JP6295832B2 - Aluminum-rubber composite and method for producing the same - Google Patents
Aluminum-rubber composite and method for producing the same Download PDFInfo
- Publication number
- JP6295832B2 JP6295832B2 JP2014110330A JP2014110330A JP6295832B2 JP 6295832 B2 JP6295832 B2 JP 6295832B2 JP 2014110330 A JP2014110330 A JP 2014110330A JP 2014110330 A JP2014110330 A JP 2014110330A JP 6295832 B2 JP6295832 B2 JP 6295832B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- rubber
- chemical conversion
- rubber composite
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims description 84
- 239000005060 rubber Substances 0.000 title claims description 84
- 239000002131 composite material Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000463 material Substances 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 229910052782 aluminium Inorganic materials 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 229910000838 Al alloy Inorganic materials 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 238000007739 conversion coating Methods 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 241001247986 Calotropis procera Species 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 229920005549 butyl rubber Polymers 0.000 claims description 5
- 229920005555 halobutyl Polymers 0.000 claims description 5
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 229910018566 Al—Si—Mg Inorganic materials 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 101100162020 Mesorhizobium japonicum (strain LMG 29417 / CECT 9101 / MAFF 303099) adc3 gene Proteins 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101100434411 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) ADH1 gene Proteins 0.000 description 1
- 229910018594 Si-Cu Inorganic materials 0.000 description 1
- 229910008465 Si—Cu Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 101150102866 adc1 gene Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Description
本発明は、車両や各種産業機械等において様々な防振材として好適に使用できるアルミ−ゴム複合体及びその製造方法に関する。 The present invention relates to an aluminum-rubber composite that can be suitably used as various vibration-proofing materials in vehicles, various industrial machines, and the like, and a method for producing the same.
車両や各種産業機械等には、運転・稼働時の振動や騒音等を抑制するために多くの防振材が使われている。例えば、自動車にはトーショナルダンパー、エンジンマウント、ラバーブッシュ等の防振材が取り付けられている。このような防振材では、構造的な強さと防振性能を両立させる観点から、鉄、アルミニウム、銅、亜鉛及びステンレス等の金属並びに各種合金とゴム材料とを一体化した複合体が使用されている。最近では、主に軽量化の観点から金属としてアルミニウム及び／又はアルミニウム合金からなるアルミ系金属を使用したアルミ−ゴム複合体が多く使用されている。 Many anti-vibration materials are used in vehicles and various industrial machines in order to suppress vibration and noise during operation and operation. For example, vibration-proof materials such as torsional dampers, engine mounts, and rubber bushes are attached to automobiles. In such an anti-vibration material, from the viewpoint of achieving both structural strength and anti-vibration performance, a composite that integrates metals such as iron, aluminum, copper, zinc, and stainless steel and various alloys and rubber materials is used. ing. Recently, mainly from the viewpoint of weight reduction, an aluminum-rubber composite using an aluminum-based metal made of aluminum and / or an aluminum alloy is often used.
これらの複合体では、金属とゴム材料とが強固に接合されることが求められているが、金属の表面が腐食して、金属とゴム材料との接着剥離（界面破壊）が進行し、その機能が十分に発揮されなくなるおそれがある。そこで、通常は接着下地処理として、金属にクロメート処理等の表面処理を行うことにより腐食を抑制している。しかしながら、上記クロメート処理で用いる処理液、及び当該処理で形成される化成皮膜には発癌性物質の６価クロムが含まれており、近年、作業環境及び自然環境保全の面からその使用が厳しく制限されている。特に欧州や日本等の自動車業界では、この６価クロムを含む製品及び部材は全廃されており、その他の産業界でも使用が規制されている。 In these composites, the metal and the rubber material are required to be strongly bonded, but the metal surface is corroded, and the adhesion peeling (interfacial fracture) between the metal and the rubber material proceeds. There is a risk that the function will not be fully demonstrated. Therefore, the corrosion is usually suppressed by performing a surface treatment such as chromate treatment on the metal as an adhesive base treatment. However, the treatment liquid used in the chromate treatment and the chemical conversion film formed by the treatment contain hexavalent chromium as a carcinogenic substance. In recent years, its use is severely restricted from the viewpoint of working environment and natural environment conservation. Has been. In particular, in the automobile industry such as Europe and Japan, the products and components containing hexavalent chromium are completely abolished, and the use is restricted in other industries.
これに対し、代替処理として３価クロムやジルコニウム等を使用した化成処理が提案されているが、クロメート処理と同等の性能を得ることは難しい。従って、接着下地処理としても６価クロムフリーの代替化成処理が必要とされており、また、６価クロムを使用しない製品の開発も重要な課題となっている。 On the other hand, chemical conversion treatment using trivalent chromium, zirconium, or the like has been proposed as an alternative treatment, but it is difficult to obtain performance equivalent to chromate treatment. Therefore, a hexavalent chromium-free alternative chemical conversion treatment is required as an adhesive base treatment, and the development of a product that does not use hexavalent chromium is an important issue.
なお、本発明に関連する先行技術文献としては下記のものが挙げられる。 In addition, the following are mentioned as prior art documents relevant to the present invention.
本発明は、上記事情に鑑みなされたもので、６価クロムを含まない化成皮膜を有し、接着耐久性に優れるアルミ−ゴム複合体を提供すること、及び従来のクロメート処理に代わる化成処理工程を含むアルミ−ゴム複合体の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides an aluminum-rubber composite having a chemical conversion film not containing hexavalent chromium and having excellent adhesion durability, and a chemical conversion treatment step in place of the conventional chromate treatment. It aims at providing the manufacturing method of the aluminum rubber composite containing this.
本発明者は、上記の課題を解決するために鋭意検討した結果、アルミニウム及び／又はアルミニウム合金からなるアルミ系金属とゴム材料とを加硫接着させてなるアルミ−ゴム複合体を製造する際に、上記アルミ系金属の表面をチタン、フッ素及びリンを含む処理液を用いて化成処理することにより６価クロムを含まない化成皮膜を形成することができ、該化成皮膜を形成したアルミ系金属とゴム材料とを加硫接着して得られるアルミ−ゴム複合体が、化成処理として従来のクロメート処理を実施した場合と同等の優れた接着耐久性を示すことを見出し、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventor has produced an aluminum-rubber composite formed by vulcanizing and bonding an aluminum-based metal made of aluminum and / or an aluminum alloy and a rubber material. The surface of the aluminum-based metal can be subjected to a chemical conversion treatment using a treatment liquid containing titanium, fluorine and phosphorus, whereby a chemical conversion film not containing hexavalent chromium can be formed. The present inventors have found that an aluminum-rubber composite obtained by vulcanizing and bonding a rubber material exhibits excellent adhesion durability equivalent to that obtained when a conventional chromate treatment is performed as a chemical conversion treatment, and has reached the present invention.
従って、本発明は下記のアルミ−ゴム複合体及びその製造方法を提供する。
１．アルミニウム及び／又はアルミニウム合金からなるアルミ系金属とゴム材料とを加硫接着してなり、防振材に用いられるアルミ−ゴム複合体において、
上記アルミ系金属と上記ゴム材料との間にチタン、フッ素及びリンを含む化成皮膜が形成されるものであって、該化成皮膜におけるチタンの含有量が０．３０〜１．００質量％、フッ素の含有量が１．００〜４．２０質量％、リンの含有量が１．００〜３．２０質量％であると共に、上記ゴム材料が、天然ゴム、ブタジエンゴム、スチレン・ブタジエンゴム、クロロプレンゴム、ブチルゴム及びハロゲン化ブチルゴムの群から選ばれる１種又は２種以上であることを特徴とするアルミ−ゴム複合体。
２．自動車用のトーショナルダンパー、エンジンマウント又はラバーブッシュの用途に使用される防振材に用いられる１記載のアルミ−ゴム複合体。
３．上記アルミ系金属に対する化成皮膜の付着量が１０〜５００ｍｇ／ｍ2である１又は２記載のアルミ−ゴム複合体。
４．アルミニウム及び／又はアルミニウム合金からなるアルミ系金属とゴム材料とを加硫接着してなり、防振材に用いられるアルミ−ゴム複合体の製造方法であって、
上記アルミ系金属の表面に化成皮膜を形成する化成処理工程と、該化成処理工程で化成皮膜を形成したアルミ系金属とゴム材料とを加硫接着させる接着工程とを含み、
上記化成処理工程において、チタン、フッ素及びリンを含む処理液であって、フッ素イオン濃度が２５ｍｇ／ｌを超え４００ｍｇ／ｌ以下である処理液を用いると共に、上記ゴム材料が、天然ゴム、ブタジエンゴム、スチレン・ブタジエンゴム、クロロプレンゴム、ブチルゴム及びハロゲン化ブチルゴムの群から選ばれる１種又は２種以上であることを特徴とするアルミ−ゴム複合体の製造方法。
５．自動車用のトーショナルダンパー、エンジンマウント又はラバーブッシュの用途に使用される防振材に用いられる４記載のアルミ−ゴム複合体の製造方法。
６．上記処理液のｐＨを２．５〜５．０とする４又は５記載のアルミ−ゴム複合体の製造方法。
７．上記化成処理工程において、上記アルミ系金属を上記処理液に３０秒〜１０分間浸漬させる４〜６のいずれかに記載のアルミ−ゴム複合体の製造方法。
Accordingly, the present invention provides the following aluminum-rubber composite and a method for producing the same.
1. In rubber composite, - aluminum and / or an aluminum-based metal and rubber material made of an aluminum alloy Ri Na vulcanization bonded aluminum used in the vibration proof material
A shall be formed of titanium, chemical conversion film containing fluorine and phosphorus is between the aluminum-based metal and the rubber material, the content of titanium in said chemical conversion coating is 0.30 to 1.00 wt%, the fluorine Content of 1.00 to 4.20 mass%, phosphorus content of 1.00 to 3.20 mass%, and the rubber material is natural rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber An aluminum-rubber composite comprising one or more selected from the group of butyl rubber and halogenated butyl rubber.
2. 2. The aluminum-rubber composite according to 1, which is used for a vibration-proof material used for a torsional damper, an engine mount or a rubber bush for an automobile .
3. 3. The aluminum-rubber composite according to 1 or 2, wherein the amount of chemical conversion film attached to the aluminum-based metal is 10 to 500 mg / m 2 .
4). Aluminum and / or an aluminum-based metal made of aluminum alloy and the rubber material is vulcanized Ri Na, aluminum used in vibration-proof material - A method of manufacturing a rubber composite,
A chemical conversion treatment step of forming a chemical conversion film on the surface of the aluminum metal, and an adhesion step of vulcanizing and bonding the aluminum metal formed with the chemical conversion coating and the rubber material in the chemical conversion treatment step,
In the chemical conversion treatment step, a treatment liquid containing titanium, fluorine and phosphorus , which has a fluorine ion concentration of more than 25 mg / l and not more than 400 mg / l, and the rubber material is natural rubber, butadiene rubber A method for producing an aluminum-rubber composite, which is one or more selected from the group consisting of styrene / butadiene rubber, chloroprene rubber, butyl rubber and halogenated butyl rubber.
5. 5. The method for producing an aluminum-rubber composite according to 4, which is used for a vibration-proof material used for a torsional damper, an engine mount or a rubber bush for an automobile.
6). The method for producing an aluminum-rubber composite according to 4 or 5, wherein the pH of the treatment liquid is 2.5 to 5.0.
7). The method for producing an aluminum-rubber composite according to any one of 4 to 6, wherein in the chemical conversion treatment step, the aluminum metal is immersed in the treatment liquid for 30 seconds to 10 minutes.
本発明によれば、環境負荷が低く、接着耐久性に優れるアルミ−ゴム複合体を提供することができる。 According to the present invention, it is possible to provide an aluminum-rubber composite having a low environmental load and excellent adhesion durability.
以下、本発明につき更に詳しく説明する。
本発明のアルミ−ゴム複合体は、表面にチタン、フッ素及びリンを含む化成皮膜を形成したアルミニウム及び／又はアルミニウム合金からなるアルミ系金属とゴム材料とを加硫接着させて一体化することにより得られるものである。
Hereinafter, the present invention will be described in more detail.
The aluminum-rubber composite of the present invention is obtained by vulcanizing and bonding an aluminum-based metal composed of aluminum and / or an aluminum alloy having a chemical film containing titanium, fluorine, and phosphorus on the surface, and integrating the rubber material. It is obtained.
まず、アルミニウム及び／又はアルミニウム合金からなるアルミ系金属は、特に制限されるものではないが、アルミニウムのほか、アルミニウム合金として、例えば、Ａｌ−Ｓｉ系合金（ＡＤＣ１）、Ａｌ−Ｓｉ−Ｍｇ系合金（ＡＤＣ３）、Ａｌ−Ｍｇ系合金（ＡＤＣ５）、Ａｌ−Ｍｇ−Ｍｎ系合金（ＡＤＣ６）、Ａｌ−Ｓｉ−Ｃｕ系合金（ＡＤＣ１０、ＡＤＣ１０Ｚ、ＡＤＣ１２、ＡＤＣ１２Ｚ）及びＡｌ−Ｓｉ−Ｃｕ−Ｍｇ系合金（ＡＤＣ１４）のダイカスト材や、１０００番台〜７０００番台の展伸材アルミニウム合金等を挙げることができる。本発明では、上記のアルミニウム及びアルミニウム合金のいずれも使用することができ、とりわけ耐食性が低いＡＤＣ１２、ＡＤＣ１４及び２０００番台のアルミニウム合金を使用する場合においてより高い効果を発揮することができる。 First, an aluminum-based metal made of aluminum and / or an aluminum alloy is not particularly limited. In addition to aluminum, examples of aluminum alloys include Al-Si alloys (ADC1) and Al-Si-Mg alloys. (ADC3), Al-Mg alloy (ADC5), Al-Mg-Mn alloy (ADC6), Al-Si-Cu alloy (ADC10, ADC10Z, ADC12, ADC12Z) and Al-Si-Cu-Mg alloy The die-cast material of (ADC14), the wrought aluminum alloy of 1000s to 7000s, etc. can be mentioned. In the present invention, any of the above-described aluminum and aluminum alloys can be used, and in particular, when using the ADC12, ADC14, and 2000 series aluminum alloys having low corrosion resistance, higher effects can be exhibited.
上記アルミ系金属の表面に形成される化成皮膜は、チタン、フッ素及びリンを含むものであり、かつクロムを含まないものである。該化成皮膜において、上記チタンの含有量は、特に制限されるものではないが、化成皮膜の付着量に対して０．３０〜１．００質量％とすることが好ましく、より好ましくは０．３０〜０．８０質量％、更に好ましくは０．４０〜０．６０質量％とすることができる。また、上記フッ素の含有量は、特に制限されるものではないが、化成皮膜の付着量に対して１．００〜４．２０質量％とすることが好ましく、より好ましくは１．５０〜４．００質量％、更に好ましくは１．５０〜３．００質量％とすることができる。上記リンの含有量は、特に制限されるものではないが、化成皮膜の付着量に対して１．００〜３．２０質量％とすることが好ましく、より好ましくは１．５０〜３．００質量％、更に好ましくは２．００〜３．００質量％とすることができる。本発明では、チタン、フッ素及びリンを上記の割合で含有する化成皮膜を形成することにより、得られるアルミ−ゴム複合体に優れた接着耐久性を付与することができる。 The chemical conversion film formed on the surface of the aluminum-based metal contains titanium, fluorine and phosphorus, and does not contain chromium. In the chemical film, the content of titanium is not particularly limited, but is preferably 0.30 to 1.00% by mass, more preferably 0.30 with respect to the amount of chemical film deposited. -0.80 mass%, More preferably, it can be 0.40-0.60 mass%. Moreover, the content of the fluorine is not particularly limited, but is preferably 1.00 to 4.20% by mass, more preferably 1.50 to 4.20% with respect to the adhesion amount of the chemical conversion film. The amount may be 00% by mass, more preferably 1.50 to 3.00% by mass. The content of the phosphorus is not particularly limited, but is preferably 1.00 to 3.20% by mass, more preferably 1.50 to 3.00% by mass with respect to the amount of conversion coating deposited. %, More preferably 2.00 to 3.00 mass%. In the present invention, excellent adhesion durability can be imparted to the resulting aluminum-rubber composite by forming a chemical conversion film containing titanium, fluorine and phosphorus in the above proportions.
上記アルミ系金属に対する化成皮膜の付着量は、特に制限されるものではないが、１０〜５００ｍｇ／ｍ2とすることが好ましく、より好ましくは３０〜２００ｍｇ／ｍ2とすることができる。化成皮膜の付着量が多すぎた場合は、製品のコストアップに繋がるほか、加硫接着後に皮膜の凝集破壊発生の可能性が高まる。一方、化成皮膜の付着量が少なすぎた場合は、腐食環境での接着耐久性が低下するおそれがある。 Adhesion amount of chemical conversion coating for the aluminum-based metal, but is not particularly limited, preferably to 10 to 500 mg / m 2, more preferably, to 30 to 200 mg / m 2. If the amount of the chemical conversion coating is too large, the cost of the product will be increased, and the possibility of the occurrence of cohesive failure of the coating after vulcanization adhesion will increase. On the other hand, if the amount of the chemical conversion film deposited is too small, the adhesion durability in a corrosive environment may be reduced.
一方、上記アルミ系金属と接着されるゴム材料は、アルミ−ゴム複合体が外部から受ける負荷を自身の変形により軽減する機能を担うものであり、用途等に応じて所望の弾性、強度、耐久性を有するゴム材料が適宜選択され、特に限定されるものではない。上記ゴム材料に配合されるゴム成分としては、天然ゴム、ブタジエンゴム、スチレン・ブタジエンゴム、クロロプレンゴム、ＥＰＤＭ、ブチルゴム、ハロゲン化ブチルゴム等の公知のゴム成分から選ばれる１種を単独で又は２種以上を任意の比率で混合して使用することができる。本発明においては、天然ゴム、スチレン・ブタジエンゴムを好適に用いることができる。また、上記ゴム材料には、本発明の目的を逸脱しない範囲で、加硫剤、加硫促進剤、耐熱老化防止剤、ワックス、着色剤、充填剤、可塑剤、軟化剤、粘着付与剤等の公知の添加剤を適宜添加配合してもよい。 On the other hand, the rubber material bonded to the aluminum-based metal has a function of reducing the load that the aluminum-rubber composite receives from the outside by its own deformation, and has a desired elasticity, strength and durability depending on the application. The rubber material having properties is appropriately selected and is not particularly limited. As the rubber component to be blended with the rubber material, one or two kinds selected from known rubber components such as natural rubber, butadiene rubber, styrene / butadiene rubber, chloroprene rubber, EPDM, butyl rubber, halogenated butyl rubber, etc. The above can be mixed and used by arbitrary ratios. In the present invention, natural rubber and styrene-butadiene rubber can be suitably used. Further, the rubber material includes a vulcanizing agent, a vulcanization accelerator, a heat resistant anti-aging agent, a wax, a colorant, a filler, a plasticizer, a softening agent, a tackifier and the like without departing from the object of the present invention. These known additives may be appropriately added and blended.
次に、上記のアルミ−ゴム複合体の製造方法について詳述する。
まず、必要とする形状及び合金構成のアルミ系金属、並びに必要とする形状及び材質のゴム材料を選択する。上記アルミ系金属の形状は、その使用目的に応じて任意の形状とすることができ、特に限定されるものではない。次に、上記で選択したアルミ系金属の表面にある酸化皮膜や油脂等の汚れを、脱脂、ブラスト処理、エッチング処理及びスマット除去等を適宜組み合わせた公知の前処理工程を実施して除去する。そして、表面を清浄にしたアルミ系金属を次の化成処理工程に供する。
Next, the manufacturing method of said aluminum-rubber composite is explained in full detail.
First, an aluminum metal having a required shape and alloy structure and a rubber material having a required shape and material are selected. The shape of the aluminum metal can be any shape depending on the purpose of use, and is not particularly limited. Next, dirt such as oxide film and oils and fats on the surface of the aluminum metal selected above is removed by performing a known pretreatment process appropriately combining degreasing, blasting, etching and smut removal. And the aluminum-type metal which cleaned the surface is provided to the next chemical conversion treatment process.
化成処理工程では、アルミ系金属の表面にチタン、フッ素及びリンを含む処理液を用いて化成皮膜を形成する。なお、上記処理液はクロムを含まないものである。化成処理の方法としては、ロールコート法、スピンコート法、スプレー法及び浸漬法等を用いることができ、本発明では浸漬法を好適に採用できる。浸漬法の場合、浸漬時間は、特に制限されるものではないが、３０秒〜１０分間とすることが好ましく、より好ましくは３〜４分間とすることができる。浸漬時間が短すぎると、十分な量の皮膜が形成されないおそれがあり、密着性、接着耐久性が低下するおそれがある。一方、浸漬時間が長すぎると、表面の黄色が強くなり、皮膜成分の析出、表面に粉が付着したような外観異常が発生する可能性がある。 In the chemical conversion treatment step, a chemical conversion film is formed on the surface of the aluminum-based metal using a treatment liquid containing titanium, fluorine, and phosphorus. In addition, the said process liquid does not contain chromium. As a chemical conversion treatment method, a roll coating method, a spin coating method, a spray method, a dipping method, or the like can be used. In the present invention, a dipping method can be suitably employed. In the case of the immersion method, the immersion time is not particularly limited, but is preferably 30 seconds to 10 minutes, more preferably 3 to 4 minutes. If the immersion time is too short, a sufficient amount of film may not be formed, and the adhesion and adhesion durability may be reduced. On the other hand, when the immersion time is too long, the yellow color on the surface becomes strong, and there is a possibility that the appearance abnormality such as precipitation of film components and adhesion of powder on the surface may occur.
上記処理液のｐＨは、特に制限されるものではないが、２．５〜５．０とすることが好ましく、より好ましくは３．０〜４．５とすることができる。処理液のｐＨが低すぎると、表面の黄色が強くなり、皮膜成分の析出、表面に粉が付着したような外観異常が発生する可能性がある。一方、処理液のｐＨが高すぎると皮膜反応が不十分となり、目的とする皮膜が十分に形成されない可能性がある。 The pH of the treatment liquid is not particularly limited, but is preferably 2.5 to 5.0, and more preferably 3.0 to 4.5. When the pH of the treatment liquid is too low, the surface yellow color becomes strong, and there is a possibility that the appearance abnormality such as precipitation of coating components and adhesion of powder on the surface may occur. On the other hand, if the pH of the treatment liquid is too high, the film reaction becomes insufficient, and the target film may not be sufficiently formed.
上記処理液のフッ素イオン濃度は、特に制限されるものではないが、２５ｍｇ／ｌを超え４００ｍｇ／ｌ以下とすることが好ましく、より好ましくは７０ｍｇ／ｌ以上３００ｍｇ／ｌ以下とすることができる。処理液のフッ素イオン濃度が低すぎると皮膜量が減少し、化成皮膜が十分に形成されないことがある。一方、フッ素イオン濃度が高すぎると、外観が黄色味を帯び、表面に粉が付着したような状態になることがあり、用途によっては外観上好ましくない場合がある。 The fluorine ion concentration of the treatment liquid is not particularly limited, but is preferably more than 25 mg / l and 400 mg / l or less, more preferably 70 mg / l or more and 300 mg / l or less. When the fluorine ion concentration of the treatment liquid is too low, the amount of the film is reduced, and the chemical conversion film may not be sufficiently formed. On the other hand, if the fluorine ion concentration is too high, the appearance may be yellowish and the surface may be in a state where powder is attached, which may be undesirable in some applications.
処理液の温度は、特に制限されるものではないが、４０〜６０℃とすることが好ましく、より好ましくは４５〜５５℃とすることができる。処理液の温度が低すぎると、反応性が低く、皮膜の形成性が悪くなり、接着耐久性が低下するおそれがある。一方、処理液の温度が高すぎると、皮膜付着量が増加し、接着後に皮膜凝集破壊が発生するおそれがある。 The temperature of the treatment liquid is not particularly limited, but is preferably 40 to 60 ° C, more preferably 45 to 55 ° C. When the temperature of the treatment liquid is too low, the reactivity is low, the film formability is deteriorated, and the adhesion durability may be lowered. On the other hand, if the temperature of the treatment liquid is too high, the amount of film adhesion increases, and there is a risk of film cohesion failure occurring after adhesion.
本発明では、上記のチタン、フッ素及びリンを含む処理液として、ケミボンダー５７０２（日本シー・ビー・ケミカル社製）、Ａｌｏｄｉｎｅ５２００（ＨＥＮＫＥＬ社製）等を好適に使用することができる。 In the present invention, Chemibonder 5702 (manufactured by Nippon CB Chemical Co., Ltd.), Alodine 5200 (manufactured by HENKEL Co., Ltd.) or the like can be suitably used as the treatment liquid containing titanium, fluorine and phosphorus.
上記化成処理により化成皮膜が形成されたアルミ系金属は、その表面の化成皮膜上に余分な処理液が残らないように洗浄され、次工程の接着工程に供される。 The aluminum-based metal on which the chemical conversion film is formed by the chemical conversion treatment is washed so that no excessive treatment liquid remains on the chemical conversion film on the surface, and is supplied to the subsequent bonding step.
接着工程では、上記化成処理工程でアルミ系金属の表面に形成した化成皮膜上に加硫用ゴム接着剤を塗布した後、適宜な方法で上記ゴム材料と加硫接着する。その方法は、特に制限されるものではないが、接着剤を塗布したアルミ系金属に所定の形状に成形したゴム材料を直接貼り合わせ、その状態で所定時間加熱する方法や、射出成形用の金型内に接着剤を塗布したアルミ系金属をセットし、ゴム材料を射出注入した後、所定時間加熱する方法等を採用することができる。 In the bonding step, a rubber adhesive for vulcanization is applied on the chemical conversion film formed on the surface of the aluminum-based metal in the chemical conversion treatment step, and then vulcanized and bonded to the rubber material by an appropriate method. Although the method is not particularly limited, a rubber material molded into a predetermined shape is directly bonded to an aluminum metal coated with an adhesive, and heated in that state for a predetermined time, or a metal for injection molding. A method of heating for a predetermined time after setting an aluminum-based metal coated with an adhesive in a mold and injecting and injecting a rubber material can be employed.
上記接着剤としては、公知のものを使用することができ、特に制限されるものではないが、本発明では２液性接着剤のＣＨ２０００／ＣＨ６１０８（ロード社製）等を好適に用いることができる。 As the above-mentioned adhesive, known ones can be used, and are not particularly limited. In the present invention, a two-component adhesive such as CH2000 / CH6108 (manufactured by Lord) can be suitably used. .
また、加硫条件は、選択されるゴム材料の配合等に応じて適宜設定することができ、特に制限されるものではないが、加硫温度は１５０〜１８０℃、加硫時間は５〜３０分間とすることが好ましい。 The vulcanization conditions can be appropriately set according to the composition of the selected rubber material and the like, and are not particularly limited. However, the vulcanization temperature is 150 to 180 ° C., and the vulcanization time is 5 to 30. It is preferable to use minutes.
なお、上記構成の本発明のアルミ−ゴム複合体を製造する際には、従来公知の製造設備を採用することができる。また、該複合体を構成するアルミ系金属及びゴム材料の形状や材質等については、上記に限定されるものではなく、本発明の目的を逸脱しない範囲において、設備仕様や製品仕様等に応じて最適なものを採用すればよい。更には、上記アルミ−ゴム複合体の構造は、その使用目的に応じて任意に設定することができ、特に制限されるものではない。本発明では、例えば、金属製の外筒体の内側に内筒体を配置し、これら両筒体間にゴム層を接着形成して、これら外筒体、内筒体及びゴム層を一体化させた構造、２枚の金属板の間に板状のゴム材料を挟んで一体化させた構造、及び複数枚の金属板と板状のゴム材料とを交互に積層した構造等を挙げることができる。 In addition, when manufacturing the aluminum-rubber composite of this invention of the said structure, a conventionally well-known manufacturing equipment is employable. Further, the shape and material of the aluminum-based metal and the rubber material constituting the composite are not limited to the above, and in accordance with the equipment specifications, product specifications, etc. within the scope of the present invention. The most suitable one should be adopted. Furthermore, the structure of the aluminum-rubber composite can be arbitrarily set according to the purpose of use, and is not particularly limited. In the present invention, for example, an inner cylinder is disposed inside a metal outer cylinder, a rubber layer is bonded and formed between the two cylinders, and the outer cylinder, the inner cylinder, and the rubber layer are integrated. And a structure in which a plate-shaped rubber material is sandwiched between two metal plates and integrated, and a structure in which a plurality of metal plates and a plate-shaped rubber material are alternately stacked.
本発明のアルミ−ゴム複合体は、車両や各種産業機械等において使用される防振材、例えば、自動車用のトーショナルダンパー、エンジンマウント、ラバーブッシュ等の用途に好適に使用されるものであるが、これらに限定されるものではない。 The aluminum-rubber composite of the present invention is suitably used for vibration-proof materials used in vehicles, various industrial machines, etc., for example, torsional dampers for automobiles, engine mounts, rubber bushes and the like. However, it is not limited to these.
以下、本発明について実施例及び比較例を挙げて詳細に説明するが、本発明は下記実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.
［実施例１〜６、比較例１〜４］
アルミ−ゴム複合体のアルミ系金属及びゴム材料は以下のものを使用した。
・アルミ系金属
６０×２５×２ｍｍの板状のＡＤＣ１２材を使用した。
・ゴム材料
表１に示した配合のゴム組成物を常法に従って混練りし、２７０×１５０×４ｍｍの板状に成形した。
[Examples 1-6, Comparative Examples 1-4]
The following were used for the aluminum-based metal and rubber material of the aluminum-rubber composite.
-Aluminum-based metal A plate-shaped ADC12 material of 60 × 25 × 2 mm was used.
Rubber material The rubber composition having the composition shown in Table 1 was kneaded according to a conventional method and formed into a plate shape of 270 × 150 × 4 mm.
表１に示した各成分の詳細は以下の通りである。
天然ゴム：ＲＳＳ＃１
カーボンブラック：ＦＥＦ級カーボンブラック、旭カーボン（株）製「Ｎ５５０」、ヨウ素吸収量４３ｇ／ｋｇ、ＤＢＰ吸収量（Ａ法）１２１ｍｌ／１００ｇ
ＷＡＸ：Ｒｈｅｉｎ Ｃｈｅｍｉｅ社製「Ａｎｔｉｌｕｘ６５４」
老化防止剤ＲＤ：２，２，４−トリメチル−１，２−ジヒドロキノリン重合体、大内新興化学工業（株）製「ノクラック２２４」
老化防止剤６ＰＰＤ：Ｎ−フェニル−Ｎ’−（１，３−ジメチルブチル）−ｐ−フェニレンジアミン、大内新興化学工業（株）製「ノクラック６Ｃ」
加硫促進剤：Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド（ＣＢＳ）、大内新興化学工業（株）製「ノクセラーＣＺ」
Details of each component shown in Table 1 are as follows.
Natural rubber: RSS # 1
Carbon black: FEF grade carbon black, “N550” manufactured by Asahi Carbon Co., Ltd., iodine absorption amount 43 g / kg, DBP absorption amount (A method) 121 ml / 100 g
WAX: “Antilux 654” manufactured by Rhein Chemie
Anti-aging agent RD: 2,2,4-trimethyl-1,2-dihydroquinoline polymer, “NOCRACK 224” manufactured by Ouchi Shinsei Chemical Co., Ltd.
Anti-aging agent 6PPD: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator: N-cyclohexyl-2-benzothiazylsulfenamide (CBS), “Noxeller CZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.
１．前処理工程
前処理として脱脂、エッチングを実施して表面の酸化皮膜や油脂等の汚れを除去した。処理条件は以下の通りである。
・脱脂
処理液：アルカリ性脱脂液
液温：６０〜７０℃
時間：７〜２０分間
・エッチング
処理液：硝酸系エッチング液
液温：室温
時間：１〜２分間
２．化成処理工程
前処理を行ったアルミ系金属を表２に示したｐＨ及びフッ素イオン濃度に調整した温度５０℃の処理液に１８０秒間浸漬させた。処理液としては、ケミボンダー５７０２（日本シー・ビー・ケミカル社製）を使用した。また、処理液としてコンバーコートＮｏ．１（日本シー・ビー・ケミカル社製）を使用し、６価クロムを含有する化成皮膜を形成したアルミ系金属、及び化成処理を実施せず、ブラスト処理のみとしたアルミ系金属も比較のために用意した。
３．接着工程
上記化成処理工程で化成皮膜を形成したＡＤＣ１２材の接着面に２液性接着剤のＣＨ２０００／ＣＨ６１０８（ＬＯＲＤ社製）を塗布し、上記で成形したゴム材料を貼り合わせた後、１６０℃で２０分間加熱保持して加硫接着して、アルミ系金属とゴム材料とが加硫接着されたアルミ−ゴム複合体の評価サンプルを得た。また、６価クロムを含有する化成皮膜を形成したアルミ系金属及びブラスト処理のみを実施したアルミ系金属についても上記と同様の手順でゴム材料と接着して評価サンプルを得た。
1. Pretreatment process As pretreatment, degreasing and etching were carried out to remove dirt such as oxide film and oil on the surface. The processing conditions are as follows.
Degreasing treatment liquid: alkaline degreasing liquid temperature: 60-70 ° C
Time: 7-20 minutes Etching Treatment liquid: Nitric acid based etchant Liquid temperature: Room temperature Time: 1-2 minutes Chemical conversion treatment step The pretreated aluminum metal was immersed in a treatment solution at a temperature of 50 ° C. adjusted to the pH and fluorine ion concentration shown in Table 2 for 180 seconds. As the treatment liquid, Chemibonder 5702 (manufactured by Nippon CB Chemical Co., Ltd.) was used. In addition, as a treatment liquid, convert coat No. 1 (Nihon CB Chemical Co., Ltd.) using an aluminum metal with a chemical conversion film containing hexavalent chromium, and an aluminum metal without chemical conversion treatment and only blasting Prepared.
3. Adhesion Step After applying the two-component adhesive CH2000 / CH6108 (manufactured by LORD) to the adhesion surface of the ADC12 material on which the chemical conversion film was formed in the chemical conversion treatment step, the rubber material molded as described above was bonded, and then 160 ° C. And then vulcanized and bonded for 20 minutes to obtain an evaluation sample of an aluminum-rubber composite in which an aluminum-based metal and a rubber material were vulcanized and bonded. Moreover, the aluminum type metal which formed the chemical conversion film containing hexavalent chromium, and the aluminum type metal which performed only the blasting process were adhere | attached with the rubber material in the same procedure as the above, and the evaluation sample was obtained.
上記で得た評価サンプルは、化成皮膜におけるチタン、フッ素及びリンの含有量を測定すると共に、接着耐久性を評価した。評価結果は表２に示した。 The evaluation sample obtained above measured the contents of titanium, fluorine and phosphorus in the chemical conversion film, and evaluated the adhesion durability. The evaluation results are shown in Table 2.
・チタン、フッ素及びリンの含有量
蛍光Ｘ線分析装置により、化成皮膜のチタン、フッ素及びリンの含有量を測定した。測定条件は以下の通りである。
（株）リガク製 ＺＳＸ Ｐｒｉｍｕｓ IIを使用。
試料表面φ１０ｍｍの測定孔に上面照射真空測定で４．０ｋｗ（５０ｋｖ、６０ｍＡ）のＸ線を照射し、ＦＰ法で定量した。
-Content of titanium, fluorine and phosphorus The content of titanium, fluorine and phosphorus in the chemical conversion film was measured with a fluorescent X-ray analyzer. The measurement conditions are as follows.
Uses ZSX Primus II manufactured by Rigaku Corporation.
X-rays of 4.0 kw (50 kv, 60 mA) were irradiated to the measurement hole having a sample surface diameter of 10 mm by top surface irradiation vacuum measurement, and quantified by the FP method.
・接着耐久性
接着初期の評価サンプルとＪＩＳ Ｚ２３７１に準拠した塩水噴霧試験（ＳＳＴ）を１０００時間実施した後の評価サンプルについてピーリング試験を行い評価した。塩水噴霧試験（ＳＳＴ）及びピーリング試験の条件は以下の通りである。
〔塩水噴霧試験〕
３５℃の濃度５％塩化ナトリウム水溶液を連続して１０００時間噴霧した。
〔ピーリング試験〕
評価サンプルのゴム材の端部をペンチでつまみ、９０°の角度で引きはがし、破断面のゴム材の面積を測定した。そして、その面積から接着面におけるゴム破壊（Ｒ）と界面破壊（ＭＣ）の面積の割合を求めた。ゴム破壊（Ｒ）の面積が大きいほど接着性に優れる。また、塩水噴霧試験後に接着性が低下しにくいものほど接着耐久性に優れる。
-Adhesion durability The peeling sample was evaluated and evaluated about the evaluation sample after implementing the salt spray test (SST) based on the evaluation sample of an adhesion | attachment initial stage, and JISZ2371 for 1000 hours. Conditions for the salt spray test (SST) and the peeling test are as follows.
[Salt spray test]
A 35% strength aqueous 5% sodium chloride solution was continuously sprayed for 1000 hours.
[Peeling test]
The end portion of the rubber material of the evaluation sample was pinched with pliers and peeled off at an angle of 90 °, and the area of the rubber material on the fracture surface was measured. And the ratio of the area of rubber fracture (R) and interface fracture (MC) on the bonding surface was determined from the area. The larger the area of rubber breakage (R), the better the adhesion. In addition, the adhesive durability is more excellent as the adhesive is less likely to decrease after the salt spray test.
２）Ｒは「ゴム破壊」、ＭＣは「界面破壊」を表し、数字は接着面における面積の割合を表す。
＊比較例３における化成皮膜の付着量はクロム付着量を示す。
2) R represents “rubber failure”, MC represents “interfacial failure”, and the number represents the ratio of the area on the bonded surface.
* The amount of chemical conversion film deposited in Comparative Example 3 represents the amount of chromium deposited.
Claims (7)
上記アルミ系金属と上記ゴム材料との間にチタン、フッ素及びリンを含む化成皮膜が形成されるものであって、該化成皮膜におけるチタンの含有量が０．３０〜１．００質量％、フッ素の含有量が１．００〜４．２０質量％、リンの含有量が１．００〜３．２０質量％であると共に、上記ゴム材料が、天然ゴム、ブタジエンゴム、スチレン・ブタジエンゴム、クロロプレンゴム、ブチルゴム及びハロゲン化ブチルゴムの群から選ばれる１種又は２種以上であることを特徴とするアルミ−ゴム複合体。 In rubber composite, - aluminum and / or an aluminum-based metal and rubber material made of an aluminum alloy Ri Na vulcanization bonded aluminum used in the vibration proof material
A shall be formed of titanium, chemical conversion film containing fluorine and phosphorus is between the aluminum-based metal and the rubber material, the content of titanium in said chemical conversion coating is 0.30 to 1.00 wt%, the fluorine Content of 1.00 to 4.20 mass%, phosphorus content of 1.00 to 3.20 mass%, and the rubber material is natural rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber An aluminum-rubber composite comprising one or more selected from the group of butyl rubber and halogenated butyl rubber.
上記アルミ系金属の表面に化成皮膜を形成する化成処理工程と、該化成処理工程で化成皮膜を形成したアルミ系金属とゴム材料とを加硫接着させる接着工程とを含み、
上記化成処理工程において、チタン、フッ素及びリンを含む処理液であって、フッ素イオン濃度が２５ｍｇ／ｌを超え４００ｍｇ／ｌ以下である処理液を用いると共に、上記ゴム材料が、天然ゴム、ブタジエンゴム、スチレン・ブタジエンゴム、クロロプレンゴム、ブチルゴム及びハロゲン化ブチルゴムの群から選ばれる１種又は２種以上であることを特徴とするアルミ−ゴム複合体の製造方法。 Aluminum and / or an aluminum-based metal made of aluminum alloy and the rubber material is vulcanized Ri Na, aluminum used in vibration-proof material - A method of manufacturing a rubber composite,
A chemical conversion treatment step of forming a chemical conversion film on the surface of the aluminum metal, and an adhesion step of vulcanizing and bonding the aluminum metal formed with the chemical conversion coating and the rubber material in the chemical conversion treatment step,
In the chemical conversion treatment step, a treatment liquid containing titanium, fluorine and phosphorus , which has a fluorine ion concentration of more than 25 mg / l and not more than 400 mg / l, and the rubber material is natural rubber, butadiene rubber A method for producing an aluminum-rubber composite, which is one or more selected from the group consisting of styrene / butadiene rubber, chloroprene rubber, butyl rubber and halogenated butyl rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014110330A JP6295832B2 (en) | 2014-05-28 | 2014-05-28 | Aluminum-rubber composite and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014110330A JP6295832B2 (en) | 2014-05-28 | 2014-05-28 | Aluminum-rubber composite and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015224371A JP2015224371A (en) | 2015-12-14 |
| JP6295832B2 true JP6295832B2 (en) | 2018-03-20 |
Family
ID=54841378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014110330A Active JP6295832B2 (en) | 2014-05-28 | 2014-05-28 | Aluminum-rubber composite and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6295832B2 (en) |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1162504A (en) * | 1980-11-25 | 1984-02-21 | Mobuyuki Oda | Treating tin plated steel sheet with composition containing titanium or zirconium compounds |
| US4341558A (en) * | 1981-02-27 | 1982-07-27 | Hooker Chemicals & Plastics Corp. | Metal surface coating agent |
| DE3236247A1 (en) * | 1982-09-30 | 1984-04-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR SURFACE TREATMENT OF ALUMINUM |
| AU4751885A (en) * | 1984-10-09 | 1986-04-17 | Parker Chemical Company | Treating extruded aluminium metal surfaces |
| JPH0748677A (en) * | 1993-07-05 | 1995-02-21 | Nippon Parkerizing Co Ltd | Aluminum di can and common surface treatment solution and process for tin di can |
| DE4412138A1 (en) * | 1994-04-08 | 1995-10-12 | Henkel Kgaa | Chromium-free process for no-rinse treatment of aluminum and its alloys as well as suitable aqueous bath solutions |
| JP3315529B2 (en) * | 1994-06-03 | 2002-08-19 | 日本パーカライジング株式会社 | Composition for surface treatment of aluminum-containing metal material and surface treatment method |
| JPH08276533A (en) * | 1995-04-07 | 1996-10-22 | Nippon Paint Co Ltd | Coated sheet metal |
| JP3437023B2 (en) * | 1995-11-20 | 2003-08-18 | 日本ペイント株式会社 | Aluminum-based metal surface treatment bath and treatment method |
| JPH1161432A (en) * | 1997-08-28 | 1999-03-05 | Nippon Steel Corp | Metal plate surface-treated with inorganic/organic composite |
| JP3026941B2 (en) * | 1996-09-17 | 2000-03-27 | 株式会社荒井製作所 | Composite member of aluminum alloy and synthetic rubber and method of manufacturing the same |
| JP5022571B2 (en) * | 2005-03-25 | 2012-09-12 | ニチアス株式会社 | Method for manufacturing gasket and washer |
| JP2007285513A (en) * | 2006-03-22 | 2007-11-01 | Tokai Rubber Ind Ltd | Rubber member with metal fitting and method of fabricating the same |
| JP4521010B2 (en) * | 2007-04-09 | 2010-08-11 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
| JP4646966B2 (en) * | 2007-12-13 | 2011-03-09 | 日本パーカライジング株式会社 | Metal surface treatment agent, surface treatment method of metal material, and surface treatment metal material |
-
2014
- 2014-05-28 JP JP2014110330A patent/JP6295832B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015224371A (en) | 2015-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Surface protection of Mg alloys in automotive applications: A review | |
| US20050179010A1 (en) | Surface base-coat formulation for metal alloys | |
| JPH10506416A (en) | Organic phosphonic or phosphinic acid coatings for aluminum alloy vehicle assemblies. | |
| JP6644631B2 (en) | Aqueous solution for metal surface treatment and method for treating metal surface | |
| CN101041895B (en) | Rubber component having fittings and manufacturing method thereof | |
| JP6295832B2 (en) | Aluminum-rubber composite and method for producing the same | |
| JP2005226064A (en) | Vulcanizing and bonding composition | |
| JP5152287B2 (en) | Vulcanized adhesive composition | |
| JPH07166125A (en) | Resin-coated aluminium or aluminium alloy material excellent in press forming properties and corrosion resistance and its production | |
| JP2004511653A (en) | Acid pretreatment for adhesive bonding of vehicle assemblies | |
| EP3228678A1 (en) | Material for gasket | |
| CN101062600B (en) | Rubber part having an aluminum-based metal component and method of producing the same | |
| JP2017155289A (en) | Method for manufacturing surface treated aluminum alloy plate | |
| JP2008248285A (en) | Rubber member including aluminum-based metal component and production method for the same | |
| JP5806016B2 (en) | Powder coating and powder coating method | |
| JP2005530047A (en) | Surface treatment method for aluminum alloy plates and strips | |
| JP6834247B2 (en) | Surface treatment agents for metal materials, metal joints and methods for adhering metal materials | |
| JP4222446B2 (en) | Method for producing aluminum-rubber composite | |
| JP6278882B2 (en) | Surface-treated aluminum alloy plate and manufacturing method thereof | |
| JP2001199003A (en) | Organic composite coated steel panel excellent in solvent resistance | |
| Lazarz et al. | Corrosion Performance of a Magnesium Tower Brace | |
| KR102552559B1 (en) | Methods of treating surfaces of hot dipped galvanized iron to enhance the adhesiveness | |
| JP6251829B2 (en) | Aluminum surface treatment material and manufacturing method thereof | |
| JP2897042B2 (en) | Method for producing rubber composite | |
| WO2017183532A1 (en) | Surface-treated aluminum material and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161219 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170922 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171003 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171201 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180123 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180205 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6295832 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |