JPH0830544B2 - Multi-layer rubber hose - Google Patents
Multi-layer rubber hoseInfo
- Publication number
- JPH0830544B2 JPH0830544B2 JP2089567A JP8956790A JPH0830544B2 JP H0830544 B2 JPH0830544 B2 JP H0830544B2 JP 2089567 A JP2089567 A JP 2089567A JP 8956790 A JP8956790 A JP 8956790A JP H0830544 B2 JPH0830544 B2 JP H0830544B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- layer
- acrylic rubber
- plasticizer
- epichlorohydrin
- 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 - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims description 37
- 239000005060 rubber Substances 0.000 title claims description 37
- 229920000800 acrylic rubber Polymers 0.000 claims description 43
- 229920000058 polyacrylate Polymers 0.000 claims description 43
- 239000004014 plasticizer Substances 0.000 claims description 31
- 229920005558 epichlorohydrin rubber Polymers 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 27
- 150000002148 esters Chemical class 0.000 claims description 14
- -1 epichlorohydrin compound Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 56
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005561 epichlorohydrin homopolymer Polymers 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ROPPTGKKZZDFJN-UHFFFAOYSA-N trinonyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCCC)C(C(=O)OCCCCCCCCC)=C1 ROPPTGKKZZDFJN-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- SMYKBXMWXCZOLU-UHFFFAOYSA-N tris-decyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCCCC)C(C(=O)OCCCCCCCCCC)=C1 SMYKBXMWXCZOLU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2319/00—Synthetic rubber
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、ゴムホースに関する。特に耐寒性を要求さ
れる燃料系・ベーパ系ホースに好適なゴムホースであ
る。TECHNICAL FIELD The present invention relates to a rubber hose. It is a rubber hose suitable for fuel-type / vapor-type hoses that require particularly cold resistance.
＜従来の技術＞ 耐劣化ガソリン性等の見地から、第１図に示す如く、
内管層１を、アクリルゴムとフッ化ビニリデン樹脂との
ポリマーブレンドのゴム配合物で、外管層２を耐ガス透
過性・耐オゾン性等の見地からエピクロロヒドリンゴム
のゴム配合物で、内管層１と外管層２との間に糸層３と
ともに介在する中間層５を、内管層１と外管層２との間
の接着性等・耐候性等の見地からアクリルゴムのゴム配
合物で形成した多層ゴムホースが提案されている（特開
昭62−51439号公報等参照）。<Prior Art> From the viewpoint of deterioration gasoline resistance, etc., as shown in FIG.
The inner tube layer 1 is a rubber compound of a polymer blend of acrylic rubber and vinylidene fluoride resin, and the outer tube layer 2 is a rubber compound of epichlorohydrin rubber from the viewpoint of gas permeation resistance, ozone resistance, etc. The intermediate layer 5 that is interposed between the inner tube layer 1 and the outer tube layer 2 together with the thread layer 3 is made of acrylic rubber from the viewpoint of adhesion, weather resistance, etc. between the inner tube layer 1 and the outer tube layer 2. A multilayer rubber hose made of a rubber compound has been proposed (see JP-A-62-51439, etc.).
そして、上記各ゴム配合物には、加工性および耐寒性
の見地から主としてエステル系可塑剤が配合されてい
る。ここで、エピクロロヒドリンゴムの場合、一般に耐
寒性に優れているとされているが、アクリルゴムの場
合、一般に耐寒性に良好でない。And, from the standpoints of processability and cold resistance, ester-based plasticizers are mainly added to the above rubber compounds. Here, epichlorohydrin rubber is generally said to be excellent in cold resistance, but acrylic rubber is generally not good in cold resistance.
そこで、上記エステル系可塑剤としては、エピクロロ
ヒドリンゴムの場合は特に限定されず、汎用可塑剤であ
るフタル酸ジ−２−エチルヘキシル等のフタル酸エステ
ル系等を使用でき、配合量も少量でよいが、アクリルゴ
ムの場合、一般的に耐寒性に優れているとされているセ
バシン酸ジオクチル（DOS）、アジピン酸ジオクチル（D
OA）等の脂肪族二塩基酸エステル系が主流であり、相対
的に多量の配合を必要とした。Therefore, the ester plasticizer is not particularly limited in the case of epichlorohydrin rubber, and a phthalate ester such as di-2-ethylhexyl phthalate which is a general-purpose plasticizer can be used, and the compounding amount is small. Good, but in the case of acrylic rubber, dioctyl sebacate (DOS) and dioctyl adipate (D) are generally said to have excellent cold resistance.
Aliphatic dibasic acid ester systems such as OA) are the mainstream, and a relatively large amount of compound is required.
＜発明が解決しようとする課題＞ しかし、上記、脂肪族二塩基酸エステル系の可塑剤で
は、アクリルゴムに対して多量に可塑剤を配合すること
が困難で、十分な耐寒性（通常、衝撃ぜい化試験＜JISK
6301＞でTb:−36℃以上）を得がたいとともに上記の如
くアクリルゴム層に直接的に接触してエピクロロヒドリ
ンゴム層が形成されている場合、昨今のより厳格な耐寒
性能の要求度の高まりから、アクリルゴム層の耐寒性が
経時的に低下することが分ってきた。<Problems to be Solved by the Invention> However, with the above-mentioned aliphatic dibasic acid ester plasticizer, it is difficult to add a large amount of plasticizer to acrylic rubber, and sufficient cold resistance (usually impact) Embrittlement test <JISK
6301>, it is difficult to obtain Tb: −36 ° C. or higher), and when the epichlorohydrin rubber layer is formed by directly contacting the acrylic rubber layer as described above, the demand for more stringent cold resistance performance has increased. From this, it has been found that the cold resistance of the acrylic rubber layer decreases with time.
本発明は、上記にかんがみて、アクリルゴム層の耐寒
性の経時劣化がほとんどない多層ゴムホースを提供する
ことを目的とする。In view of the above, an object of the present invention is to provide a multi-layer rubber hose in which the cold resistance of the acrylic rubber layer hardly deteriorates with time.
＜課題を解決するための手段＞ 本発明者らは、上記課題を解決するために、可塑剤に
よる耐寒性の向上を検討して鋭意開発に努力をした結
果、特定の可塑剤を使用すれば初期および経時耐寒性が
向上することを見出し、下記構成の本発明に想到した。<Means for Solving the Problems> In order to solve the above problems, the present inventors have studied harder the cold resistance with a plasticizer and have made intensive efforts to develop it. As a result, if a specific plasticizer is used, The inventors have found that the initial and aging cold resistance is improved, and have conceived the present invention having the following constitution.
アクリルゴム配合物で形成されるアクリルゴム層と、
該アクリルゴム層に直接的に接触してエピクロロヒドリ
ンゴム配合物で形成されてなるエピクロロヒドリンゴム
層との積層構造を具備し、前記両ゴム配合物はエステル
系可塑剤の配合処方である多層ゴムホースにおいて、 少くとも前記アクリルゴム層におけるエステル系可塑
剤が、エーテルエステル系又は３価以上の芳香族多価カ
ルボン酸エステル系から１種又は２種以上が選択されて
なり、前記アクリルゴム配合物及び前記エピクロロヒド
リンゴム配合物における可塑剤の配合量が、それぞれ、
原料ゴム（ポリマー）100重量部に対して、25〜45重量
部、13〜28重量部である、ことを特徴とする。An acrylic rubber layer formed of an acrylic rubber compound,
It has a laminated structure with an epichlorohydrin rubber layer formed of an epichlorohydrin rubber compound in direct contact with the acrylic rubber layer, and both rubber compounds are compounded formulations of an ester plasticizer. In the multi-layer rubber hose, at least one ester plasticizer in the acrylic rubber layer is selected from ether ester compounds or aromatic polyvalent carboxylic acid ester compounds having a valence of 3 or more. And the amount of the plasticizer in the epichlorohydrin rubber compound,
It is characterized in that it is 25 to 45 parts by weight and 13 to 28 parts by weight with respect to 100 parts by weight of the raw material rubber (polymer).
＜手段の詳細な説明＞ A.本発明の多層ゴムホースは、アクリルゴム配合物で形
成されるアクリルゴム層と、該アクリルゴム層に直接的
に接触してエピクロロヒドリンゴム配合物で形成されて
なるエピクロロヒドリンゴム層との積層構造を具備し、
前記両ゴム配合物はエステル系可塑剤の配合処方である
ことを前提的構成要件とする。<Detailed Description of Means> A. The multilayer rubber hose of the present invention comprises an acrylic rubber layer formed of an acrylic rubber compound and an epichlorohydrin rubber compound which is in direct contact with the acrylic rubber layer. It has a laminated structure with an epichlorohydrin rubber layer
It is a prerequisite that both rubber compounds are compounded formulations of ester plasticizers.
ここで、燃料ホース等の場合は、耐油性等の見地か
ら、通常は、アクリルゴム層が内側になるが（第１図参
照）、外管層も燃料に接触するフユエルポンプ等の場合
は、エピクロロヒドリンゴム層が内側ないし、エピクロ
ロヒドリンゴム層がアクリルゴム層でサンドイッチされ
る場合も考えられる。Here, in the case of a fuel hose, etc., the acrylic rubber layer is usually on the inside from the viewpoint of oil resistance (see FIG. 1), but in the case of a fuel pump etc. in which the outer tube layer also contacts the fuel, It is also conceivable that the chlorohydrin rubber layer is not inside and the epichlorohydrin rubber layer is sandwiched by the acrylic rubber layer.
（１）上記アクリルゴムには、アクリル酸アルキルエス
テルと２−クロロエチルビニルエーテルとの共重合体で
「ACM」の略号で示されるタイプ、および、アクリル酸
アルキルエステルとアクリロニトリルの共重合体で「AN
M」の略号で示されるタイプ、いずれのタイプのものも
含まれる。耐寒性の見地からは、ACMが望ましい。(1) The acrylic rubber is a copolymer of alkyl acrylate and 2-chloroethyl vinyl ether, which is represented by the abbreviation "ACM", and a copolymer of alkyl acrylate and acrylonitrile, "AN".
Includes types indicated by the abbreviation "M" and any type. ACM is preferable from the viewpoint of cold resistance.
具体的には、前述の特開昭62−51439号公報に例示さ
れているもの、即ち、アクリル酸アルキルエステル及
び／又はアクリル酸アルコキシ置換アルキルエステル化
合物30〜99.9％、架橋性モノマー例１〜10％、およ
び、前記、と重合可能な他のエチレン性化合物０
〜70％の重量組成を有するものが使用可能である。Specifically, those exemplified in the above-mentioned JP-A-62-51439, namely, acrylic acid alkyl ester and / or acrylic acid alkoxy-substituted alkyl ester compound 30 to 99.9%, crosslinkable monomer examples 1 to 10 %, And other ethylenic compound polymerizable with the above
Those having a weight composition of ~ 70% can be used.
（２）上記エピクロロヒドリンゴムには、エピクロロヒ
ドリン単独重合体で「CO」の略号で示されるタイプ、エ
ピクロロヒドリンとエチレンオキシドとの共重合体で、
「ECO」の略号で示されるタイプ等、汎用のものを使用
可能である。(2) The epichlorohydrin rubber is a type of epichlorohydrin homopolymer represented by the abbreviation "CO", a copolymer of epichlorohydrin and ethylene oxide,
A general-purpose type such as the type indicated by the abbreviation "ECO" can be used.
（３）上記（１）および（２）の各原料ゴムには、補強
剤（ex.カーボンブラツク）、可塑剤、加工助剤、加硫
促進剤、加硫剤、老化防止剤、その他の副資材を配合
し、ロール、バンバリーミキサー、インターミキサー等
を使用して混練することにより、ゴムホース用材料を調
製する。(3) Reinforcing rubbers (ex. Carbon black), plasticizers, processing aids, vulcanization accelerators, vulcanizing agents, antioxidants, and other auxiliary substances are included in the raw material rubbers of (1) and (2) above. A material for a rubber hose is prepared by blending the materials and kneading them using a roll, a Banbury mixer, an intermixer or the like.
各ゴムホース用材料は、複数台の押出機または多色押
出機を用いて押出され、多層ゴムホースとされる。Each rubber hose material is extruded using a plurality of extruders or a multicolor extruder to obtain a multilayer rubber hose.
B.本発明の多層ゴムホースは、上記A.の前提的構成にお
いて、少くとも前記アクリルゴム配合物におけるエステ
ル系可塑剤がエーテルエステル系又は３価以上の芳香族
多価カルボン酸エステル系から１種又は２種以上が選択
されてなり、前記アクリルゴム配合物及び前記エピクロ
ロヒドリンゴム配合物における可塑剤の配合量が、それ
ぞれ、原料ゴム（ポリマー）100重量部に対して、25〜4
5重量部、13〜28重量部である、構成を特徴的構成とす
る。B. The multilayer rubber hose of the present invention is, in the preconditional constitution of A. above, at least one ester plasticizer in the acrylic rubber composition is an ether ester type or a trivalent or higher polyvalent aromatic carboxylic acid ester type. Alternatively, two or more kinds are selected, and the compounding amount of the plasticizer in the acrylic rubber compound and the epichlorohydrin rubber compound is 25 to 4 with respect to 100 parts by weight of the raw rubber (polymer).
The characteristic constitution is 5 parts by weight and 13 to 28 parts by weight.
（１）上記エーテルエステル系可塑剤とは、重合可塑剤
の一種で、具体的には、「アデカサイザ−RS107」の商
品名でアデカ化学（株）から市販されているものを挙げ
ることができる。(1) The ether ester plasticizer is a type of polymerization plasticizer, and specific examples thereof include those commercially available from ADEKA CHEMICAL CO., LTD. Under the trade name of "ADEKA CIZER-RS107".
（２）上記３価以上の芳香族多価カルボン酸エステルと
は、ベンゼン、ナフタリン等の芳香族環に３個以上のカ
ルボキシル基が付加した芳香族多価カルボン酸化合物に
おいて、カルボキシル基の全部又は一部（望ましくは全
部）を長鎖の脂肪族アルコール（望ましくは直鎖状）で
エステル化したものをいう。(2) The above-mentioned trivalent or higher polyvalent aromatic carboxylic acid ester is an aromatic polyvalent carboxylic acid compound in which three or more carboxylic groups are added to an aromatic ring such as benzene or naphthalene. Part (preferably all) is esterified with a long-chain aliphatic alcohol (preferably linear).
ここで、アルコールの炭素数が多いほど、一般的に、
可塑剤の耐寒性は向上するが、ゴムポリマーとの相溶性
が低下するため、上記アルコールの炭素数は、４〜12と
する。また、アルキル基は直鎖状の方が、耐寒性の見地
から望ましい。Here, the higher the carbon number of the alcohol, the more
Although the cold resistance of the plasticizer is improved, the compatibility with the rubber polymer is reduced, so the carbon number of the alcohol is set to 4 to 12. Further, it is preferable that the alkyl group has a straight chain form from the viewpoint of cold resistance.
具体的には、下記に例示のトリメリト酸エステル
系、下記に例示のピロメリト酸エステル系のものを使
用可能である。Specifically, the trimellitic acid ester-based compounds exemplified below and the pyromellitic acid ester-based compounds exemplified below can be used.
トリメリト酸トリオクチル、トリメリト酸トリノニ
ル、トリメリト酸トリデシル、トリメリト酸トリイソデ
シル、トリメリト酸ウンデシル等。Trioctyl trimellitate, trinonyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, undecyl trimellitate and the like.
ピロメリト酸テトラオクチル、ピロメリト酸テトラノ
ニル、ピロメリト酸テトラデシル、ピロメリト酸トリデ
シル、ピロメリト酸テトライソデシル、ピロメリト酸テ
トラウンデシル、ピロメリト酸トリウンデシル等。Tetraoctyl pyromellitic acid, tetranonyl pyromellitic acid, tetradecyl pyromellitic acid, tridecyl pyromellitic acid, tetraisodecyl pyromellitic acid, tetraundecyl pyromellitic acid, triundecyl pyromellitic acid and the like.
（３）アクリルゴム層を形成するアクリルゴム配合物に
おける上記可塑剤の配合量は、原料ゴム（ポリマー）10
0部に対して、25〜45部、望ましくは30〜40部とする。2
5部未満では、アクリルゴム層に充分な耐寒性を得がた
く、45部を超えるとゴム自体の加硫物性および相関接着
等に悪影響を与える。(3) The compounding amount of the above-mentioned plasticizer in the acrylic rubber compound forming the acrylic rubber layer is such that the raw rubber (polymer) 10
It is 25 to 45 parts, preferably 30 to 40 parts, relative to 0 parts. 2
If it is less than 5 parts, it is difficult to obtain sufficient cold resistance in the acrylic rubber layer, and if it exceeds 45 parts, the vulcanized physical properties of the rubber itself and the correlation adhesion are adversely affected.
（４）また、エピクロロヒドリンゴム層を形成する配合
物においても、上記に例示の耐寒性可塑剤を配合しても
よいが、自体、耐寒性を有するため、他の相溶性の良好
なフタル酸エステル系等の可塑剤であつてもよい。(4) Also, in the compound forming the epichlorohydrin rubber layer, the cold-resistant plasticizer exemplified above may be compounded, but since it has cold resistance, it is possible to use other phthalates having good compatibility. It may be an acid ester type plasticizer.
この配合物における可塑剤の配合量は、原料ゴム（ポ
リマー）100部に対して、13〜28部、望ましくは15〜25
部とする。13部未満では、アクリルゴム層からの可塑剤
の移行が促進されアクリルゴム層の耐寒性が経時的に低
下するおそれがあり、また、28部を超えると可塑剤がブ
リードして、ゴム自体の加硫物性、および層間接着等に
悪影響を与える。The blending amount of the plasticizer in this blend is 13 to 28 parts, preferably 15 to 25 parts, relative to 100 parts of the raw rubber (polymer).
Part. If it is less than 13 parts, migration of the plasticizer from the acrylic rubber layer may be promoted, and the cold resistance of the acrylic rubber layer may decrease over time.If it exceeds 28 parts, the plasticizer bleeds and the rubber itself It has a bad influence on vulcanization physical properties and interlayer adhesion.
（５）上記アクリルゴム層からエピクロロヒドリンゴム
層への可塑剤の移行を考慮して、アクリルゴム層tiとエ
ピクロロヒドリンゴム層tOとの肉厚比は、アクリルゴム
層肉厚ti、エピクロロヒドリンゴム層肉厚tOとしたと
き、ti/tO＝2/1〜1/5（より望ましくは、1/2〜1/3）が
望ましい。アクリルゴム層が上記数値範囲より厚すぎる
と、エピクロロヒドリンゴム層が、相対的に薄くなりす
ぎエピクロロヒドリンゴム層の作用を奏し難くなり、薄
すぎると、可塑剤のエピクロロヒドリンゴム層への移行
が促進されて望ましくない。(5) In consideration of the migration of the plasticizer from the acrylic rubber layer to the epichlorohydrin rubber layer, the thickness ratio of the acrylic rubber layer t i and the epichlorohydrin rubber layer t O is the acrylic rubber layer thickness t When i is the thickness of the epichlorohydrin rubber layer t O , t i / t O = 2/1 to 1/5 (more preferably 1/2 to 1/3) is desirable. If the acrylic rubber layer is too thicker than the above numerical range, the epichlorohydrin rubber layer becomes relatively thin and it becomes difficult to exert the action of the epichlorohydrin rubber layer, and if it is too thin, it becomes a plasticizer epichlorohydrin rubber layer. The migration is promoted undesirably.
＜発明の作用・効果＞ 本発明の多層ゴムホースは、上記の如く、アクリルゴ
ム配合物で形成されるアクリルゴム層と、該アクリルゴ
ム層に直接的に接触してエピクロロヒドリンゴム配合物
で形成されてなるエピクロロヒドリンゴム層との積層構
造を具備し、前記両ゴム配合物はエステル系可塑剤の配
合処方である多層ゴムホースにおいて、少くとも前記ア
クリルゴム層におけるエステル系可塑剤として、エーテ
ルエステル系又は３価以上の芳香族多価カルボン酸エス
テル系の内から１種又は２種以上を選択し、前記アクリ
ルゴム配合物及び前記エピクロロヒドリンゴム配合物に
おける可塑剤の配合量が、それぞれ、原料ゴム（ポリマ
ー）100部に対して、25〜45部、13〜28部であるものを
使用する構成により、後述の実施例で示す如く、アクリ
ルゴム配合物からなるアクリルゴム層の初期及び経時双
方の耐寒性が向上する。<Operation and Effect of the Invention> As described above, the multilayer rubber hose of the present invention is formed of the acrylic rubber layer formed of the acrylic rubber compound and the epichlorohydrin rubber compound of which the acrylic rubber layer is in direct contact. In a multi-layer rubber hose having a laminated structure with an epichlorohydrin rubber layer, wherein both rubber blends are a blending formulation of an ester plasticizer, an ether ester is used as an ester plasticizer in at least the acrylic rubber layer. 1 or 2 or more types are selected from among the polyvalent aromatic polycarboxylic acid ester systems having a valence of 3 or more, and the compounding amounts of the plasticizers in the acrylic rubber compound and the epichlorohydrin rubber compound are respectively, With a composition in which 25 to 45 parts and 13 to 28 parts are used with respect to 100 parts of the raw rubber (polymer), as shown in the examples below, the acrylic resin is used. Initial and over time both cold resistance of acrylic rubber layer formed of a beam formulation is improved.
＜実施例・比較例＞ 以下、本発明の効果を確認するために行なつた試験例
について説明をする。<Examples / Comparative Examples> Hereinafter, test examples conducted to confirm the effects of the present invention will be described.
（１）第１・２表に示すアクリルゴム系、エピクロロヒ
ドリンゴム系の各ゴム配合物について、常態物性試験
（HS、TB、EB）、圧縮永久ひずみ試験（CS）および、低
温衝撃ぜい化試験（Tb）をJIS−Ｋ−6301に準じて行な
つた。(1) an acrylic rubber system shown in the first-2 table for each rubber formulation epichlorohydrin rubber, physical properties in normal state test (H S, T B, E B), compression set test (CS) and a low temperature An impact embrittlement test (T b ) was conducted according to JIS-K-6301.
下記に、上記物性略号の一覧を示す。 The following is a list of the above physical property abbreviations.
HS（Ａ）：かたさ（スプリング式JIS A）、 TB:引張り強さ（kgf/cm2） EB:破断時の伸び（％） CS:圧縮永久ひずみ率（％） Tb:ぜい化温度（℃） なお、試験片作成の際の加硫条件は、150℃×60分と
した。H S (A): Hardness (spring type JIS A), T B : Tensile strength (kgf / cm 2 ) E B : Elongation at break (%) CS: Compression set (%) T b : Embrittlement Curing temperature (° C.) The vulcanization conditions at the time of preparing the test piece were 150 ° C. × 60 minutes.
第１・２表にそれぞれ、物性試験の結果を示す。 The results of the physical property tests are shown in Tables 1 and 2, respectively.
（２）第３表に示す配合ゴムの組合せで、ECO層/ACM層/
ECO層（各2mmt）の積層体を形成し、加硫成形（条件:15
0℃×60分）し、試験片を調製し、40℃雰囲気に５日間
放置後、アクリルゴム層をスライスして試験片を調製
し、上記低温衝撃ぜい化試験を行なつた。(2) With the combination of compounded rubbers shown in Table 3, ECO layer / ACM layer /
Form a laminate of ECO layers (2 mmt each) and vulcanize (condition: 15
(0 ° C. × 60 minutes) to prepare a test piece, which was left in an atmosphere of 40 ° C. for 5 days, and the acrylic rubber layer was sliced to prepare a test piece, and the above-mentioned low temperature impact embrittlement test was conducted.
その結果を示す第３表から、本発明の実施例は、全体
として耐寒性に優れていることが分る。From Table 3 showing the results, it can be seen that the examples of the present invention as a whole have excellent cold resistance.
第１図は本発明を適用可能な燃料ホース（多層ゴムホー
ス）の一例を示す斜視図である。 １……内管層、 ５……中間層（アクリルゴム層）、 ２……外管層（エピクロロヒドリンゴム層）。FIG. 1 is a perspective view showing an example of a fuel hose (multilayer rubber hose) to which the present invention can be applied. 1 ... Inner tube layer, 5 ... Intermediate layer (acrylic rubber layer), 2 ... Outer tube layer (epichlorohydrin rubber layer).
Claims (1)
ゴム層と、該アクリルゴム層に直接的に接触してエピク
ロロヒドリン配合物で形成されてなるエピクロロヒドリ
ンゴム層との積層構造を具備し、前記両ゴム配合物はエ
ステル系可塑剤の配合処方である多層ゴムホースにおい
て、 少くとも前記アクリルゴム層におけるエステル系可塑剤
が、エーテルエステル系又は３価以上の芳香族多価カル
ボン酸エステル系から１種又は２種以上が選択されてな
り、 前記アクリルゴム配合物及び前記エピクロロヒドリンゴ
ム配合物における可塑剤の配合量が、それぞれ、原料ゴ
ム（ポリマー）100重量部に対して、25〜45重量部、13
〜28重量部である ことを特徴とする多層ゴムホース。1. A laminated structure comprising an acrylic rubber layer formed of an acrylic rubber compound and an epichlorohydrin rubber layer formed of an epichlorohydrin compound in direct contact with the acrylic rubber layer. In the multi-layer rubber hose, wherein the both rubber compounds are a compounding formulation of an ester-based plasticizer, at least the ester-based plasticizer in the acrylic rubber layer is an ether ester-based or trivalent or higher polyvalent aromatic carboxylic acid ester. One or two or more are selected from the system, and the compounding amount of the plasticizer in each of the acrylic rubber compound and the epichlorohydrin rubber compound is 25 with respect to 100 parts by weight of the raw rubber (polymer). ~ 45 parts by weight, 13
~ 28 parts by weight multi-layer rubber hose.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089567A JPH0830544B2 (en) | 1990-04-04 | 1990-04-04 | Multi-layer rubber hose |
| AU73837/91A AU625146B1 (en) | 1990-04-04 | 1991-03-27 | Multilayer rubber article |
| CA002039292A CA2039292A1 (en) | 1990-04-04 | 1991-03-28 | Multilayer rubber article |
| DE4110746A DE4110746A1 (en) | 1990-04-04 | 1991-04-03 | Multilayer rubber prod. - has layers of acrylic] and epichlorohydrin] rubbers plasticised with ether-ester(s) and ester(s) of aromatic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089567A JPH0830544B2 (en) | 1990-04-04 | 1990-04-04 | Multi-layer rubber hose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03288084A JPH03288084A (en) | 1991-12-18 |
| JPH0830544B2 true JPH0830544B2 (en) | 1996-03-27 |
Family
ID=13974392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2089567A Expired - Fee Related JPH0830544B2 (en) | 1990-04-04 | 1990-04-04 | Multi-layer rubber hose |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH0830544B2 (en) |
| AU (1) | AU625146B1 (en) |
| CA (1) | CA2039292A1 (en) |
| DE (1) | DE4110746A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19934238C1 (en) * | 1999-07-21 | 2001-01-25 | Fte Automotive Gmbh | Device for actuating a clutch, in particular for motor vehicles |
| US8652624B2 (en) | 2007-11-14 | 2014-02-18 | Dow Global Technologies Llc | Articles and methods of making the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0659727B2 (en) * | 1985-08-30 | 1994-08-10 | 日本合成ゴム株式会社 | Rubber laminate and hose made of the same |
| JPH01159245A (en) * | 1987-12-16 | 1989-06-22 | Tokai Rubber Ind Ltd | Rubber hose |
-
1990
- 1990-04-04 JP JP2089567A patent/JPH0830544B2/en not_active Expired - Fee Related
-
1991
- 1991-03-27 AU AU73837/91A patent/AU625146B1/en not_active Ceased
- 1991-03-28 CA CA002039292A patent/CA2039292A1/en not_active Abandoned
- 1991-04-03 DE DE4110746A patent/DE4110746A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| CA2039292A1 (en) | 1991-10-05 |
| DE4110746C2 (en) | 1993-07-08 |
| JPH03288084A (en) | 1991-12-18 |
| AU625146B1 (en) | 1992-07-02 |
| DE4110746A1 (en) | 1991-10-10 |
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| LAPS | Cancellation because of no payment of annual fees |