WO1999054132A1 - Stratifie de caoutchouc nitrile reticule - Google Patents

Stratifie de caoutchouc nitrile reticule Download PDF

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Publication number
WO1999054132A1
WO1999054132A1 PCT/JP1999/002057 JP9902057W WO9954132A1 WO 1999054132 A1 WO1999054132 A1 WO 1999054132A1 JP 9902057 W JP9902057 W JP 9902057W WO 9954132 A1 WO9954132 A1 WO 9954132A1
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WO
WIPO (PCT)
Prior art keywords
nitrile rubber
crosslinked
nitrile
weight
monomer
Prior art date
Application number
PCT/JP1999/002057
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English (en)
Japanese (ja)
Inventor
Tsuyoshi Konno
Original Assignee
Nippon Zeon Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1999054132A1 publication Critical patent/WO1999054132A1/fr

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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/04—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a layer being specifically extensible by reason of its structure or arrangement, e.g. by reason of the chemical nature of the fibres or filaments

Definitions

  • the present invention relates to a rubber laminate comprising two layers of crosslinked nitrile rubber, and more particularly, to a rubber laminate having excellent cold resistance and automobile fuel permeability.
  • NBR acrylonitrile butadiene copolymer rubber
  • a mixture of NBR and polyvinyl chloride resin (Commonly referred to as polyblend) is widely used.
  • fluorine rubber which has excellent fuel permeation resistance
  • Fluororubber has insufficient cold resistance: NBR or polyblend as outer layer and fluoro rubber as inner layer to obtain hose with excellent fuel permeability and cold resistance Laminated hoses are being considered.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a crosslinked rubber made of a crosslinked rubber composition having excellent fuel permeability and excellent cold resistance and also excellent crosslink adhesion. It is to provide a laminate.
  • the present inventors have conducted intensive studies to achieve this object, and as a result, formed an outer layer with a crosslinked rubber layer containing NBR having a relatively large amount of ⁇ -ethylene unsaturated nitrile monomer units. It has been found that the purpose can be achieved by using a crosslinked rubber laminate formed of a crosslinked rubber layer containing NBR containing an extremely large amount of / 3-ethylenically unsaturated ditolyl monomer in the inner layer in contact with fuel. The present invention has been completed based on this finding.
  • the outer layer has an ⁇ , -ethylenically unsaturated nitrile monomer content of 15 to 45% by weight. /.
  • the nitrile rubber contained in the crosslinkable nitrile rubber composition for forming the inner layer is formed from a crosslinked product of the crosslinkable nitrile rubber composition for forming the inner layer.
  • a crosslinked nitrile rubber laminate having a large amount of ⁇ -ethylenically unsaturated nitrile monomer units is provided.
  • the nitrile rubber used in the present invention is a rubber obtained by copolymerizing a, an ethylenically unsaturated nitrile monomer with another monomer.
  • Examples of the monomer copolymerized with the ⁇ , ⁇ ethylenically unsaturated nitrile monomer include a conjugated diene monomer, a non-conjugated diene monomer and ⁇ -olefin.
  • Examples of the a,; 3-ethylenically unsaturated nitrile monomers include acrylonitrile, methacrylonitrile, ⁇ - chloroacrylonitrile, and the like, with acrylonitrile being preferred. These may be used in combination of two or more.
  • conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,1,3-butadiene, 1,3-pentadiene, and the like. Tage is preferred.
  • the non-conjugated diene monomer preferably has 5 to 12 carbon atoms, and examples thereof include 1,4-pentadiene and 1,4-hexadiene.
  • Hyolefin preferably has 2 to 12 carbon atoms, and examples thereof include ethylene, propylene, 1-butene, 4-methynoleic 1-pentene, 1-hexene, and 1-octene.
  • Other monomers copolymerizable with the ⁇ , iS-ethylenically unsaturated nitrile monomer include unsaturated carboxylic acid esters, aromatic vinyl monomers, and fluorine-containing vinyl monomers. , Unsaturated monocarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and copolymerizable antioxidants.
  • the unsaturated carboxylic esters include acrylates and methacrylates having an alkyl group having 1 to 18 carbon atoms, such as methyl acrylate, ethyl acrylate, n-dodecyl acrylate, methyl methacrylate, and ethyl methacrylate; Acrylates and methacrylates having an alkoxyalkyl group having 2 to 12 carbon atoms, such as methoxymethyl acrylate and methoxethyl methacrylate; hysanoethyl acrylate,] 3-cyanoethyl acrylate Acrylates and methacrylates having 2- to 12-carbon cyanoalkyl groups such as acrylates and cyanobutyl methacrylates; and hydroxys such as 2-hydroxyhexyl acrylate and hydroxypropyl acrylate Acrylate having alkyl group Ma maleic acid monoethyl, dimethyl maleate, dimethyl fumarate, Itakon acid dimethyl chill,
  • aromatic bier monomers styrene, monomethylstyrene, bierpyri Gin and the like.
  • non-conjugated diene monomer include burnorbornene, dicyclopentadiene, and 1,4-hexadiene.
  • fluorine-containing vinyl monomers include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.
  • unsaturated monocarboxylic acid include acrylic acid and methacrylic acid.
  • Examples of unsaturated dicarboxylic acids include itaconic acid, fumaric acid, and maleic acid.
  • Examples of the anhydride of unsaturated dicarboxylic acid include maleic anhydride.
  • the copolymerizable antioxidants include N— (4-anilinophenyl) acrylamide, N— (4-anilinophenyl) methacrylamide, N— (4-anilinophenyl) cinnamamide, N— (4— Anilinophenyl) crotonamide, N-phenyl 4- (3-bulbenzyloxy) aniline, N-phenyl 4- (4-bierbenziloxy) aniline and the like. These copolymerizable monomers may be used in combination of two or more.
  • nitrile rubber has a carbon-carbon unsaturated bond in the main chain, but by hydrogenating nitrile rubber, The carbon-carbon unsaturated bond can be changed to a saturated bond, and it can also be used as a nitrile-containing highly saturated rubber with improved properties such as heat resistance and sour gasoline resistance.
  • nitrile group-containing highly saturated rubber those having an iodine value of 0 to 120 are preferred, and those having an iodine value of 5 to 100 are more preferred.
  • the iodine value is an index indicating the degree of unsaturation of carbon-carbon bonds of rubber, and is a numerical value indicating the amount of iodine that can be added to 100 g of rubber in grams.
  • a particularly preferred nitrile rubber is a copolymer rubber of an ⁇ , -ethylenically unsaturated nitrile monomer and a co-gen monomer, particularly a copolymer rubber of acrylonitrile and butadiene (NBR).
  • NBR acrylonitrile and butadiene
  • the nitrile rubber can be produced by copolymerizing the above monomer by a conventionally known polymerization method, for example, emulsion polymerization or the like using a radical initiator.
  • a crosslinkable nitrile rubber composition containing at least the above nitrile rubber is used to form the inner layer and the outer layer.
  • Nitrile rubber The Mooney viscosity (ML 1 + 4 , 100 ° C.) is not particularly limited, but is preferably 15 to 140, more preferably 17 to 120, and particularly preferably 20 to 95. . If the Mooney viscosity is too low or too high, processing may be difficult.
  • the crosslinkable nitrile rubber composition for forming the inner layer has an ⁇ ,] 3-ethylenically unsaturated nitrile monomer unit amount of 43 to 60% by weight, preferably 43 to 53% by weight in the rubber. /. And more preferably 44-52 weight 0 /. It is. ⁇ ,] 3-Ethylenically unsaturated nitrile monomer If the unit amount is too small, the crosslinked nitrile rubber laminate may not have sufficient fuel permeability resistance, and if it is too large, the crosslinked nitrile rubber laminate may have cold resistance. In some cases, it became worse.
  • the crosslinkable nitrile rubber composition for forming the outer layer has a ct,] 3-ethylenically unsaturated nitrile monomer unit amount of 15 to 45% by weight, preferably 22 to 43% by weight in the rubber. %, More preferably 28 to 42% by weight. /. It is. [3] If the unit amount of 3-ethylenically unsaturated nitrile monomer is too small, the oil resistance of the crosslinked nitrile rubber laminate may be insufficient. Cold resistance may be insufficient.
  • the nitrile rubber for forming the inner layer has a larger unit amount of] -ethylenically unsaturated nitrile monomer than the nitrile rubber for forming the outer layer. It is necessary that the difference is 2 weight. Or more, more preferably 3% by weight or more.
  • the nitrile rubber contained in the crosslinkable nitrile rubber composition for forming the inner layer or the outer layer is defined as a mixture with a vinyl chloride resin (usually referred to as a polypropylene).
  • a vinyl chloride resin usually referred to as a polypropylene
  • the vinyl chloride resin used in the preparation of the polyprend in the present invention is not particularly limited.
  • the one having a force average degree of polymerization of 600 to 2000 is preferable.
  • Nitrile content in the polyblend preferably 9 5-5 0 weight 0 I, 8 5-6 0 weight. /. Still more preferably, the amount of chloride Bulle resin is preferably 5 to 5 0 wt%, and more preferably is 1 5-4 0 weight 0 I les.
  • nitrile rubber In polyblends, ⁇ , / 3-ethylenically unsaturated nitrile is used as nitrile rubber.
  • the method for producing such a polyblend is not particularly limited, but is usually a drive-lens method in which nitrile rubber and polychlorinated vinyl powder are mixed at a high temperature with a kneading machine such as a Banbury mixer, or a mixture of these in a latex state and coagulation and drying.
  • a known method such as a latex coprecipitation method in which a heat treatment is performed using a kneader such as an extruder or a Banbury mixer can be used.
  • the cross-linkable nitrile rubber composition for forming the inner layer and the outer layer is formed of the above-mentioned nitrile rubber and a cross-linking system, and if necessary, various compounds commonly used in the rubber and plastic industry.
  • the agent can be prepared by mixing and kneading with a conventional mixer such as a roll or a Banbury mixer.
  • the cross-linking system is a general term for compounds related to rubber cross-linking, such as a cross-linking agent, other compounds required for cross-linking, and compounds for controlling the speed of cross-linking.
  • cross-linking agent for nitrile rubber known sulfur cross-linking agents and organic peroxide cross-linking agents, which are usually used as NBR cross-linking agents, can be used without any limitation.
  • sulfur crosslinking agent examples include sulfur or a sulfur-donating compound (thiuram compound, morpholine compound, etc.).
  • the sulfur cross-linking agent is usually used together with a cross-linking aid such as zinc white and stearic acid and a cross-linking accelerator such as a thiuram compound, a guanidine compound, a sulfonamide compound, a thiazole compound, and a dithiolbamate.
  • the use amount of the sulfur crosslinking agent is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, and particularly preferably 100 to 100 parts by weight of nitrile rubber. Is from 0.3 to 5 parts by weight. If the amount of the sulfur crosslinking agent is too small, crosslinking may not be performed sufficiently. If the amount is too large, scorch may be generated at the time of crosslinking.
  • the amount of the crosslinking accelerator used is not particularly limited either, but is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, particularly preferably 1 to 8 parts by weight per 100 parts by weight of nitrile rubber. 5 to 6 parts by weight.
  • organic peroxide crosslinking agent usually, an organic peroxide or a combination of the organic peroxide and a crosslinking aid is used.
  • organic peroxides examples include dicumyl peroxide, g-tert-butyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, and 2,4-dichloro mouth benzoyl peroxide.
  • crosslinking assistant a compound having a polyunsaturated bond in the molecule used in ordinary organic peroxide crosslinking is used.
  • polyfunctional monomers such as ethylene dimethacrylate, diaryl phthalate, tonoleylene bismaleide, metaphenylene bismaleide, and divinylbenzene, and liquid vinyl polybutadiene.
  • the use amount of the organic peroxide is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, per 100 parts by weight of nitrilegol. Particularly preferably, it is 0.3 to 5 parts by weight. If the amount of the organic peroxide is too small, the crosslinking may be insufficient. If the amount is too large, scorch may be generated at the time of the crosslinking.
  • the amount of the crosslinking aid used is not particularly limited, but is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, particularly preferably 1.5 to 10 parts by weight per 100 parts by weight of the nitrile rubber. 5 parts by weight.
  • a reinforcing agent such as carbon black or silica
  • a filler such as calcium carbonate
  • a softening agent such as calcium carbonate
  • a plasticizer such as polymethyl methacrylate
  • an anti-aging agent such as sodium bicarbonate
  • a stabilizer such as a plasticizer
  • a processing aid such as sodium bicarbonate
  • the type and amount of the compounding agent other than the crosslinked system are not particularly limited, and can be appropriately selected and determined so as to satisfy the characteristics and the like required for the crosslinked nitrile rubber laminate.
  • rubber components other than the above-mentioned nitrile rubber for example, chloroprene rubber, chloros / levonidyl polyethylene, chloridinyl polyethylene, ethylenoxide zepichlorhydrin copolymer rubber, ethyl acrylate / 2 —Rubbers such as black ethyl vinyl ether copolymer rubber and EPDM can be used in the crosslinkable nitrile rubber composition for forming the inner layer and the Z or outer layer as long as the effects of the present invention are not impaired. .
  • chloroprene rubber chloros / levonidyl polyethylene
  • chloridinyl polyethylene chloridinyl polyethylene
  • ethylenoxide zepichlorhydrin copolymer rubber ethyl acrylate / 2
  • Rubberers such as black ethyl vinyl ether copolymer rubber and EPDM
  • crosslinked nitrile rubber laminate of the present invention two layers of a crosslinked product of the crosslinkable nitrile rubber composition for forming the inner layer and a crosslinked product of the crosslinkable nitrile rubber composition for forming the outer layer are crosslinked. Since the same type of nitrile rubber is contained in the crosslinkable nitrile rubber composition for forming each layer, a special method is required for firmly bonding the inner layer and the outer layer during the production of the crosslinked nitrile rubber laminate. However, they have the advantage that they can be easily bonded and obtained by laminating and crosslinking two types of compositions.
  • the crosslinked nitrile rubber laminate of the present invention is produced by forming a laminate of a crosslinkable nitrile rubber composition and crosslinking.
  • the crosslinkable nitrile rubber composition forming the inner layer and the outer layer is mixed with the crosslinkable rubber composition having a predetermined thickness according to the intended use of the molded article.
  • the articles may be formed into sheets and laminated to form a sheet, or may be formed into a hose by extruding the inner layer into a tube and covering the outer layer with a two-layer extrusion method.
  • these molding methods conventionally known molding methods can be used, and there is no particular limitation.
  • the sheet-like laminate is heated using a hot press or a vulcanizing can, or the hose-like laminate is cured using a vulcanizing can, both crosslinkable nitrile rubber compositions for forming an inner layer and an outer layer.
  • a crosslinked nitrile rubber laminate is obtained.
  • the cross-linking conditions are not particularly limited; the cross-linking by hot pressing is usually performed at a temperature of 140 ° C. to 200 ° C. and 20 to: L under a pressure of 50 kgf / cm 2 . Under the conditions of 5 to 60 minutes, and vulcanization with a vulcanizer, the crosslinking is usually performed at a temperature of 130 ° C to 160 ° C. It is carried out under a pressure of 8 to 5.5 kgf / cm 2 under conditions of 30 to 120 minutes.
  • the laminate of the present invention formed into a tube by a two-layer extrusion method is used as an inner tube rubber layer, and polyester fiber or the like is added thereto.
  • the reinforcing yarn layer is knitted by braiding at an appropriate knitting angle, and a crosslinkable rubber composition containing rubber components such as epichloronohydrin rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, and acrylic rubber is further provided on the outer side. It can be extruded and coated as a weatherable outer rubber layer.
  • a metal mandrel of a predetermined shape may be inserted before crosslinking.
  • a woven fabric such as polyester or polyamide is used as a base fabric layer, and the base fabric layer is punched into a predetermined shape to form an inner layer and an outer layer.
  • the sheet is sandwiched between two cross-linkable nitrile rubber composition sheets for forming, or the two cross-linkable nitrile rubber composition sheets for forming the inner layer and the outer layer are laminated and punched into a predetermined shape, and at least one of the sheets is punched out.
  • the above base cloth can be overlapped on the surface and press-crosslinked.
  • the thus obtained crosslinked nitrile rubber laminate of the present invention is used in contact with an automobile fuel such as a fuel hose or a diaphragm and is suitable as a rubber product.
  • an automobile fuel such as a fuel hose or a diaphragm
  • the production method of these rubber products is not particularly limited, and conventionally known production methods can be used.
  • NBR or polyprend and each compounding agent other than the crosslinking system are mixed and kneaded using a small Banbury mixer, and the resulting mixture is mixed and kneaded with a roll using a roll.
  • a crosslinkable nitrile rubber composition was prepared.
  • Each crosslinkable nitrile rubber composition was prepared uncrosslinked sheet one bets of uniform thickness of about 1 m m through the gap of each a 6 inch roll, overlapping each uncrosslinked sheet one preparative combination according to Table 2 These were combined and press-crosslinked at 160 ° C. for 20 minutes to obtain a uniform cross-linked nitrile rubber laminate having a thickness of 2 mm.
  • the cold resistance and gasoline permeability of each crosslinked nitrile rubber laminate were measured by the following methods.
  • N BR-I (1) 1 00 ⁇ 70 ⁇ ⁇
  • the inner diameter of the inner layer was 4 Omm by the two-layer extrusion molding method.
  • a hose having a thickness of l mm and an outer layer thickness of 3 mm was prepared.
  • the amount of decrease in the fuel oil C was extremely small, but in the hose of the comparative example, the amount of decrease in the fuel oil C was very large, and the fuel permeation resistance was poor.
  • the hose was immersed in the above-mentioned low-temperature bath in the same condition as above in the straight state for the same time as above. None was observed, but the results were the same as those in Table 2.
  • the crosslinked rubber laminate of the present invention can greatly reduce the cost of a conventional laminate made of a blend of a polyamide and a fluororesin, as compared with a laminate made of a conventional polyblend and a polyamide resin. It is suitable as a diaphragm.

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  • Laminated Bodies (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

L'invention concerne un stratifié de caoutchoucs nitriles réticulés, obtenu par stratification d'une composition de caoutchouc nitrile réticulable, de façon à former une couche extérieure contenant un caoutchouc nitrile, qui contient de 15 à 45 % en poids de motifs de monomère nitrile α, β éthyléniquement insaturé, sur une composition de caoutchouc nitrile réticulable, de façon à former une couche intérieure renfermant un caoutchouc nitrile, qui contient de 43 à 60 % en poids de motifs de monomère nitrile α, β éthyléniquement insaturé, la teneur cette composition étant supérieure de la composition de caoutchouc nitrile réticulable formant la couche extérieure. L'invention concerne également un stratifié obtenu par réticulation des compositions, de façon à lier la couche extérieure et la couche intérieure par réticulation.
PCT/JP1999/002057 1998-04-20 1999-04-19 Stratifie de caoutchouc nitrile reticule WO1999054132A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10962298A JPH11300892A (ja) 1998-04-20 1998-04-20 加硫ニトリル系ゴム積層体
JP10/109622 1998-04-20

Publications (1)

Publication Number Publication Date
WO1999054132A1 true WO1999054132A1 (fr) 1999-10-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1111005A1 (fr) * 1999-12-22 2001-06-27 Zeon Corporation Composé de caoutchouc et tuyau pour de l'essence
US6333386B1 (en) 1999-06-28 2001-12-25 Tokai Rubber Industries, Ltd. Rubber composition, hose of low fuel permeation, and electroconductive hose of low fuel permeation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001131347A (ja) * 1999-11-08 2001-05-15 Tokai Rubber Ind Ltd ゴム組成物及び自動車用燃料輸送ホース
JP3800944B2 (ja) 2000-09-28 2006-07-26 東海ゴム工業株式会社 積層ゴムホースの製造方法及び積層ゴムホース

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS555853A (en) * 1978-06-29 1980-01-17 Tokai Rubber Ind Ltd Rubber hose for connecting gasoline circulation pipe
JPH04171381A (ja) * 1990-10-31 1992-06-18 Toyoda Gosei Co Ltd 燃料系ホース
JPH0724961A (ja) * 1993-07-09 1995-01-27 Nippon Zeon Co Ltd オイル系ホ−ス

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS555853A (en) * 1978-06-29 1980-01-17 Tokai Rubber Ind Ltd Rubber hose for connecting gasoline circulation pipe
JPH04171381A (ja) * 1990-10-31 1992-06-18 Toyoda Gosei Co Ltd 燃料系ホース
JPH0724961A (ja) * 1993-07-09 1995-01-27 Nippon Zeon Co Ltd オイル系ホ−ス

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6333386B1 (en) 1999-06-28 2001-12-25 Tokai Rubber Industries, Ltd. Rubber composition, hose of low fuel permeation, and electroconductive hose of low fuel permeation
EP1111005A1 (fr) * 1999-12-22 2001-06-27 Zeon Corporation Composé de caoutchouc et tuyau pour de l'essence

Also Published As

Publication number Publication date
JPH11300892A (ja) 1999-11-02

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