AU625146B1 - Multilayer rubber article - Google Patents
Multilayer rubber article Download PDFInfo
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- AU625146B1 AU625146B1 AU73837/91A AU7383791A AU625146B1 AU 625146 B1 AU625146 B1 AU 625146B1 AU 73837/91 A AU73837/91 A AU 73837/91A AU 7383791 A AU7383791 A AU 7383791A AU 625146 B1 AU625146 B1 AU 625146B1
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- AU
- Australia
- Prior art keywords
- rubber
- article
- multilayer
- rubber layer
- acrylic
- 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.)
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- 229920001971 elastomer Polymers 0.000 title claims description 51
- 239000005060 rubber Substances 0.000 title claims description 51
- 239000004014 plasticizer Substances 0.000 claims description 62
- 229920000800 acrylic rubber Polymers 0.000 claims description 60
- 229920000058 polyacrylate Polymers 0.000 claims description 60
- 229920005558 epichlorohydrin rubber Polymers 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 34
- -1 ether ester Chemical class 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 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 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 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 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 3
- 229920001519 homopolymer Polymers 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 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 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920005561 epichlorohydrin homopolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001771 impaired effect Effects 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 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 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
- 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
- 238000004073 vulcanization Methods 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)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
AUSTRALIA
Patents Act COMPLETE SPECIFICATM 5 1 4
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: 367 Collins Street o 01 o 0 0 0 0 o0 0 Qa o 4 0 o o Applicant(s): Toyoda Gosei Co., Ltd.
1, Nagahata, Ochlai, Haruhi-cho, Nishikasugai-gun, Aichi-ken, JAPAN Address for Service is: PHILLIPS ORIODE FITZPATRICK Patent and Trade Mark Attorneys I °o 367 Collins Street S. Melbouine 3000 AUSTRALIA Complete Specification for the invention entitled: MULTILAYER RUBBER ARTICLE Our Ref 211556 POF Code: 1096/59061 i The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 1 6006 |i fioc'p 1 BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to a multilayer rubber article, for example, a tubular rubber article, comprising at least one acrylic rubber layer and an epichlorohydrin rubber layer, in which the low-temperature resistance of the acrylic rubber layer is not substantially reduced after an extended period of time.
0n BACKGROUND INFORMATION o0 10 There has been proposed, for example, in 0o at 0 Japanese Patent Application Kokai (Laid-Open) No.
0 62-51439, a multilayer rubber hose comprising an inner tubular layer 1 formed of an acrylic rubber composition of a polymer blend of an acrylic rubber and 15 a vinylidene fluoride resin having resistance to fractionated gasoline, an outer tubular layer 2 formed 0 001 of an epichiorohydrin rubber composition having resistance to gas permeation and ozone resistance, and an intermediate layer 5 and a yarn layer 3, placed between 20 the inner tubular layer 1 and the outer tubular layer 2, the intermediate layer 5 being formed of a rubber composition of an acrylic rubber adhering to the inner tubular layer 1 and the outer tubular layer 2, and having weather resistance, etc. (see Figure 1).
An ester type plasticizer is inc?.ided in each I it i i 1 of the above rubber compositions, primarily to enhance the processability and low-temperature resistance of the rubber compositions.
Epichlorohydrin rubbers are generally considered to have excellent low-temperature resistance. Therefore, there are no particular limitations on the ester type plasticizers included in the epichlorohydrin rubber composition. For example, there can be used phthalic acid ester type plasticizers, such as di-2-ethylhexyl phthalate, which are general-purpose plasticizers.
"o Moreover, the amount of the plasticizer blended in the "o o epichlorohydrin rubber composition may be small.
0 O 0o Acrylic rubbers, on the other hand, generally o 0 do not have satisfactory low-temperature resistance.
00 o o. 15 Aliphatic dibasic acid ester type plasticizers, such as dioctyl sebacate (DOS) and dioctyl adipate (DOA), are usually included in this compositicn. These plasticizers Sare generally considered to have excellent low-temperature resistance. However, a relatively large amount of these 04 44 o 20 plasticizers must be included in the acrylic rubber composition.
OBJECT OF THE INVENTION O0 It may be seen from the above, that according to the prior art, a relatively large amount of aliphatic dibasic acid ester type plasticizer must be added to the acrylic acid composition. However, it is difficult to blend large amounts of these plasticizers with an acrylic rubber; thus, it is difficult to obtain sufficient 2 1 low-temperature resistance [generally, a brittleness temperature (Tb) of -36 0 C or higher, as measured by the impact brittleness test (JIS K7301)]. Furthermore, it is known that when an epichlorohydrin rubber layer is formed in direct contact with an acrylic rubber layer, as described above, the low-temperature resistance of the acrylic rubber layer deteriorates over time. Thus, there is an unmet need for an acrylic rubber layer having high low-temperature resistance, suitable for inclusion in a multilayer rubber article, which may be in direct o contact with an epichlorohydrin rubber layer without a substantial decrease in its low-temperature resistance over time.
0 44 00 *1 S* The present invention fills this need, as it 0* i* 15 provides a multilayer rubber article, for example a tubular article, in which the low-temperature resistance of the acrylic rubber layer substantially does not 4' deteriorate over an extensive period of time.
i i.
SUMMARY OF THE INVENTION In order to solve the problems described above, Sthe present inventors have performed extensive experiments to improve the low-temperature resistance of the acrylic rubber layer in a multilayer rubber article by using plasticizers and have devoted themselves to development of these plasticizers. As a result of these efforts, it has been discovered that the initial low-temperature resistance and the low-temperature resistance of the 3 1 acrylic rubber layer after an extended period of time improves with the inclusion of one or more specific plasticizers in the acrylic rubber composition.
Thus, in accordance with the present invention, there is disclosed: a multilayer rubber article comprising: at least one acrylic rubber layer formed of an acrylic rubber composition, an epichlorohydrin rubber layer formed of an epichlorohydrin rubber composiiton which can be in direct contact with the acrylic rubber layer, ao wherein each of the two rubber compositions contains at I" o least one ester type plasticizer, and at least the ester a"0 type plasticizer in the acrylic rubber layer is selected 0 o° from the group consisting of ether ester type 00 0 15 plasticizers and plasticizers of esters of aromatic carboxylic acids having three or more hydroxyl groups.
0 BRIEF DESCRIPTION OF THE DRAWINGS 00 0 0 'Fig. 1 is a perspective view showing an example 0 of a fuel hose (a multilayer rubber hose) to which the present invention may be applied. In this figure, S1 designates the inner tubular layer, 0 41 2 designates an intermediate layer (an acrylic rubber layer), and 3 designates the outer tubular layer (an epichlorohydrin rubber layer).
-4- C 1 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The multilayer rubber article of the present invention comprises at least one acrylic rubber layer formed of an acrylic rubber composition, and an epichlorohydrin rubber layer formed of an epichlorohydrin Srubber composition which can be in direct contact with the acrylic rubber layer, wherein each of the two rubber compositions contains at least one ester type plasticizer.
The rubber article of the present invention can be tubular in shape, for example, a hose. In the o, case of the multilayer rubber article being used as rubber o0 o a hose,' for example, a fuel hose or the like, the acrylic 0 Q a oO rubber layer is usually formed as the inside layer (see V Figure However, in the case of the multilayer rubber 0 15 hose being used in a fuel pump or the like, the epichlorohydrin rubber layer may be formed as the inside layer or may be sandwiched between acrylic rubber layers.
The acrylic rubber composition can include, for example, copolymers of an acrylic acid alkyl ester and 20 2-chloroethyl vinyl ether (ACM's), and copolymers of an acrylic acid alkyl ester and acrylonitrile (ANM's).
ACM's are preferred from the viewpoint of low-temperature resistance.
As a specific example, there can be used the acrylic rubber exemplified in the above publication (Japanese Patent Unexamined Publication No. 62-51439), an acrylic rubber including an acrylic acid alkyl ester and/or an acrylic acid alkoxy-substituted S- 5
I
1 alkyl ester in a proportion of 30 to 99% by weight, (b) a crosslinkable monomer in a proportion of 1 to 10% by weight, and another ethylenic compound copolymerizable with the above monomers and in a proportion of 0 to 70% by weight.
The generally used epichlorohydrin rubbers, for example, epichlorohydrin homopolymers and copolymers of epichlorohydrin and ethylene oxide (ECO's) can be used as the epichlorohydrin rubber.
To prepare the materials for the rubber article, the acrylic rubber and the epichlorohydrin rubber each may be blended with auxiliary materials such as 1 2 reinforcing agents carbon black), plasticizers, processing aids, vulcanization accelerators, vulcanizing *j S 15 agents, antioxidants, etc., then kneaded with a roll mill, Banbury mixer, intermixer or the like.
The individual materials used in the rubber article may then be extruded into a multilayer rubber hose using a plurality of extruders or a multi-color extruder.
As noted above, at least the ester type plasticizer in the acrylic rubber composition is selected from the group consisting of ether ester type plasticizers and plasticizers of esters of aromatic carboxylic acids having three or more hydroxyl groups.
The ether ester type plasticizers are polymerizable plasticizers. A specific example thereof is a plasticizer commercially available by the name of 6 r, 1 i i r 1 ADEKA CIZER RS107, available from Asahi Denka Co., Ltd.
The esters of aromatic carboxylic acids having three or more hydroxyl groups are preferably aromatic carboxylic acids having three or more carboxyl groups substituted on the aromatic ring (for example, a benzene ring or a naphthalene ring) in which some, and preferably all, of the carboxyl groups are esterified with a long-chain aliphatic alcohol (preferably a straight-chain aliphatic alcohol).
In general, the larger the number of carbon atoms of the alcohol, the higher the low-temperature 'o resistance of the plasticizer, but the lower the 0 S compatibility of the plasticizer with a rubber polymer.
o 6 Therefore, the number of carbon atoms of the alcohol is preferably 4 to 12. The alkyl group is preferably linear from the viewpoint of low-temperature resistance.
Specific examples of aromatic carboxylic acids Swhich can be used include trimellitic acid ester type plasticizers and pyromellitic acid ester type plasticizers.
S* 20 Specific examples of trimellitic acid ester type plasticizers include, for example, trioctyl L rtrimellitate, trinonyl trimellitate, tridecyl trimellitate, 4 triisodecyl trimellitate, undecyl trimellitate, etc.
Specific examples of pyromellitic acid ester type plasticizers include, for example, tetraoctyl pyromellitate, tetranonyl pyromellitate, tetradecyl pyromellitate, tridecyl pyromellitate, tetraisodecyl pyromellitate, tetraundecyl pyromellitate, triundecyl 7 L 1 pyromellitate, etc.
The proportion of the above plasticizers incorporated into the acrylic rubber composition to form the acrylic rubber layer is 25 to 45 parts, preferably 30 to 40. parts, per 100 parts of starting rubber (polymer).
When the proportion of plasticizer is less than 25 parts, the acrylic rubber layer has insufficient low-temperature resistance. When the proportion of plasticizer exceeds parts, the vulcanizability of the rubber itself, the interlaminar bonding, etc., is impaired.
The low-temperature resistant plasticizers o o co o exemplified above may also be included in the rubber 0 o E0 composition forming the epichlorohydrin rubber layer.
°oUo Since epichlorohydrin rubbers themselves have high So% 15 low-temperature resistance, there may also be included other plasticizers such as phthalic acid ester type plasticizers which have good compatibility with the rubber.
S 4 The proportion of the plasticizers included in o' 0 Sthe rubber composition of the epichlorohydrin rubber layer VOia, 0 4 0 20 is 13 to 28 parts, preferably 15 to 25 parts, per 100 parts of starting rubber (polymer). When the proportion Sof plasticizer is less than 13 parts, the transfer of the plasticizers from the acrylic rubber layer may accelerate, resulting in deterioration of the lowtemperature resistance of the acrylic rubber layer with the lapse of time. When the proportion of plasticizer exceeds 28 parts, the plasticizer bleeds, thereby exerting an undesirable influence on the vulcanizability of the 8
A,?
1 rubber itself, the interlaminar bonding, etc.
With regard to the transfer of the plasticizers from the acrylic rubber layer to the epichlorohydrin rubber layer, the thickness ratio of the acrylic rubber layer to the epichlorohydrin rubber layer t o is preferably as follows: tl/t 0 2/1 to 1/5 (more preferably 1/2 to 1/3) wherein tl is the thickness of the acrylic rubber layer and t 0 is the thickness of the epichlorohydrin 0o rubber layer. When the thickness of the acrylic rubber o 0 10 layer is higher than the above range, the thickness of 0 0 0 o' the epichlorohydrin rubber layer decreases to such an Sextent that the effect of the epichlorohydrin rubber D 0 o o layer is difficult to obtain. When the acrylic rubber layer is too thin, the transfer of the plasticizers to the 15 epichlorohydrin rubber layer is disadvantageously 0 Cos accelerated.
As described above, the multilayer rubber 00 00 So* article of the present invention comprises at least one aurylic rubber layer formed of an acrylic rubber oot 20 composition, and an epichlorohydrin rubber layer formed 00 2 o "o of an epichlorohydrin rubber composition which can be in direct contact with the acrylic rubber layer, wherein each of the two rubber compositions contains at least one ester type plasticizer, and at least the ester type plasticizer in the acrylic rubber layer includes one or more members selected from the group consisting of ether ester type plasticizers and plasticizers of esters of aromatic carboxylic acids having three or more -9-
J'!
1 hydroxyl groups. As described in the examples provided below, by virtue of such a constitution, the acrylic rubber layer formed of the acrylic rubber composition has an improved low-temperature resistance both in the early stages and after an extended period of time.
EXAMPLES
Tests were carried out to confirm the improved properties of the present invention.
*For each of the acrylic rubber compositions 0 0 a 10 and epichlorohydrin rubber compositions listed in Tables a0 0 9 o 1 and 2 below, dry physical property tests (Hs, Tb' E a compression set test (Cs) and a low-temperature impact brittleness test (Tb) were carried out in accordance with the procedure of JIS-K-6301. The physical properties 15 identified by the above abbreviations are listed below: 00 f H Hardness [measured by a spring type oo e,
S
o hardness tester (JIS 2 T tensile strength (kgf/cm), 0 0 EB elongation at break 00 4 20 CS compression set and a Tb brittleness temperature (OC).
The test pieces were vulcanized at a temperature of 150°C for 60 minutes.
The results of the physical property tests are shown in Tables 1 and 2 below.
i i I.
o Q00 0 0 90 0 a 0 o Table 1 00-0 0 0 0 0 o A 0* Comparative Comparative Example Example Example Example 1 2 3 1 2 4 5 3 4 ACM 100 100 100 100 100 100 100 100 100 Carbon Black (HAF) 80 80 80 80 80 80 80 80 Plasticizer -Ether ester type 30 35 40 20 Pyromellitic acid ester type Recipe Trimellic acid ester type DOS es t er type Dispersing agent 1 1 1 1 1 1 1 1 1 Vulcanizing agent 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 H (JIS-A) 63 57 55 A65 nonpro- 63 63 Serious 63 s 2) bleed- TB(kgf/cm 2 99 97 87 106 cess- 110 108 ing 103 (MPa) (10.4) able (10.8) (10.7)unmeas- (10.1) Test 450 510 540 410 500 440 urable 470 Results Compression set
CS(%)
120 0 C x 22 Hr 30 36 39 27 38 37 41 low-temperature no-failure temperature -38 -44 -46 -36 -42 -38 -33 r jr I :1 Table 2 o00 0 o os 0 0 0 0 0 0 an o o o 0 0 e oa 'on r a 0 0 0 0 0. O 0 00 0 0 Epichlorohydrin rubber A B C composition ECO 100 100 100
MAF
Carbon black 55 55 Ether ester type Recipe plasticizer 15 20 Processing aid 2 2 2 Antioxidant 1 1 1 MgO 3 3 3 CaCO 3 5 5 Vulcanizing agent 1.8 1.8 1.8 Dry physical properties H (JIS-A) 63 63 T (kgf/cm 2 108 106 98 Test (MPa) (10.5) (10.4) (9.6) Results 400 430 450 sults B Compression set CS 120 0 C x 22 Hr 25 28 36 low-temperature no-failure temperature -38 -44 -46 d3Li 1 A laminate of ECO layer/ACM layer/ECO layer (thickness of each layer: 2mm) was formed using each combination of the compounded rubbers listed in Table 3 below. The compounded rubbers were vulcanized and molded (conditions 150 0 C x 60 minutes) to form test pieces.
12 i -11 i iiOil il iliiiiiiii__ il )W_ I I A 1 The test pieces were allowed to stand in a atmosphere for 5 days, following which the acrylic rubber layer of each test piece was sliced. These slices were then subjected to the above described low-temperature impact brittleness test.
The test results are shown in Table 3, where it may be seen that the examples of the present invention generally have excellent low-temperature resistance.
0 0 0 0 0 O0 0 0 o o
DO>
Table 3 Test No.
ACM layer (Tb) ECO layer (the amount of plasticizer blended) Lowtemperatureresistance of ACM layer Tb 0
C)
00 0 o000 0 0 04 0 0 o 0 0 094 1 Example 1 (-38 0 C) A (15 parts) -36 2 Example 1 B (20 parts) -38 3 Example 1 (-38 0 C) C (25 parts) -38 4 Example 2 (-44C) A (15 parts) -38 5 Example 2 (-44 0 C) B (20 parts) -42 6 Example 2 (-44 0 C) C (25 parts) -42 7 Example 3 (-46 0 C) A (15 parts) 8 Example 3 (-46 0 C) B (20 parts) -44 9 Example 3 (-46 0 C) C (25 parts) -44 Example 4 B (20 parts) 11 Example 5 (-38 0 C) B (20 parts) -36 12 Comparative Example 4 (-33 0 C) B (20 parts) 13 Comparative Example 4 (-33 0 C) B (20 parts) 13
~I
Claims (17)
1. A multilayer rubber article comprising: at least one acrylic rubber layer formed of an acrylic rubber composition, and an epichlorohydrin rubber layer formed of an epichlorohydrin rubber composition in direct contact with the acrylic rubber layer, wherein each of the two rubber compositions contains at least one ester type plasticizer, and the ester type plasticizer in the acrylic rubber layer is selected from the group consisting of ether ester type plasticizers and plasticizers of esters of aromatic carboxylic acid having three or more hydroxyl groups.
2. The multilayer rubber article of Claim 1, wherein the acrylic rubber composition comprises at least one of a copolymer of an acrylic acid alkyl ester and 2-chloroethyl vinyl ether, and a copolymer of an acrylic acid alkyl ester and acrylonitrile.
3. The multilayer rubber article of Claim 1 or 2, wherein the ester type plasticizer in the acrylic rubber layer S is a polymerizable plasticizer. 1 o
4. The multilayer rubber article of Claim 1 or 2, wherein the ester type plasticizer in the acrylic rubber layer is an aromatic carboxylic acid having three or more carboxyl S groups substituted on an aromatic ring.
5. The multilayer rubber article of Claim 4, wherein at least one of the carboxyl groups is esterified with a long-chain aliphatic alcohol.
6. The multilayer rubber article of Claim 5, wherein the number of carbon atoms of the alcohol is 4 to 12.
7. The multilayer rubber article of Claim 4, wherein 14 0¢, vA m L -i OIL- 15 the aromatic carboxylic acid is a trimellitic acid ester type plasticizer or a pyromellitic acid ester type plasticizer.
8. The multilayer rubber article of any one of Claims 1 to 7, wherein the epichlorohydrin rubber composition comprises at least one of a homopolymer of epichlorohydrin, a copolymer of epichlorohydrin or a copolymer of ethylene oxide.
9. The multilayer article of any one of Claims 1 to 8, wherein the plasticizer is added to the acrylic rubber composition in a proportion of 25 to 45 parts per 100 parts of starting rubber. The multilayer article of any one of Claims 1 to 9, wherein the plasticizer is added to the epichlorohydrin rubber composition in a proportion of 13 to 28 parts per 100 parts of starting rubber.
S
11. The multilayer article of any one of Claims 1 to r' wherein the thickness ratio of the acrylic rubber layer t 1 I to the epichlorohydrin rubber layer t 0 is t /t 2/1 to 1/5, wherein tl is the thickness of the acrylic rubber layer and t 0 is the thickness of the epichlorohydrin rubber layer.
12. The multilayer article of Claim 11, wherein the 4 thickness ratio of the acrylic rubber layer t I to the epichlorohydrin rubber layer t o is t/t 0 1/2 to 1/3, g* wherein tl is che thickness of the acrylic rubber layer and t is the thickness of the epichlorohydrin rubber layer.
13. The multilayer article of 3ny one of Claims 1 to 12, wherein the article is tubular in form.
14. The multilayer article of Claim 13, wherein the tubular article is a hose. The hose of Claim 14, wherein the acrylic rubber layer is formed as inside layer.
S Jc i cr\ C Ii 4 ^^Bff i i. -16
16. The hose of Claim 14, wherein the epichlorohydrin rubber layer is formed as inside layer or is sandwiched between acrylic rubber layers.
17. A multilayer rubber article according to Claim 1 substantially as herein described with reference to any one of the examples. DATED: 15 April 1992 PHILLIPS ORMONDE FITZPATRICK Patent Attorneys For: TOYODA GOSEI CO., LTD (2430h) j, S, P. la~I P K I IL
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089567A JPH0830544B2 (en) | 1990-04-04 | 1990-04-04 | Multi-layer rubber hose |
| JP2-89567 | 1990-04-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU625146B1 true AU625146B1 (en) | 1992-07-02 |
Family
ID=13974392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU73837/91A Ceased AU625146B1 (en) | 1990-04-04 | 1991-03-27 | Multilayer rubber article |
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 |
| DE4110746A1 (en) | 1991-10-10 |
| JPH0830544B2 (en) | 1996-03-27 |
| JPH03288084A (en) | 1991-12-18 |
| DE4110746C2 (en) | 1993-07-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |