JPS5933304B2 - rubber laminate - Google Patents
rubber laminateInfo
- Publication number
- JPS5933304B2 JPS5933304B2 JP2578080A JP2578080A JPS5933304B2 JP S5933304 B2 JPS5933304 B2 JP S5933304B2 JP 2578080 A JP2578080 A JP 2578080A JP 2578080 A JP2578080 A JP 2578080A JP S5933304 B2 JPS5933304 B2 JP S5933304B2
- Authority
- JP
- Japan
- Prior art keywords
- nbr
- blended
- rubber
- fluororubber
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001971 elastomer Polymers 0.000 title claims description 37
- 229920001973 fluoroelastomer Polymers 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 5
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 claims description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims 1
- 229920006027 ternary co-polymer Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- -1 t-butylperoxy Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】
この発明は、ゴム積層体に関し、さらに詳しくは、フッ
素ゴム層とＮＢＲ層とを重ねて加硫接着したゴム積層体
に関し、自動車用燃料ホースやダイヤフラム等に適用可
能なものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber laminate, and more particularly to a rubber laminate in which a fluororubber layer and an NBR layer are laminated and vulcanized and bonded, and is applicable to automobile fuel hoses, diaphragms, etc. It is something.
この明細書における「ＮＢＲ」は、アクリロニトルブタ
ジエンゴムの略記である。"NBR" in this specification is an abbreviation for acrylonitrobutadiene rubber.
昨今の燃料回路系ホース、特に電子噴射装置を備えた燃
料回路系に適用する自動車用燃料ホースは、内部を流通
するガソリンがエンジンの高温又内圧の増大に伴ない劣
化しやすく、耐サワーガソリン性が要求される。Modern fuel circuit hoses, especially automotive fuel hoses that are applied to fuel circuit systems equipped with electronic injection devices, tend to deteriorate due to the gasoline flowing inside them as the engine's high temperature and internal pressure increase, and sour gasoline resistance is poor. is required.
また、燃料ホースには、燃料事情の悪化に伴ない耐アル
コール添加ガソリン性、大気汚染に対する法規制に伴な
う耐ガソリン透過性の向上が要求される等、従来に比し
て種々の可酷な条件下における諸性能が要求されている
。このような諸性能を満たすゴム材料としてフッ素ゴム
がある。フッ素ゴムは、耐熱性、耐ガソリン性、耐サワ
ーガソリン性、耐ガソリン透過性に優れている。特に、
フッ化ビニリデン、六フッ化プロピレン、四フッ化エチ
レンの三元共重合体からなるフッ素ゴムは、耐メタノー
ル性を含む耐アルコール性に優れていることが知られて
いる。しかし、上記フッ素ゴムは、他のＮＢＲ等のゴム
材料に比して、１０〜２０部と非常に高価であるため、
ＮＢＲ等の通常のゴム材料を基体層として、その上にフ
ッ素ゴムの薄層を形成するゴム積層体として使用するこ
とが考えられる。しかし、フッ素ゴムとＮＢＲ等他のゴ
ム材料とは、通常の方法では接着しないか、または接着
力が非常に弱い。In addition, fuel hoses are required to have improved resistance to alcohol-added gasoline due to worsening fuel conditions, and improved gasoline permeation resistance due to air pollution regulations. Various performances are required under such conditions. Fluororubber is a rubber material that satisfies these various properties. Fluororubber has excellent heat resistance, gasoline resistance, sour gasoline resistance, and gasoline permeation resistance. especially,
Fluororubber made of a terpolymer of vinylidene fluoride, propylene hexafluoride, and ethylene tetrafluoride is known to have excellent alcohol resistance including methanol resistance. However, the above fluororubber is very expensive at 10 to 20 parts compared to other rubber materials such as NBR.
It is conceivable to use a rubber laminate in which a normal rubber material such as NBR is used as a base layer and a thin layer of fluororubber is formed thereon. However, fluororubber and other rubber materials such as NBR do not adhere to each other using normal methods, or have very weak adhesive strength.
このため、上記フッ素ゴムは、その優れた諸性能にもか
かわらず、適用範囲が限定されている。この発明の目的
は、上記にかんがみて、層間接着力が良好なフッ素ゴム
層とＮＢＲ層とからなるゴム積層体を提供することにあ
る。For this reason, the range of application of the above-mentioned fluororubber is limited despite its excellent performance. In view of the above, an object of the present invention is to provide a rubber laminate consisting of a fluororubber layer and an NBR layer that has good interlayer adhesive strength.
この発明の要旨は、フツ化ビニリデン、六フツ化プロピ
レン、四フツ化エチレンの三元共重合体からなるフツ素
ゴムに過酸化物系加硫剤が配合されたゴム配合物、又は
、ＮＢＲが前記ゴム配合物にブレンドされたブレンドゴ
ム配合物からなるフツ素ゴム層と、ＮＢＲにシリカ系充
填剤及び金一属酸化物が配合されたゴム配合物からなる
ＮＢＲ層とを重ねて加硫接着したゴム積層体にある。The gist of this invention is a rubber compound in which a peroxide-based vulcanizing agent is blended with a fluororubber made of a terpolymer of vinylidene fluoride, propylene hexafluoride, and ethylene tetrafluoride, or a rubber compound in which a peroxide-based vulcanizing agent is blended with A fluororubber layer made of a blended rubber compound blended with the above rubber compound and an NBR layer made of a rubber compound in which a silica filler and monometallic oxide are blended with NBR are stacked and vulcanized and bonded. It is made of rubber laminate.
以下、さらに、この発明について詳細に説明をする。な
お「部」は、特に記載しないかぎり「重量音関を示す。This invention will be further explained in detail below. Note that "part" indicates "weight scale" unless otherwise specified.
（１）フツ素ゴム層を形成するゴム配合物は、フツ素ゴ
ムに、過酸化物加硫剤を、他の副資材とともに配合した
ものである。(1) The rubber compound forming the fluororubber layer is a mixture of fluororubber and a peroxide vulcanizing agent along with other auxiliary materials.
上記フツ素ゴムは、フツ化ビニリデン、六フツ化プロピ
レン、四フツ化エチレンの三元共重合体で、過酸化物加
硫可能に処理がなされているものである。The fluororubber is a terpolymer of vinylidene fluoride, propylene hexafluoride, and ethylene tetrafluoride, and has been treated to be peroxide vulcanizable.
具体的には、バイトンＧＨ（商品名：デユポン社製造）
が挙げられる。過酸化物系加硫剤としては、２，５−ジ
メチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン
−３（純度４０％）、α，ｄ−ビス（ｔ−ブチルペルオ
キシ）−ｐ−ジイソプロピルベンゼン（純度４００１）
）等の有機過酸化物を使用し、配合量はフツ素ゴム１０
０部に対し１〜５部とする。Specifically, Viton GH (product name: manufactured by Dupont)
can be mentioned. Peroxide-based vulcanizing agents include 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3 (purity 40%), α,d-bis(t-butylperoxy)-p- Diisopropylbenzene (purity 4001)
), etc., and the blending amount is 10% of fluorocarbon rubber.
0 parts to 1 to 5 parts.
上記加硫剤とともに、フツ素ゴムに配合する副資材は、
加硫促進助剤、受酸剤、補強剤としてのカーボンブラツ
ク等である。（） ＮＢＲ層を形成するゴム配合物は、
ＮＢＲにシリカ系充填剤及び金属酸化物を配合したもの
である。Along with the above vulcanizing agent, the auxiliary materials added to the fluoro rubber are:
These include carbon black as a vulcanization accelerator, an acid acceptor, and a reinforcing agent. () The rubber compound forming the NBR layer is
This is NBR mixed with silica filler and metal oxide.
ここでシリカ系充填剤としては、ニツプシールＶＮ−３
−ＡＱ（商品名：日本シリカ（株）製）、カーフレック
ス６７（商品名：塩野義製薬（株）製）等を使用し、そ
のＮＢＲｌＯＯ部に対する配合比は５〜３０部である。Here, as the silica-based filler, NIPSEAL VN-3
-AQ (trade name: manufactured by Nippon Silica Co., Ltd.), Carflex 67 (trade name: manufactured by Shionogi & Co., Ltd.), etc. are used, and the blending ratio is 5 to 30 parts to NBRlOO parts.
また、金属酸化物としては、ＭｇＯ，Ａｌ２Ｏ３，Ｐｂ
Ｏ等を使用し、そのＮＢＲｌＯＯ部に対する配合比は５
〜３０部である。In addition, metal oxides include MgO, Al2O3, Pb
O, etc. are used, and the blending ratio to NBRlOO is 5.
~30 copies.
上記シリカ系充填剤、金属酸化物とともにＮＢＲに配合
する副資材は、加硫剤、加硫促進剤、加硫促進助剤、補
強剤としてのカーボンブラツク、可塑剤等である。The auxiliary materials that are mixed into NBR together with the silica filler and metal oxide include a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator, carbon black as a reinforcing agent, and a plasticizer.
この発明のゴム積層体は、上記（）のゴム配合物を冷却
部ロールで混合してロール分出したシート（ＮＢＲ層）
上に、やはり上記（１）のゴム配合物を冷却ロールで混
合しロール分出したシート（フツ素ゴム層）を重ねて、
加硫接着したものである。The rubber laminate of the present invention is a sheet (NBR layer) obtained by mixing the rubber compound described in () above with a roll in the cooling section and separating the mixture with a roll.
On top of this, a sheet (fluororubber layer) made by mixing the rubber compound of (1) above with a cooling roll and distributing it with a roll is layered,
It is vulcanized and bonded.
なお、この積層体は、ホース等の場合は、押出機により
２層同時押出し、又は、第１押出機と第２押出機により
第１層上に第２層を押し出して成形する。加硫（加圧蒸
気）条件は、温度１４５〜１７０℃、時間３０〜９０１
Ｔ１１ｎとする。In the case of a hose or the like, this laminate is formed by simultaneously extruding two layers using an extruder, or by extruding a second layer on top of the first layer using a first extruder and a second extruder. Vulcanization (pressurized steam) conditions are temperature 145-170℃, time 30-901℃.
Let it be T11n.
このようにして成形した積層体は、後述の実施例で示す
ように、層間接着力が良好である。The laminate formed in this manner has good interlayer adhesion, as shown in Examples below.
また、この発明者らは、上記フツ素ゴム配合物（１）に
上記ＮＢＲゴム配合物（）を、ＮＢＲ含量５〜３００１
％となるようにブレンドしたブレンドゴム配合物を、フ
ツ素ゴム層とした場合は、予想以上にＮＢＲ層との層間
接着性が向上することを見出した。ここで、ＮＢＲ含量
５ｖ０１％以下では、余りその効果がでず、またＮＥＲ
含量３０ｖ０１％以上としても接着性（ま向上せず、か
えつてフツ素ゴム層の物性に悪影響を与える。In addition, the inventors added the above NBR rubber compound () to the above fluoro rubber compound (1) with an NBR content of 5 to 3001.
It has been found that when a fluororubber layer is made of a blended rubber compound blended so as to give Here, if the NBR content is less than 5v01%, the effect is not so great, and the NER
Even if the content is 30v01% or more, the adhesion (or adhesion) will not be improved, and will instead have an adverse effect on the physical properties of the fluoro rubber layer.
以下、実施例を比較例とともに記載し、この発明の効果
を確認する。Examples will be described below along with comparative examples to confirm the effects of the present invention.
実施例及び比較例に用いたフツ素ゴム層及びＮＢＲゴム
層を形成するコム配合物の組成は、それぞれ第１・２表
の通りである。The compositions of the comb formulations forming the fluoro rubber layer and the NBR rubber layer used in the Examples and Comparative Examples are shown in Tables 1 and 2, respectively.
テストピースは、フツ素ゴム層とＮＢＲゴム層をそれぞ
れ２ｍｍのシート状にロール分出したものを、重ねて、
１５０℃×６０ｍｉｎ１４．５ｋ９／ｃ！Ｌで加圧加硫
して作成した。The test piece was made by rolling a fluoro rubber layer and an NBR rubber layer into 2 mm sheets, and stacking them together.
150℃×60min14.5k9/c! It was created by pressure vulcanization with L.
なお、ブレンドゴム配合物で作成した、フツ素ゴム層の
第４表に示す物性試験のテストピースは、ブレンドゴム
配合物を、ロール分出し、１７『Ｃ×１５ｎ１ｎ１１０
０ｋ９／〜の圧力で加圧加硫し７て得た厚さ２ｍｍのも
のを使用した。In addition, the test piece for the physical property test shown in Table 4 of the fluoro rubber layer prepared from the blended rubber compound was prepared by rolling out the blended rubber compound,
A material having a thickness of 2 mm obtained by pressure vulcanization at a pressure of 0 k9/~ was used.
各試験方法は下記の如くである。Each test method is as follows.
（１）接者性・・・・・・ＪｌＳＫ６３Ｏｌによる。(1) Accessibility: According to JlSK63Ol.
（２）耐油性試験後接着性・・・・・・燃料油（Ｆｕｅ
ｌＤ）（３）耐寒・ヒ・・・・・・ＪＩＳＫ６３Ｏｌに
よる。（４）耐熱老化性・・・・・・１２『ＣＸ２８８
ｈ放置後、△ＥＢ（物性の保持率）を計測した。（５）
耐サワーガソリン性・・・・・・ガソリン（ラウロイル
パーオキシド含有量１ｗｔ％）に８０℃×１４４ｈ（但
し３２ｈごとに液交換）浸漬後の△ＥＢを計測した。(2) Adhesion after oil resistance test...Fuel oil (Fue)
1D) (3) Cold resistance/Heat resistance...according to JISK63Ol. (4) Heat aging resistance...12 "CX288
After standing for h, ΔEB (retention rate of physical properties) was measured. (5)
Sour gasoline resistance: ΔEB was measured after immersion in gasoline (lauroyl peroxide content: 1 wt%) at 80° C. for 144 hours (however, the liquid was replaced every 32 hours).
（６）耐アルコールガソリン性・・・・・・ガソリン（
メタノール含有量２０ｖ０１％）に４０℃×２８８ｈ浸
漬後、△（体積変化率）を計
測した。(6) Alcohol resistance to gasoline...gasoline (
After immersion in methanol content 20v01% at 40° C. for 288 hours, Δ (volume change rate) was measured.
第３表に示すように、実施例１のフツ素ゴム層とＮＢＲ
ゴム層との層間接着力は、他のフツ素層とＮＢＲゴム層
との組合せである比較例１〜５に比して格段に強い接着
力を有する。As shown in Table 3, the fluororubber layer of Example 1 and the NBR
The interlayer adhesive force with the rubber layer is much stronger than that of Comparative Examples 1 to 5, which are combinations of other fluorine layers and NBR rubber layers.
また、実施例１における、フツ素ゴム層にＮＢＲを５〜
３０Ｖ０１％ブレンドした実施例２〜６の層間接着力は
、予想以上に層間接着力が向上することがわかる。In addition, in Example 1, 5 to 5 NBR was added to the fluoro rubber layer.
It can be seen that the interlayer adhesion strength of Examples 2 to 6, which were blended with 30V01%, was improved more than expected.
Claims (1)
合物（Ｂ）からなるＮＢＲ層とを重ねて加硫接着した構
成のゴム積層体。 （Ａ）フッ化ビニリデン、六フッ化プロピレン、四フッ
化エチレンの三元共重合体からなる過酸化物加硫可能な
フッ素ゴムに、過酸化物系加硫剤が他の副資材とともに
配合されたゴム配合物。 （Ｂ）ＮＢＲに、シリカ系充填剤及び金属酸化物が他の
副資材とともに配合されたゴム配合物。２ 下記ブレン
ド配合物（Ａ）からなるフッ素ゴム層と、下記配合物（
Ｂ）からなるＮＢＲ層とを重ねて加硫接着した構成のゴ
ム積層体。 （Ａ）フッ化ビニリデン、六フッ化プロピレン、四フッ
化エチレンの三元共重合体からなる過酸化物加硫可能な
フッ素ゴムに過酸化物系加硫剤が他の副資材とともに配
合されたゴム配合物に、ＮＢＲポリマを、ＮＢＲ／（フ
ッ素ゴム＋ＮＢＲ）＝０．０５〜０．３０（容量比）の
割合でブレンドしたブレンドゴム配合物。 （Ｂ）ＮＢＲに、シリカ系充填剤及び金属酸化物が他の
副資材ととも配合されたゴム配合物。[Scope of Claims] 1. A rubber laminate having a structure in which a fluororubber layer made of the following compound (A) and an NBR layer made of the following compound (B) are laminated and vulcanized and bonded. (A) A peroxide-based vulcanizing agent is blended with a peroxide-curable fluororubber consisting of a terpolymer of vinylidene fluoride, propylene hexafluoride, and ethylene tetrafluoride along with other auxiliary materials. rubber compound. (B) A rubber compound in which a silica filler and a metal oxide are blended with NBR along with other auxiliary materials. 2 A fluororubber layer consisting of the following blended compound (A) and a fluororubber layer made of the following blended compound (A)
A rubber laminate having a structure in which the NBR layer consisting of B) is stacked and vulcanized and bonded. (A) A peroxide-based vulcanizing agent is blended with a peroxide-curable fluororubber consisting of a ternary copolymer of vinylidene fluoride, propylene hexafluoride, and ethylene tetrafluoride along with other auxiliary materials. A blended rubber compound in which an NBR polymer is blended with a rubber compound at a ratio of NBR/(fluororubber+NBR)=0.05 to 0.30 (volume ratio). (B) A rubber compound in which a silica filler and a metal oxide are blended with NBR along with other auxiliary materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2578080A JPS5933304B2 (en) | 1980-02-29 | 1980-02-29 | rubber laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2578080A JPS5933304B2 (en) | 1980-02-29 | 1980-02-29 | rubber laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56121762A JPS56121762A (en) | 1981-09-24 |
| JPS5933304B2 true JPS5933304B2 (en) | 1984-08-15 |
Family
ID=12175344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2578080A Expired JPS5933304B2 (en) | 1980-02-29 | 1980-02-29 | rubber laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5933304B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003039858A1 (en) * | 2001-11-05 | 2003-05-15 | Daikin Industries, Ltd. | Rubber laminate |
-
1980
- 1980-02-29 JP JP2578080A patent/JPS5933304B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56121762A (en) | 1981-09-24 |
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