JPH03288084A - Multilayer rubber hose - Google Patents
Multilayer rubber hoseInfo
- Publication number
- JPH03288084A JPH03288084A JP2089567A JP8956790A JPH03288084A JP H03288084 A JPH03288084 A JP H03288084A JP 2089567 A JP2089567 A JP 2089567A JP 8956790 A JP8956790 A JP 8956790A JP H03288084 A JPH03288084 A JP H03288084A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- layer
- acrylic rubber
- acrylic
- rubber layer
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 35
- 239000005060 rubber Substances 0.000 title claims abstract description 35
- 229920000800 acrylic rubber Polymers 0.000 claims abstract description 44
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 44
- 239000004014 plasticizer Substances 0.000 claims abstract description 29
- 229920005558 epichlorohydrin rubber Polymers 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims description 19
- -1 ether ester Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 47
- 230000000704 physical effect Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 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
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- CTJJGIVJOBVMEO-UHFFFAOYSA-N tetraoctyl benzene-1,2,4,5-tetracarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC(C(=O)OCCCCCCCC)=C(C(=O)OCCCCCCCC)C=C1C(=O)OCCCCCCCC CTJJGIVJOBVMEO-UHFFFAOYSA-N 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
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。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a rubber hose. This rubber hose is especially suitable for fuel and vapor hoses that require 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N1と外管N2との間に糸@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
62−51433号公報等参照)。<Prior art> From the standpoint of resistance to deterioration of gasoline, as shown in FIG. From the viewpoint of gas permeability and ozone resistance, the intermediate layer 5 is made of a rubber compound of epichlorohydrin rubber and is interposed between the inner tube N1 and the outer tube N2 together with the thread @3. A multilayer rubber hose made of a rubber compound of acrylic rubber has been proposed from the viewpoint of adhesion with layer 2, weather resistance, etc. (see Japanese Patent Application Laid-Open No. 62-51433, 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。Each of the above-mentioned rubber compounds mainly contains an ester plasticizer from the viewpoint of processability and cold resistance. Here, in the case of epichlorohydrin rubber, it is generally said that it has excellent cold resistance, but in the case of acrylic rubber, it generally does not have good 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
フタル酸ジー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、−船釣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(
DOA)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 above ester plasticizer is not particularly limited in the case of epichlorohydrin rubber, and phthalate esters such as di-2-ethylhexyl phthalate, which is a general-purpose plasticizer, can be used, and the amount added may be small. However, in the case of acrylic rubber, - dioctyl sebacate (DOS), which is said to have excellent cold resistance for boat fishing, and dioctyl adipate (
Aliphatic dibasic acid esters such as DOA) are the mainstream;
Relatively large amounts of formulation were 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、衝軍ぜい化試験<JIS
K6301>でTbニー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C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。<Problem to be solved by the invention> However, with the above-mentioned aliphatic dibasic acid ester plasticizer, it is difficult to blend a large amount of plasticizer into acrylic rubber, and it is difficult to obtain sufficient cold resistance (usually Military embrittlement test <JIS
K6301>, it is difficult to obtain a Tb knee of 36°C or higher), and when the epichlorohydrin rubber layer is formed in direct contact with the acrylic rubber layer as described above, due to the recent increasing demands for stricter cold resistance performance. It has been found that the cold resistance of the acrylic rubber layer decreases over 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 multilayer rubber hose in which the cold resistance of the acrylic rubber layer hardly deteriorates over time.
<IIn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 IIn> In order to solve the above problems, the present inventors have studied and worked hard to improve cold resistance using plasticizers, and as a result, have found that:
It was discovered that the initial and aging cold resistance can be improved by using a specific plasticizer, and the present invention having the following structure was conceived.
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1111又は2種以上が選択され
てなるものである、ことを特徴とする。It has a laminated structure of an acrylic rubber layer formed of an acrylic rubber compound and an epichlorohydrin rubber layer formed of an epichlorohydrin rubber compound in direct contact with the acrylic rubber layer, The rubber compound is a multilayer rubber hose in which the ester plasticizer is compounded, and at least the ester plasticizer in the acrylic rubber layer is an ether ester or an aromatic polycarboxylic acid ester having a valence of 3 or more. It is characterized by being formed by selecting more than one species.
く手段の詳細な説明〉
A1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 the means for achieving this> A1 The multilayer rubber hose of the present invention comprises an acrylic rubber layer formed of an acrylic rubber compound, and an epichlorohydrin rubber compound in direct contact with the acrylic rubber layer. It has a laminated structure with an epichlorohydrin rubber layer, and a prerequisite component is that both of the rubber compounds are formulated with an ester plasticizer.
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ツ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 fuel hoses, etc., from the standpoint of oil resistance etc.
Usually, the acrylic rubber layer is on the inside (see Figure 1).
, in the case of a tsuyuel pump where the outer tube layer also comes into contact with the fuel,
It is also conceivable that the epichlorohydrin rubber layer is on the inside, or that the epichlorohydrin rubber layer is sandwiched between acrylic rubber layers.
(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
rAcMJ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との共重合体でr
ANMJ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 above-mentioned acrylic rubber includes a copolymer of acrylic acid alkyl ester and 2-chloroethyl vinyl ether, indicated by the abbreviation rAcMJ, and a copolymer of acrylic acid alkyl ester and acrylonitrile, r
From the viewpoint of cold resistance, ACM is desirable, including any type indicated by the abbreviation ANMJ.
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/又はアクルル酸アルコキシR換アルキルエステ
ル化合物30〜99.9%、■架橋性モノマー例1〜1
0%、および、゛■前記■、■と共重合可能な他のエチ
レン性化合物θ〜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 Japanese Patent Application Laid-open No. 62-51439, namely: (30 to 99.9% of acrylic acid alkyl ester and/or acrylic acid alkoxy R-substituted alkyl ester compound), (2) Crosslinkability Monomer examples 1-1
It is possible to use a compound having a weight composition of 0%, and 70% of another ethylenic compound θ which can be copolymerized with (1) and (2) above.
(2)上記エピクロロヒドリンゴムには、エビクロロヒ
ドリン単独重合体で「CO」の略号で示されるタイプ、
エビクロロヒドリンとエチレンオキシドとの共重合体で
、rEcOJの略号で示される等、汎用のものを使用可
能である。(2) The above epichlorohydrin rubber includes shrimp chlorohydrin homopolymer of the type indicated by the abbreviation "CO",
A copolymer of shrimp chlorohydrin and ethylene oxide, which is represented by the abbreviation rEcOJ, and other general-purpose products can be used.
(3)上記(1)および(2)の各原料ゴムには、補強
剤(ex、カーボンブラック)、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−、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) Each of the raw rubbers mentioned in (1) and (2) above contains reinforcing agents (ex, carbon black), plasticizers, processing aids, vulcanization accelerators, vulcanizing agents, anti-aging agents, and other additives. A material for a rubber hose is prepared by blending the materials and kneading them using a roll, Banbury mixer, intermixer, etc.
各ゴムホース用材料は、複数台の押出機また多色押出機
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 multiple extruders or multicolor extruders to form a multilayer rubber hose.
B、 本発明(7)多層ゴムホースは、上記A、の前捏
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る、構成を特徴的構成とする。B. The multilayer rubber hose of the present invention (7) has the above-mentioned preliminary configuration in A, wherein at least the ester plasticizer in the acrylic rubber compound is an ether ester type or a trivalent or higher aromatic polycarboxylic acid ester type. A configuration in which one or more of the following are selected is defined as a characteristic configuration.
(1)上記エーテルエステル系可塑剤とは、重合形可塑
剤の一種で、具体的には、「アデカサイザ−R5107
Jの商品名でアデカ化学■から市販されているものを挙
げることができる。(1) The above ether ester plasticizer is a type of polymeric plasticizer, specifically, “Adekasizer-R5107
Examples include those commercially available from Adeka Kagaku ■ under the trade name J.
(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(望ましくは直鎮状)で
エステル化したものをいう。(2) The above-mentioned aromatic polyvalent carboxylic acid ester having a valence of 3 or more refers to an aromatic polyvalent carboxylic acid compound in which 3 or more carboxyl groups are added to an aromatic ring such as benzene or naphthalene. A part (preferably all) of the alcohol is esterified with a long-chain aliphatic alcohol (preferably straight chain).
ここで、アルコールの炭素数が多いほど、−船釣に、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、i1寒性の見
地から望ましい。Here, as the number of carbon atoms in the alcohol increases, the cold resistance of the plasticizer improves, but the compatibility with the rubber polymer decreases, so the number of carbon atoms in the alcohol is set to 4 to 12. Further, it is preferable that the alkyl group be linear from the viewpoint of i1 coldness.
具体的には、下記のに例示のトリメリド酸エステル系、
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 esters listed below,
It is possible to use pyromellitic acid esters as exemplified in (1) below.
■トリメリド酸トリオクチル、トリメリド酸トリノニル
、トリメリド酸トリデシル、トリメリド酸トリイソデシ
ル、トリメリド酸つンデシル等■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。■Trioctyl trimellidate, trinonyl trimellidate, tridecyl trimellidate, triisodecyl trimellidate, tundecyl trimellidate, etc. ■Tetraoctyl pyromellitate, tetranonyl pyromellitate, tetradecyl pyromellitate, tridecyl pyromellitate, tetraisodecyl pyromellitate, tetraun pyromellitate Decyl, triundecyl pyromellitate, etc.
(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)1
00部に対して、25〜45部、望ましくは30〜40
部とする。25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 amount of the above plasticizer in the acrylic rubber compound forming the acrylic rubber layer is 1
00 parts, 25 to 45 parts, preferably 30 to 40 parts
Department. If it is less than 25 parts, it will be difficult to obtain sufficient cold resistance in the acrylic rubber layer, and if it exceeds 45 parts, it will have an adverse effect on the vulcanized physical properties of the rubber itself, interrelated adhesion, etc.
(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ってもよい。(4) Also, in the formulation forming the epichlorohydrin rubber layer, the cold-resistant plasticizers listed above may be blended, but since they themselves have cold resistance, other phthalates with good compatibility may be used. It may also be an acid ester plasticizer or the like.
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1
5〜25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 amount of plasticizer in this compound is 13 to 28 parts, preferably 1 part to 100 parts of raw rubber (polymer).
5 to 25 parts. If it is less than 13 parts, the migration of the plasticizer from the acrylic rubber layer may be accelerated and the cold resistance of the acrylic rubber layer may decrease over time.If it exceeds 28 parts, the plasticizer may bleed, causing damage to the rubber itself. Adversely affects vulcanized 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N t
I とエピクロロヒドリンゴムff1t、との肉厚比は
、アクリルゴム層肉厚jliエピクロロヒドリンゴム層
肉厚t。とじたとき、tI/16=2/1〜115(よ
り望ましくは、172〜1/3〉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、相体的に薄くなりすきエピクロロヒドリ
ンゴム層の作用を奏し難くなり、薄す?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) Considering the transfer of the plasticizer from the acrylic rubber layer to the epichlorohydrin rubber layer, the acrylic rubber N t
The thickness ratio between I and epichlorohydrin rubber ff1t is acrylic rubber layer thickness jli and epichlorohydrin rubber layer thickness t. When closed, tI/16 = 2/1 to 115 (more preferably 172 to 1/3). If the acrylic rubber layer is too thick than the above numerical range, the epichlorohydrin rubber layer As the layer becomes thinner, it becomes difficult for the epichlorohydrin rubber layer to perform its function, and as the layer becomes thinner, migration of the plasticizer to the epichlorohydrin rubber layer is promoted, which is undesirable.
〈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
ル系の内からから1種又は2種以上を選択して使用する
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。<Actions and Effects of the Invention> As described above, the multilayer rubber hose of the present invention includes an acrylic rubber layer formed of an acrylic rubber compound, and an epichlorohydrin rubber compound formed in direct contact with the acrylic rubber layer. In the multilayer rubber hose, both of the rubber compounds have a laminated structure with an epichlorohydrin rubber layer containing an ester plasticizer, at least an ether ester as the ester plasticizer in the acrylic rubber layer. As shown in the examples below, an acrylic rubber layer made of an acrylic rubber compound can be formed by selecting one or two or more from the group consisting of polycarboxylic acid esters and trivalent or higher aromatic polycarboxylic acid esters. Cold resistance both initially and over time 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った試験例に
ついて説明をする。<Examples/Comparative Examples> Test examples conducted to confirm the effects of the present invention will be described below.
(1)!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、Ta%E21)、圧縮永久ひずみ試験(CS)お
よび、低温衝撃ぜい化試験(Tb)試験をJIS−に−
[1301に準じて行なった。(1)! A normal physical property test (
Hs, Ta%E21), compression set test (CS), and low temperature impact embrittlement test (Tb) test to JIS-
[Performed according to 1301.]
下記(、上記物性略号の一覧を示す。Below (, a list of the above physical property abbreviations is shown.
H8(^):かたさ(スプリング式JIS^)、T、:
弓目長り強さ (kgf/C1)Ea :破断時の伸び
(%)
C5:圧縮永久ひずみ率(%)
Tb:ぜい化温度(1)
なお、試験片作成の際の加硫条件は、150℃×60分
とした。H8 (^): Hardness (spring type JIS^), T:
Curved length strength (kgf/C1) Ea: Elongation at break (%) C5: Compression set rate (%) Tb: Brittleness temperature (1) The vulcanization conditions when creating the test piece are as follows: , 150°C x 60 minutes.
第1・2表にそれぞれ、物性試験の結果を示す鋏片を調
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
を行なった。Tables 1 and 2 show the results of the physical property tests, respectively.A scissor piece was prepared, and after being left in an atmosphere of 40℃ for 5 days, the acrylic rubber layer was sliced to prepare a test piece, and the above-mentioned low-temperature impact embrittlement test was carried out. I did it.
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 are excellent in cold resistance as a whole.
(2)3N3表に示す配合ゴムの組合せで、ECO層/
ACM層/ECO層(各2m5t)の積層体を形成し、
加硫成形(条件:150℃×60分)し、試第2表(2) With the combination of compounded rubber shown in the 3N3 table, ECO layer/
Form a laminate of ACM layer/ECO layer (each 2m5t),
Vulcanization molding (conditions: 150℃ x 60 minutes) and test Table 2
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−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)。
特
許
出
願
人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). patent applicant
Claims (1)
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
るものである、 ことを特徴とする多層ゴムホース。[Claims] Laminated structure of an acrylic rubber layer formed from an acrylic rubber compound and an epichlorohydrin rubber layer formed from an epichlorohydrin rubber compound in direct contact with the acrylic rubber layer. In a multilayer rubber hose in which both of the rubber compounds are formulated with an ester plasticizer, at least the ester plasticizer in the acrylic rubber layer is an ether ester type or an aromatic polycarboxylic acid having a valence of 3 or more. A multilayer rubber hose characterized by being made of one or more esters selected from the group consisting of esters.
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 true JPH03288084A (en) | 1991-12-18 |
JPH0830544B2 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) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8652624B2 (en) | 2007-11-14 | 2014-02-18 | Dow Global Technologies Llc | Articles and methods of making the same |
Families Citing this family (1)
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 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6251439A (en) * | 1985-08-30 | 1987-03-06 | ジェイエスアール株式会社 | Rubber laminate and hose consisting of said laminate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6251439A (en) * | 1985-08-30 | 1987-03-06 | ジェイエスアール株式会社 | Rubber laminate and hose consisting of said laminate |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8652624B2 (en) | 2007-11-14 | 2014-02-18 | Dow Global Technologies Llc | Articles and methods of making the same |
Also Published As
Publication number | Publication date |
---|---|
DE4110746A1 (en) | 1991-10-10 |
CA2039292A1 (en) | 1991-10-05 |
AU625146B1 (en) | 1992-07-02 |
JPH0830544B2 (en) | 1996-03-27 |
DE4110746C2 (en) | 1993-07-08 |
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