent in liquid A,
Coating liquids (liquid C) were prepared in which Coronate 2513 was mixed in an amount of 8 parts by weight based on a total of 100!1.1 parts of linear saturated polyester in liquid A.
別に、関西ペイント■製の塗布型クロメート処理液、コ
スマー１００によりクロム付着量が１００−ｇ／イとな
るようにクロメート処理した０、８鶴厚の冷延鋼板を２
枚用意した。Separately, two cold-rolled steel sheets with a thickness of 0.8 mm were chromate-treated with Cosmer 100, a coating type chromate treatment solution manufactured by Kansai Paint ■, so that the amount of chromium deposited was 100-g/I.
I prepared one.
この冷延鋼板のそれぞれについて、そのクロメート処理
面に、上で用意したＡ液をバーコーターにより乾燥塗膜
厚みが１５μｍとなるように塗装した。得られた２枚の
塗装鋼板を１１０℃の熱風オーブン中で１０分間焼付し
て、溶媒の連敗と樹脂の焼付架橋とを行った０次いで、
オーブンから取り出した冷延鋼板を、その塗装面どうし
が接するように重ね合わせ、１７０℃の熱プレスにより
３０ｋｇ／ｃｄの圧力で１０分間熱圧着し、室温まで同
じ加圧下に冷却した。このようにして、０．８鶴厚の冷
延鋼板の間に３０μ−の芯材樹脂層が挟まった制振鋼板
を得た。The chromate-treated surface of each of the cold-rolled steel sheets was coated with the above-prepared liquid A using a bar coater so that the dry coating thickness was 15 μm. The two obtained coated steel plates were baked in a hot air oven at 110°C for 10 minutes to cause continuous loss of the solvent and baking crosslinking of the resin.
The cold-rolled steel plates taken out of the oven were stacked so that their coated surfaces were in contact with each other, thermocompression bonded at a pressure of 30 kg/cd for 10 minutes using a hot press at 170°C, and cooled to room temperature under the same pressure. In this way, a damping steel plate was obtained in which a 30 μm core resin layer was sandwiched between 0.8 mm thick cold rolled steel plates.
同様の方法により、Ｂ液およびＣ液をそれぞれ使用して
、上記と同じ構成の制振鋼板を製造した。A damping steel plate having the same structure as above was manufactured using the B liquid and the C liquid in the same manner.
得られた制振鋼板より、油圧電動シャーにより試験片を
切出し、損失係数と剪断接着強度を測定した。A test piece was cut out from the obtained damping steel plate using a hydraulic electric shear, and the loss coefficient and shear adhesive strength were measured.
損失係数（η）の測定は、機械インピーダンス法により
、インピーダンスヘッドにはＢ＆に社製のａｓｏｏｉを
、解析装置には明石製作所■製のＡＶＡ−■型を用いて
行った。試験片の寸法は、幅２０ｆｉ×長さ２２０鶴で
あった・
剪断接着強度の測定は、２５．４ｎ （１インチ）幅に
切断した試験片に対して、第１図に示すように１２．５
ｎの継手長さになるようにノツチ加工を施し、試験温度
２３℃、引張速度５ ｍ／ｓｉｎの条件でインストロン
型万能引張試験機により試験片両端を引張リ、接着破壊
荷重を求めることにより行った。The loss coefficient (η) was measured by a mechanical impedance method using an asooi manufactured by B&NI Co., Ltd. as an impedance head and an AVA-■ model manufactured by Akashi Seisakusho ■ as an analysis device. The dimensions of the test piece were 20fi wide x 220mm long. The shear adhesive strength was measured using a test piece cut to a width of 25.4n (1 inch) at 12mm as shown in Figure 1. 5
The joint was notched to a joint length of n, and both ends of the test piece were pulled using an Instron universal tensile tester at a test temperature of 23°C and a tensile speed of 5 m/sin, and the adhesion failure load was determined. went.
結果を次の第１表に示す。第１表において、損失係数は
３３℃、１０００ Ｈｚでの測定値である。第１表の結
果から明らかなように、２種の飽和ポリエステル樹脂を
実質的に架橋させていない比較例１の割振鋼板では、常
温付近での割振性には非常に優れているものの、剪断接
着強度が著しく劣っている。これに対して、本発明例で
ある実施例１および２の制振鋼板においては、樹脂混合
物の架橋により、比較例１の制振鋼板の損失係数を実質
的に維持したまま、剪断接着強度が飛曜的に増大してい
る。The results are shown in Table 1 below. In Table 1, the loss coefficients are measured at 33° C. and 1000 Hz. As is clear from the results in Table 1, the split steel plate of Comparative Example 1, in which the two types of saturated polyester resins are not substantially crosslinked, has excellent split properties at room temperature, but The strength is significantly lower. In contrast, in the damping steel plates of Examples 1 and 2, which are examples of the present invention, the shear adhesive strength was increased while substantially maintaining the loss coefficient of the damping steel plate of Comparative Example 1 due to crosslinking of the resin mixture. It is increasing exponentially.
第１表
３１１例」−
上記Ｂ液におけるスミマール４０５の添加量が、線状飽
和ポリエステル合計１００重量部に対して１２重量部で
あること、熱プレス温度と時間が２００℃、３０分であ
ること以外は実施例１と全く同様にして、割振鋼板を製
造した。得られた割振鋼板の剪断接着強度は、１０１．
１ ｋｇ／、ｆｆｌであり、４０℃、１０００ Ｈｚで
の損失係数は１．０５であった。Table 1 Example 311 - The amount of Sumimaru 405 added in the above B solution is 12 parts by weight based on the total 100 parts by weight of the linear saturated polyester, and the hot press temperature and time are 200°C and 30 minutes. A split steel plate was manufactured in the same manner as in Example 1 except for this. The shear adhesive strength of the obtained split steel plate was 101.
1 kg/, ffl, and the loss coefficient at 40° C. and 1000 Hz was 1.05.
大血斑土二ｌ
実施例１で使用したＢ液に、さらに住友化学工業■製の
ノボラック型エポキシ樹脂、スミエポキシＥＳＣＮ−２
２０−１８（分子量３５００、エポキシ当量２００、軟
化点７０℃）を、Ｂ液中のポリエステル樹脂１００重量
部に対して５重量部の割合で添加した塗布液（Ｄ液）を
調製した。このＤ液を用いて、予めコスマーｌＯＯによ
りクロム付着量が８０＋ｗｇ／ｒｄとなるようにクロメ
ート皮膜が形成されている０、６ ｍ厚の冷延鋼板帯の
クロメート皮膜上に、ロールコータ−により乾燥塗膜厚
みが１５μ鴎となるように塗装した。その後、３００℃
の熱風オーブン内を、実施例４においては４５秒、実施
例５においては１分３０秒間の滞留時間で通過させて、
溶媒の揮散と樹脂の焼付架橋を行った。その時の鋼板表
面での最高到達温度は、４５秒滞留の実施例４では１７
５℃、９０秒滞留の実施例５では２３５℃であった。そ
の後、比較例１と同様の方法で制振鋼板を得、剪断接着
強度と損失係数を測定した。結果を次の第２表に示す。In addition to the B solution used in Example 1, a novolac type epoxy resin manufactured by Sumitomo Chemical Co., Ltd., Sumiepoxy ESCN-2
A coating liquid (liquid D) was prepared by adding 20-18 (molecular weight 3500, epoxy equivalent weight 200, softening point 70°C) at a ratio of 5 parts by weight to 100 parts by weight of the polyester resin in liquid B. Using this D solution, dry with a roll coater on the chromate film of a 0.6 m thick cold-rolled steel sheet strip, on which a chromate film has been formed in advance with Cosmar 1OO so that the chromium adhesion amount is 80 + wg/rd. The coating was applied so that the coating film thickness was 15 μm. After that, 300℃
The sample was passed through a hot air oven with a residence time of 45 seconds in Example 4 and 1 minute and 30 seconds in Example 5,
The solvent was evaporated and the resin was crosslinked by baking. The maximum temperature reached on the steel plate surface at that time was 17 in Example 4 where the residence time was 45 seconds.
In Example 5, which was held at 5°C for 90 seconds, the temperature was 235°C. Thereafter, a damping steel plate was obtained in the same manner as in Comparative Example 1, and the shear adhesive strength and loss coefficient were measured. The results are shown in Table 2 below.
第２表
損失係数は４０℃、１０００ ｆｉｚでの測定値である
。The loss coefficients in Table 2 are measured values at 40° C. and 1000 fiz.
実施例５では、実施例１に比べて剪断接着強度がさらに
大きく増大していることがわかる。It can be seen that in Example 5, the shear adhesive strength is further increased compared to Example 1.
実ｌ桝旦二工
使用鋼板が０．６ ｍ厚の合金化溶融亜鉛めっき鋼板で
あること、熱プレス温度が１５０℃であること以外は実
施例４と全く同様にして、制振ｔｊ４板を製造した。た
だし、実施例６では塗装に先立ってクロメート処理を施
さず、実施例７では、１５ｍｇ／ｎｆのクロム付着量に
なるように塗布型クロメート処理を下地処理として施し
た。結果を次の第３表に示す。A damping TJ4 plate was prepared in exactly the same manner as in Example 4, except that the steel plate used was a 0.6 m thick alloyed hot-dip galvanized steel plate and the heat press temperature was 150°C. Manufactured. However, in Example 6, chromate treatment was not performed prior to painting, and in Example 7, coating type chromate treatment was performed as a base treatment so that the amount of chromium deposited was 15 mg/nf. The results are shown in Table 3 below.
第３表 損失係数は４０℃、１０００ Ｈｚでの測定値である。Table 3 The loss factor is a value measured at 40° C. and 1000 Hz.
第３表から、外板が亜鉛系めっき鋼板である場合には、
塗布型クロメート処理を下地として施すことにより、剪
断接着強度と損失係数がともに向上することがわかる。From Table 3, if the outer plate is a galvanized steel plate,
It can be seen that both the shear adhesive strength and the loss coefficient are improved by applying the coated chromate treatment as a base.
＝ ８および へ１２
東洋紡側製バイロン１０３Ｎの代わりに、同社製の線状
高分子ｆｌ飽和熱可塑性ポリエステル、バイロンＧＫ５
９０ （Ｔ ｇ １０℃、分子量４０００、水酸基価３
０）、またＩＩＶ５５０の代わりに線状高分子量飽和熱
可塑性ポリエステル、バイロン５５００（Ｔ ｇ−１１
’ｃ、分子量約２万、水酸基価４）をそれぞれ同量使用
し、その他は実施例４と全く同様の方法で制振鋼板を製
造した〈実施例８）、得られた割振鋼板の剪断接着強度
は８９．２ｋｇ／ｃｊ、４０℃、１０００１１２での損
失係数は０．６７であった。= 8 and 12 Instead of Byron 103N manufactured by Toyobo, a linear polymer fl saturated thermoplastic polyester manufactured by Toyobo, Byron GK5
90 (T g 10℃, molecular weight 4000, hydroxyl value 3
0), and a linear high molecular weight saturated thermoplastic polyester, Vylon 5500 (T g-11
'c, molecular weight approximately 20,000, and hydroxyl value 4) were used in the same amounts, respectively, and a damping steel plate was produced in the same manner as in Example 4 (Example 8). Shear adhesion of the obtained distributed steel plate The strength was 89.2 kg/cj, and the loss coefficient at 40° C. and 1000112 was 0.67.
比較のためにこの２種類の飽和ポリエステル樹脂を使用
して、比較例１と同様の方法で制振鋼板を製造したとこ
ろ、得られた割振鋼板の剪断接着強度は６．７ｋｇ／ｃ
＋Ｊ、４０℃、１０００ Ｈ２での損失係数は０．７８
であり、上記ポリエステル樹脂混合物の場合でも、樹脂
を実質的に架橋させないと、剪断接着強度は実施例８の
制ＷＬ鋼板の１０分の１以下と実用に供し得ない程度に
大きく低下した。For comparison, a damping steel plate was manufactured in the same manner as in Comparative Example 1 using these two types of saturated polyester resins, and the shear adhesive strength of the resulting divided steel plate was 6.7 kg/c.
Loss coefficient at +J, 40℃, 1000H2 is 0.78
Even in the case of the above-mentioned polyester resin mixture, unless the resin was substantially crosslinked, the shear adhesive strength was significantly lower than one-tenth of that of the WL steel plate of Example 8, to the extent that it could not be put to practical use.
大嵐■主
実施例３を繰り返したが、ただし塗装後の鋼板を熱風オ
ープンに通さず、溶剤の蒸発による塗膜の乾燥のみで鋼
板を重ね合わせ、３０ｋｇ／−の加圧下に１８０℃で１
０分間熱プレスすることによって、塗膜の架橋と積層体
の熱圧着とを同時に行った。Daiarashi ■Main Example 3 was repeated, but the steel plates after coating were not passed through open hot air, but the steel plates were stacked together only by drying the coating film by evaporation of the solvent, and the steel plates were stacked together at 180℃ under a pressure of 30 kg/-.
By hot pressing for 0 minutes, crosslinking of the coating film and thermocompression bonding of the laminate were simultaneously performed.
得られた制振鋼板の剪断接着強度は７０ｋｇ／ｃｄ。The shear adhesive strength of the obtained damping steel plate was 70 kg/cd.
４０℃、１０００ Ｈｚでの損失係数は１．２２であっ
た。焼付工程を省略したことによる架橋密度の低下のた
め、実施例３に比べて損失係数は向上したが、剪断接着
強度がいくらか低下した。ただし、架橋のない比較例１
の割振鋼板に比べてなお十分に高い剪断接着強度を保持
している。The loss factor at 40°C and 1000 Hz was 1.22. Although the loss factor was improved compared to Example 3 due to the reduction in crosslinking density due to the omission of the baking step, the shear adhesive strength was somewhat reduced. However, Comparative Example 1 without crosslinking
It still maintains a sufficiently high shear bond strength compared to split steel plates.
ｌ施■用
実施例１において、バイロン１０３Ｎに代えて同じ量で
東部化成側製のビスフェノールＡとエピクロルヒドリン
との縮合生成物である高分子量エポキシ樹脂ＹＰ−５０
（分子量４０，０００ 、Ｔ ｇ ８６℃）を用いるこ
と以外実施例１と全く同様の方法で割振鋼板を製造した
。得られた制振鋼板の剪断接着強度は９７ｋｇ／ｃ＋ａ
、 ４０℃、１０００ Ｈｚでの損失係数は０．６３で
あった。ＴｇｌＯ℃以上の高分子量熱可塑性ポリエステ
ルに代えて高分子量エポキシ樹脂を使用しても、はぼ同
程度の好結果が得られるととがわかる。l In Application Example 1, high molecular weight epoxy resin YP-50, which is a condensation product of bisphenol A and epichlorohydrin manufactured by Tobu Kasei Co., Ltd., was used in place of Vylon 103N in the same amount.
(Molecular weight: 40,000, T g: 86° C.) A cracked steel plate was manufactured in exactly the same manner as in Example 1 except that the same method was used as in Example 1. The shear adhesive strength of the obtained damping steel plate was 97 kg/c+a
, the loss factor at 40°C and 1000 Hz was 0.63. It can be seen that even if a high molecular weight epoxy resin is used in place of the high molecular weight thermoplastic polyester having a TglO°C or higher, almost the same good results can be obtained.
几ｔびＬレニ土
実施例１において、Ｔｇが１０℃以上のバイロン１０３
Ｎを除外したこと以外は全〈実施例１と同様の方法で制
振鋼板を製造したく比較例３）。In Example 1, Byron 103 with a Tg of 10°C or more
All except for excluding N (Comparative Example 3) in which a damping steel plate was manufactured in the same manner as in Example 1.
別の実験で、Ｔｇが０℃以下のバイロンＲＶ５５０を除
外して実施例１を繰り返し、制振鋼板を得た（比較例４
）、得られた結果を次の第４表に示す。In another experiment, Example 1 was repeated except for Byron RV550, which had a Tg of 0°C or less, to obtain a damping steel plate (Comparative Example 4).
), the results obtained are shown in Table 4 below.
なお、損失係数は４０℃、１０００ Ｈｚでの測定値で
ある。Note that the loss coefficient is a value measured at 40° C. and 1000 Hz.
第４表
第４表の結果から、いずれか一方の熱可塑性ポリエステ
ル樹脂のみでは、樹脂の架橋を行っても、常温付近での
優れた割振性と高い剪断接着強度とを両立させることが
まったくできないことがわかる。具体的には、比較例３
のＴｇが０℃以下のポリエステル樹脂のみの例では、剪
断接着強度が５ｋｇ／ａｊ以下と実用的な強度からほど
遠く、また比較例４のＴｇが１０℃以上のポリエステル
樹脂のみの例では損失係数が０．０３以下と制振性が全
く発揮されていない。Table 4 From the results in Table 4, it is clear that with only one thermoplastic polyester resin, even if the resin is crosslinked, it is completely impossible to achieve both excellent splitting properties and high shear adhesive strength near room temperature. I understand that. Specifically, Comparative Example 3
In an example using only a polyester resin with a Tg of 0°C or less, the shear adhesive strength is 5 kg/aj or less, which is far from a practical strength, and in an example of Comparative Example 4 using only a polyester resin with a Tg of 10°C or more, the loss factor is It is 0.03 or less, meaning that vibration damping properties are not exhibited at all.
（発明の効果）
本発明により、芯材樹脂として使用するガラス転移温度
の異なる２種類の特定の樹脂の混合物を架橋させること
ににより、常温付近の比較的低温での優れた制振性（損
失係数０．５以上）を維持しなから制振積層体の剪断接
着強度を著しく向上させることが可能となり、これまで
困難であった常温付近での良好な制振性と十分に高い剪
断接着強度の両立が図られた制振積層体を得ることがで
きる。この両立は、樹脂混合物の架橋を省略したり、あ
るいは一方の樹脂を省略した場合には全（得ることがで
きず、本発明により得られる予想外の効果である。(Effects of the Invention) According to the present invention, by crosslinking a mixture of two specific resins with different glass transition temperatures used as core material resins, excellent vibration damping properties (loss loss) at relatively low temperatures near room temperature are achieved. It is now possible to significantly improve the shear adhesive strength of vibration damping laminates without maintaining a coefficient of 0.5 or more, which has been difficult until now, with good vibration damping properties and sufficiently high shear adhesive strength near room temperature. It is possible to obtain a vibration damping laminate that achieves both of the following. This coexistence cannot be achieved by omitting crosslinking of the resin mixture or by omitting one of the resins, and is an unexpected effect obtained by the present invention.
本発明の制振積層体およびその製造方法はまた、従来使
用されてきた芯材樹脂種を利用し、樹脂の塗布法もロー
ルコータ−などの簡便な装置を利用して実施でき、熱圧
着法も従来と同様でよいので、従来の装置を利用して、
従来は得られなかったような常温付近で優れた制振性と
加工性を発揮する割振積層体を比較的安価に提供するこ
とができるので、制振鋼板などの制振積層体の用途拡大
に大きく寄与するであろう。The damping laminate of the present invention and its manufacturing method also utilize a core resin type that has been conventionally used, and the resin coating method can be performed using a simple device such as a roll coater, and the thermocompression bonding method can be used. can be the same as before, so using conventional equipment,
It is possible to provide distributed laminates at a relatively low cost that exhibit excellent vibration damping properties and workability near room temperature, which were not previously possible, so it is possible to expand the use of vibration damping laminates such as damping steel plates. It will make a big contribution.
第１図は、実施例で行った剪断接着強度の測定試験にお
いて試験片に施したノツチ加工を示す説明図である。
出願人 住友金属工業株式会社（ほか１名）代理人 弁
理士 広 瀬 章 −（ｌｊ ６゛／ ｊｂ）第１図FIG. 1 is an explanatory view showing the notch processing applied to the test piece in the shear adhesive strength measurement test conducted in the example. Applicant: Sumitomo Metal Industries, Ltd. (and one other person) Representative: Akira Hirose, patent attorney - (lj 6゛/ jb) Figure 1
Claims (6)
振積層体において、前記樹脂層が、（Ａ）および（Ｂ）
の合計重量に基づいて（Ａ）ガラス転移温度０℃以下の
線状高分子量飽和ポリエステル樹脂５〜９５重量％と、
（Ｂ）ガラス転移温度１０℃以上の線状高分子量飽和ポ
リエステル樹脂、高分子量エポキシ樹脂、またはこれら
の混合物５〜９５重量％とを含有する樹脂混合物を架橋
して得た樹脂から構成されることを特徴とする、複合型
制振積層体。(1) In a composite vibration damping laminate formed by sandwiching a resin layer between two metal plates, the resin layer includes (A) and (B).
(A) 5 to 95% by weight of a linear high molecular weight saturated polyester resin with a glass transition temperature of 0° C. or lower, based on the total weight of;
(B) Consists of a resin obtained by crosslinking a resin mixture containing a linear high molecular weight saturated polyester resin with a glass transition temperature of 10°C or higher, a high molecular weight epoxy resin, or a mixture thereof containing 5 to 95% by weight. A composite vibration damping laminate featuring:
請求の範囲第１項記載の複合型制振積層体。(2) The composite damping laminate according to claim 1, wherein the resin mixture further contains a crosslinking agent.
振積層体の製造方法において、（Ａ）と（Ｂ）の合計重
量に基づいて（Ａ）ガラス転移温度０℃以下の線状高分
子量飽和ポリエステル樹脂５〜９５重量％と、（Ｂ）ガ
ラス転移温度１０℃以上の線状高分子量飽和ポリエステ
ル樹脂、高分子量エポキシ樹脂、またはこれらの混合物
５〜９５重量％とを含有する樹脂混合物を前記金属板の
少なくとも一方の片面に塗装し、得られた塗膜を焼付け
て上記樹脂混合物を架橋させ、この架橋塗膜を内側にし
て前記２枚の金属板を重ね合わせ、熱圧着させて積層体
を得ることを特徴とする複合型制振積層体の製造方法。(3) In the method for manufacturing a composite vibration damping laminate in which a resin layer is sandwiched between two metal plates, based on the total weight of (A) and (B), (A) a line with a glass transition temperature of 0°C or less A resin containing 5 to 95% by weight of a linear high molecular weight saturated polyester resin, and (B) 5 to 95 weight% of a linear high molecular weight saturated polyester resin, high molecular weight epoxy resin, or a mixture thereof having a glass transition temperature of 10°C or higher. The mixture is coated on at least one side of the metal plate, the resulting coating film is baked to crosslink the resin mixture, and the two metal plates are superimposed with this crosslinked coating film on the inside, and bonded by thermocompression. 1. A method for producing a composite vibration damping laminate, the method comprising: obtaining a laminate.
請求の範囲第３項記載の方法。(4) The method according to claim 3, wherein the resin mixture further contains a crosslinking agent.
る、特許請求の範囲第３項または第４項記載の方法。(5) The method according to claim 3 or 4, wherein the crosslinked coating film is formed on both of the two metal plates.
べき面を塗布型クロメート処理により下地処理する、特
許請求の範囲第３項〜第５項のいずれかに記載の方法。(6) The method according to any one of claims 3 to 5, wherein the surface of the metal plate to be coated is subjected to a base treatment by coating-type chromate treatment before coating with the resin mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3537687A JPS63202446A (en) | 1987-02-18 | 1987-02-18 | Composite type vibration-damping laminate and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3537687A JPS63202446A (en) | 1987-02-18 | 1987-02-18 | Composite type vibration-damping laminate and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63202446A true JPS63202446A (en) | 1988-08-22 |
Family
ID=12440180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3537687A Pending JPS63202446A (en) | 1987-02-18 | 1987-02-18 | Composite type vibration-damping laminate and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63202446A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411810A (en) * | 1992-06-30 | 1995-05-02 | Toyo Boseki Kabushiki Kaisha | Viscoelastic resin composition for a vibration damping material |
| JP2008163277A (en) * | 2007-01-05 | 2008-07-17 | Nippon Tokushu Toryo Co Ltd | Two-pot room temperature-curing coating type damping paint composition |
| US7921961B2 (en) | 2004-12-03 | 2011-04-12 | Nippon Steel Corporation | Chromate-free resin-composite vibration deadening material |
-
1987
- 1987-02-18 JP JP3537687A patent/JPS63202446A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411810A (en) * | 1992-06-30 | 1995-05-02 | Toyo Boseki Kabushiki Kaisha | Viscoelastic resin composition for a vibration damping material |
| US7921961B2 (en) | 2004-12-03 | 2011-04-12 | Nippon Steel Corporation | Chromate-free resin-composite vibration deadening material |
| JP2008163277A (en) * | 2007-01-05 | 2008-07-17 | Nippon Tokushu Toryo Co Ltd | Two-pot room temperature-curing coating type damping paint composition |
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