CA1202579A - Rubber hose - Google Patents
Rubber hoseInfo
- Publication number
- CA1202579A CA1202579A CA000439238A CA439238A CA1202579A CA 1202579 A CA1202579 A CA 1202579A CA 000439238 A CA000439238 A CA 000439238A CA 439238 A CA439238 A CA 439238A CA 1202579 A CA1202579 A CA 1202579A
- Authority
- CA
- Canada
- Prior art keywords
- conjugated diene
- rubber hose
- rubber
- hydrogenated
- unsaturated nitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 18
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 18
- 150000002825 nitriles Chemical class 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 150000001993 dienes Chemical group 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 9
- 239000003502 gasoline Substances 0.000 abstract description 8
- 239000002828 fuel tank Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000002897 diene group Chemical group 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An oil-resistant rubber hose having internal and external layers made of vulcanizate of a rubber compound of partially hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydrogenated, or made of vulcanizate of a rubber compound composed of said copolymer and polyvinyl chloride resin and/or liquid NBR. This rubber hose is superior in resistance to deteriorated gasoline and low temperature, and is suitable for the automotive fuel line of the type that the fuel pump is built into the fuel tank and both the inside and outside of the fuel hose is exposed to gasoline.
An oil-resistant rubber hose having internal and external layers made of vulcanizate of a rubber compound of partially hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydrogenated, or made of vulcanizate of a rubber compound composed of said copolymer and polyvinyl chloride resin and/or liquid NBR. This rubber hose is superior in resistance to deteriorated gasoline and low temperature, and is suitable for the automotive fuel line of the type that the fuel pump is built into the fuel tank and both the inside and outside of the fuel hose is exposed to gasoline.
Description
~ ~2~57~
The present invention relates to a rubber hose - having oil-resistant internal and external layers which are superior in resistance to deteriora-ted gasoline and low tem-peratures.
The au-tomotive fuel pump is sometimes buil-t into the fuel tank. In such a case, the fuel hose connected to the fuel pump is re~uired to have oil-resistant internal and external layers. Moreoverj the fuel hose is required to be resistant to deteriorated gasoline and to low temperatures.
The deterioration of gasoline results from the high tempera-ture in the engine room. The res:i~stance to low temperatures has become necessary with the spread of automobiles into cold districts. ~eretofore, there has been no rubber hose provided Wit}l internal and external layers that meet these requirements.
According to the present invention there is provided a rubber hose comprising an inner layer and an outer layer which are made of vulcanizate of a rubber compound of partially ~0 hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydro-genated.
An oil-resistant rubber hose of this construction has internal and external layers which are resistant to deteriorated gasoline and low temperatures.
The rubber hose can also endure for a long period of time when used as a fuel hose connected to a fuel pump built into a fuel tank. In such use, both the internal layer and external layer of the hose are exposed to gasoline.
The rubber hose can also endure for a long period of time when used in extremely cold districts.
The rubber hose of this invention is superior not only in detriorated gasoline but also in resistance to the progaration of cracks. This performance is achieved by in-corporating the rubber compound with polyvinyl chloride and/or liquid NBR.
The invention will now be described in more detail, by way oE example only, with reference to the accompanying drawings, in which:-Fig. 1 is a perspective view showing one embodiment
The present invention relates to a rubber hose - having oil-resistant internal and external layers which are superior in resistance to deteriora-ted gasoline and low tem-peratures.
The au-tomotive fuel pump is sometimes buil-t into the fuel tank. In such a case, the fuel hose connected to the fuel pump is re~uired to have oil-resistant internal and external layers. Moreoverj the fuel hose is required to be resistant to deteriorated gasoline and to low temperatures.
The deterioration of gasoline results from the high tempera-ture in the engine room. The res:i~stance to low temperatures has become necessary with the spread of automobiles into cold districts. ~eretofore, there has been no rubber hose provided Wit}l internal and external layers that meet these requirements.
According to the present invention there is provided a rubber hose comprising an inner layer and an outer layer which are made of vulcanizate of a rubber compound of partially ~0 hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydro-genated.
An oil-resistant rubber hose of this construction has internal and external layers which are resistant to deteriorated gasoline and low temperatures.
The rubber hose can also endure for a long period of time when used as a fuel hose connected to a fuel pump built into a fuel tank. In such use, both the internal layer and external layer of the hose are exposed to gasoline.
The rubber hose can also endure for a long period of time when used in extremely cold districts.
The rubber hose of this invention is superior not only in detriorated gasoline but also in resistance to the progaration of cracks. This performance is achieved by in-corporating the rubber compound with polyvinyl chloride and/or liquid NBR.
The invention will now be described in more detail, by way oE example only, with reference to the accompanying drawings, in which:-Fig. 1 is a perspective view showing one embodiment
- 2 . ~. ~ 1.
5~
of the rubber hose of this invention.
DESC~IPTION OF THE PREFERRED EMBODIMENT
The internal layer 1 and the external layer 3 of the rubber hose of this invention as shown in Fig. 1 are made of vulcanizate of partially hydrogenated unsaturated nitrile copolymer rubber (referred to as hydrogenated NBR hereinafter), or vulcanizate of a polymer composition composed of hydrogenated NBR and/or liquid NBR as mentioned below.
(a) Hydrogenated NBR
Hydrogenated NBR is an unsaturated nitrile-conju-gated diene copolymer rubber produced in the usual way by emulsion polymerization or solution polymerization, .. ..
with at least 50~ of the conjugated diene units hydrog-enated. If the degree of hydrogenation is less than 50~, the properties intended in this invention are not obtained. 100~ hydrogenation is possible; but hydrog-enation less than 98% is desirable for a proper cure rate in the case of sulfur vulcanization~
The copolymer rubber to be hydrogenated is prepared by copolymerizing an unsaturated nitrile such as acrylo-nitrile and methacrylonitrile with at least one of con-jugated dienes such as 1,3-butadiene, isoprene, and 1/3~
pen~adiene, or by copolymerizing the above-mentioned un-saturated nitrile with a conjugated diene partly substi-~2~25~9 tuted with methyl ester, butyl ester, and 2-ethylhexyl ester of unsaturated carboxylic acid su~h as acrylic acid, methacrylic acid, fumaric acid, and itaconic acid, or with N-methylol acrylamide. Examples of such copoly-mer rubbers include acrylonitrile-butadiene copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylo~
nitrile-butadiene-isoprene copolymer rubber, acrylonit-rile-butadiene-methyl acrylate terpolymer rubber, and acrylonitrile-butadiene-b~tyl acrylate terpolymer rubber.
Most suitable among them is acrylonitrile-butadiene co-polymer rubber. The quantity of the unsaturated nitrile in the hydrogenated NBR is usually 10 to 70 wt%; and it is properly determined according to the object of use and the miscibility with PVC to be mixed 1n the polymer compositions (b), (c), and (d) mentioned below.
(b) A polymer composition composed of the above-men-tioned hydrogenated NBR (a) and polyvinyl chloride resin (referred to as PVC hereinafter) The PVC includes polyvinyl chloride and copoly-mers of vinyl chloride and vinyl acetate or other mono-olefinic monomers. The PVC is incorporated into the hydrogenated ~R in an amoun-t greater than 5 wt%, preferably about 20% (based on the total weight). If the quantity is less than 5 wt%, the resulting hose is not satisfactory in the resistance to deteriorated ~as-57~
oline. The more the quantity of PVC incorporated, themore is enhanced the resin-attributable properties.
However, as a matter of course, there is a limit at which the rubber composition can be vulcanized but the resulting vulcanized rubber is poor in performance~
The quantiLy of PVC to be incorporated shvuld be deter-mined according to the intended use and requirement.
The upper limit is usually 60 wt%. PVC is incorporated into the hydrogenated NBR by using a roll or Banbury mixer or by mixing in a solution, followed by coprecip-itation and drying.
~c) A polymer composition composed of the hydrogenated NBR (a) and a liquid unsaturated nitrile conjugated diene copolymer having a number-average molecular weight of 500 to 10,000 ~referred to as liquid NBR hereinafter) Any liquid NBR having a number-average molecular weight less than 500 is easily extracted by solvents from the polymer composition and does not provlde the resistance to propagation of cracks. On the other hand, any liquid NBR having a number-average molecular weight greater than 10,000 does not improve the resistance to propagation of cracks, either. A preferred value is 1,000 to 5,000~
For good miscibility with the hydrogenated NBR and for the improved properties intended in this invention, ~Z5~9 the liquid NBR should be composed of 10 to 70 wt%, pref-erably 20 to 50 wt~, of unsaturated nitrile; 20 to 80 wt%, preferably 25 to 75 wt~, of conjugated diene; and 0 to 20 wt~, preferably 0.1 to lS wt~, of vinyl monomer which is copolymerizable with unsaturated nitrile and conjugated diene. The unsaturated nitrile and conju-gated diene are as mentioned under the paragraph for hydrogenated NBR. A preferable unsaturated nitrile is acrylonitrile, and a preferable conjugated diene is butadiene or isoprene. The vinyl monomer copolymeriz-able with the unsaturated nitrile and conjugated diene includes, for example, unsaturated carboxylic acidfi such as acrylic acid, methacrylic acid, and itaconic acid/ and esters thereof; vinyl pyridine nomer such as 2-vinylpyridine; and N-methylol acrylamide. Pref-erable among them are acrylic acid and methacrylic acid.
The liquid NBR is incorporated into the hydrogenated NBR in an amount greater than 2 wt% (based on the total weight). If the quantity is less than 2 wt%, the effect of the liquld NBR is not sufficient. The upper limit is about 50 wt~ (based on the total weight), at which the resulting polymer composition is excessively low in vis~
cosity and is poor in physical properties such as perma-nent compression set. The liquid NBR can be incorporated into the hydrogenated NBR in the same way as mentioned i7~
in the above paragraph (b).
Id) A polymer composition composed of the polymer co~-position (c) [which is composed of the hydrogenated N~R
and the liquid NBR3 and PVC
The PVC and the quantity and method of its incor- :
poration are as mentioned in the above paragraph ~b).
That is to say, the PVC includes polyvinyl chloride and copolymers of vinyl chloride and vinyl acetate or other monoolefinic monomers. The PVC is lncorporated into the pnlymer composition of hydrogenated NBR and liquid NBR in an amount greater than 5 wt%, preferably about 20 wt% (based on the total weight)~
The above-mentioned hydrogenated NBR (a) and the polymer compositions 5b), (c), and (d) composed mainly of hydrogenated NBR may be incorporated with commonly used auxiliary materials including inorganic fillers such as carbon black, silica, and metal oxide; organic ~illers such as lignin; softener, plasticizer; and col-orant; together with a proper amount of sulfur or per-oxide vulcanizing agent and vulcanization accelerator.
The rubber hose of this invention is produced by the steps of forming the inner layer 1 by extruding the above-mentioned polymer ccmposition, forming the braided reinforcement layer 2, applying an adhesive, forming the external layer 3 by extruding the above-:: L2~2S~9 mentioned polymer ccmposition, and finally vulcanizingthe green hose.
The present invention has been described with reference to a three-layered rubber hose made up of an inner layer 1, a braided reinforcement layer 2, and an outer layer 3. However, this invention is not limited to it. The scope of this invention covers multi-layered rubber hose having an intermediate layer in addition to thin inner and outer layers.
5~
of the rubber hose of this invention.
DESC~IPTION OF THE PREFERRED EMBODIMENT
The internal layer 1 and the external layer 3 of the rubber hose of this invention as shown in Fig. 1 are made of vulcanizate of partially hydrogenated unsaturated nitrile copolymer rubber (referred to as hydrogenated NBR hereinafter), or vulcanizate of a polymer composition composed of hydrogenated NBR and/or liquid NBR as mentioned below.
(a) Hydrogenated NBR
Hydrogenated NBR is an unsaturated nitrile-conju-gated diene copolymer rubber produced in the usual way by emulsion polymerization or solution polymerization, .. ..
with at least 50~ of the conjugated diene units hydrog-enated. If the degree of hydrogenation is less than 50~, the properties intended in this invention are not obtained. 100~ hydrogenation is possible; but hydrog-enation less than 98% is desirable for a proper cure rate in the case of sulfur vulcanization~
The copolymer rubber to be hydrogenated is prepared by copolymerizing an unsaturated nitrile such as acrylo-nitrile and methacrylonitrile with at least one of con-jugated dienes such as 1,3-butadiene, isoprene, and 1/3~
pen~adiene, or by copolymerizing the above-mentioned un-saturated nitrile with a conjugated diene partly substi-~2~25~9 tuted with methyl ester, butyl ester, and 2-ethylhexyl ester of unsaturated carboxylic acid su~h as acrylic acid, methacrylic acid, fumaric acid, and itaconic acid, or with N-methylol acrylamide. Examples of such copoly-mer rubbers include acrylonitrile-butadiene copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylo~
nitrile-butadiene-isoprene copolymer rubber, acrylonit-rile-butadiene-methyl acrylate terpolymer rubber, and acrylonitrile-butadiene-b~tyl acrylate terpolymer rubber.
Most suitable among them is acrylonitrile-butadiene co-polymer rubber. The quantity of the unsaturated nitrile in the hydrogenated NBR is usually 10 to 70 wt%; and it is properly determined according to the object of use and the miscibility with PVC to be mixed 1n the polymer compositions (b), (c), and (d) mentioned below.
(b) A polymer composition composed of the above-men-tioned hydrogenated NBR (a) and polyvinyl chloride resin (referred to as PVC hereinafter) The PVC includes polyvinyl chloride and copoly-mers of vinyl chloride and vinyl acetate or other mono-olefinic monomers. The PVC is incorporated into the hydrogenated ~R in an amoun-t greater than 5 wt%, preferably about 20% (based on the total weight). If the quantity is less than 5 wt%, the resulting hose is not satisfactory in the resistance to deteriorated ~as-57~
oline. The more the quantity of PVC incorporated, themore is enhanced the resin-attributable properties.
However, as a matter of course, there is a limit at which the rubber composition can be vulcanized but the resulting vulcanized rubber is poor in performance~
The quantiLy of PVC to be incorporated shvuld be deter-mined according to the intended use and requirement.
The upper limit is usually 60 wt%. PVC is incorporated into the hydrogenated NBR by using a roll or Banbury mixer or by mixing in a solution, followed by coprecip-itation and drying.
~c) A polymer composition composed of the hydrogenated NBR (a) and a liquid unsaturated nitrile conjugated diene copolymer having a number-average molecular weight of 500 to 10,000 ~referred to as liquid NBR hereinafter) Any liquid NBR having a number-average molecular weight less than 500 is easily extracted by solvents from the polymer composition and does not provlde the resistance to propagation of cracks. On the other hand, any liquid NBR having a number-average molecular weight greater than 10,000 does not improve the resistance to propagation of cracks, either. A preferred value is 1,000 to 5,000~
For good miscibility with the hydrogenated NBR and for the improved properties intended in this invention, ~Z5~9 the liquid NBR should be composed of 10 to 70 wt%, pref-erably 20 to 50 wt~, of unsaturated nitrile; 20 to 80 wt%, preferably 25 to 75 wt~, of conjugated diene; and 0 to 20 wt~, preferably 0.1 to lS wt~, of vinyl monomer which is copolymerizable with unsaturated nitrile and conjugated diene. The unsaturated nitrile and conju-gated diene are as mentioned under the paragraph for hydrogenated NBR. A preferable unsaturated nitrile is acrylonitrile, and a preferable conjugated diene is butadiene or isoprene. The vinyl monomer copolymeriz-able with the unsaturated nitrile and conjugated diene includes, for example, unsaturated carboxylic acidfi such as acrylic acid, methacrylic acid, and itaconic acid/ and esters thereof; vinyl pyridine nomer such as 2-vinylpyridine; and N-methylol acrylamide. Pref-erable among them are acrylic acid and methacrylic acid.
The liquid NBR is incorporated into the hydrogenated NBR in an amount greater than 2 wt% (based on the total weight). If the quantity is less than 2 wt%, the effect of the liquld NBR is not sufficient. The upper limit is about 50 wt~ (based on the total weight), at which the resulting polymer composition is excessively low in vis~
cosity and is poor in physical properties such as perma-nent compression set. The liquid NBR can be incorporated into the hydrogenated NBR in the same way as mentioned i7~
in the above paragraph (b).
Id) A polymer composition composed of the polymer co~-position (c) [which is composed of the hydrogenated N~R
and the liquid NBR3 and PVC
The PVC and the quantity and method of its incor- :
poration are as mentioned in the above paragraph ~b).
That is to say, the PVC includes polyvinyl chloride and copolymers of vinyl chloride and vinyl acetate or other monoolefinic monomers. The PVC is lncorporated into the pnlymer composition of hydrogenated NBR and liquid NBR in an amount greater than 5 wt%, preferably about 20 wt% (based on the total weight)~
The above-mentioned hydrogenated NBR (a) and the polymer compositions 5b), (c), and (d) composed mainly of hydrogenated NBR may be incorporated with commonly used auxiliary materials including inorganic fillers such as carbon black, silica, and metal oxide; organic ~illers such as lignin; softener, plasticizer; and col-orant; together with a proper amount of sulfur or per-oxide vulcanizing agent and vulcanization accelerator.
The rubber hose of this invention is produced by the steps of forming the inner layer 1 by extruding the above-mentioned polymer ccmposition, forming the braided reinforcement layer 2, applying an adhesive, forming the external layer 3 by extruding the above-:: L2~2S~9 mentioned polymer ccmposition, and finally vulcanizingthe green hose.
The present invention has been described with reference to a three-layered rubber hose made up of an inner layer 1, a braided reinforcement layer 2, and an outer layer 3. However, this invention is not limited to it. The scope of this invention covers multi-layered rubber hose having an intermediate layer in addition to thin inner and outer layers.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A rubber hose comprising an inner layer and an outer layer which are made of vulcanizate of a rubber compound of partially hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydrogenated.
2. A rubber hose comprising an inner layer and an outer layer which are made of vulcanizate of a rubber compound composed of partially hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydrogenated and more than 5 wt% (based on the total weight) of polyvinyl chloride resin.
3. A rubber hose comprising an inner layer and an outer layer which are made of vulcanizate of a rubber compound composed of partially hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydrogenated and more than 2 wt% (based on the total weight) of liquid unsaturated nitrile-conjugated diene copolymer having a number-average molecular weight of 500 to 10,000.
4. A rubber hose comprising an inner layer and an outer layer which are made of vulcanizate of a rubber compound composed of partially hydrogenated unsaturated nitrile-conjugated diene copolymer in which at least 50% of the conjugated diene units is hydrogenated, more than 2 wt% (based on the total weight) of liquid unsaturated nitrile-conjugated diene copolymer having a number-average molecular weight of 500 to 10,000, and more than 5 wt% (based on the total weight) of polyvinyl chloride resin.
5. A rubber hose as recited in any of claims 1 to 3, wherein the rubber hose has at least one intermediate layer between said inner layer and outer layer.
6. A rubber hose as recited in claim 1, wherein the rubber hose has at least one intermediate layer between said inner layer and outer layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57-190953 | 1982-10-30 | ||
| JP19095382A JPS5980591A (en) | 1982-10-30 | 1982-10-30 | Rubber hose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1202579A true CA1202579A (en) | 1986-04-01 |
Family
ID=16266421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000439238A Expired CA1202579A (en) | 1982-10-30 | 1983-10-18 | Rubber hose |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5980591A (en) |
| CA (1) | CA1202579A (en) |
| DE (1) | DE3338865A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795635A (en) * | 1993-07-09 | 1998-08-18 | Nippon Zeon Co., Ltd. | Oil hose |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3514697A1 (en) * | 1985-04-24 | 1986-11-06 | Bayer Ag, 5090 Leverkusen | RUBBER ITEMS FROM DIFFERENT RUBBER LAYERS, THEIR PRODUCTION AND USE |
| JPH0658156B2 (en) * | 1985-07-19 | 1994-08-03 | 横浜ゴム株式会社 | Hose |
| JPH07260052A (en) * | 1994-03-22 | 1995-10-13 | Yokohama Rubber Co Ltd:The | Hydraulic hose for construction machine |
| DE202020107325U1 (en) * | 2020-12-17 | 2021-01-08 | Rehau Ag + Co | Hose line, in particular for drinking water applications |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2807395A (en) * | 1954-05-24 | 1957-09-24 | Acf Ind Inc | Electric fuel pump mounting |
| DE1129055B (en) * | 1955-06-09 | 1962-05-03 | Tokheim Corp | Vertically arranged fuel pump with a paddle wheel, immersed in the container |
| GB1226320A (en) * | 1969-11-24 | 1971-03-24 | ||
| JPS54132647A (en) * | 1978-04-06 | 1979-10-15 | Nippon Zeon Co Ltd | Vulcanizable rubber composition having improved ozon crack and oil resistance |
| JPS5811461B2 (en) * | 1978-12-26 | 1983-03-03 | 東海ゴム工業株式会社 | Rubber hose inner tube forming material for fuel |
| US4486480A (en) * | 1981-12-30 | 1984-12-04 | Toyoda Gosei Co., Ltd. | Rubber hose comprising a liquid nitrile-butadiene copolymer incorporated into a partially hydrogenated unsaturated acrylonitrile-butadiene copolymer |
-
1982
- 1982-10-30 JP JP19095382A patent/JPS5980591A/en active Granted
-
1983
- 1983-10-18 CA CA000439238A patent/CA1202579A/en not_active Expired
- 1983-10-26 DE DE19833338865 patent/DE3338865A1/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795635A (en) * | 1993-07-09 | 1998-08-18 | Nippon Zeon Co., Ltd. | Oil hose |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3338865A1 (en) | 1984-08-16 |
| JPS5980591A (en) | 1984-05-10 |
| JPH0112994B2 (en) | 1989-03-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |