WO2007026707A1 - Caoutchouc de copolymère de nitrile réticulé, composition de caoutchouc de copolymère de nitrile et procédé pour produire la composition - Google Patents

Caoutchouc de copolymère de nitrile réticulé, composition de caoutchouc de copolymère de nitrile et procédé pour produire la composition Download PDF

Info

Publication number
WO2007026707A1
WO2007026707A1 PCT/JP2006/316999 JP2006316999W WO2007026707A1 WO 2007026707 A1 WO2007026707 A1 WO 2007026707A1 JP 2006316999 W JP2006316999 W JP 2006316999W WO 2007026707 A1 WO2007026707 A1 WO 2007026707A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer rubber
tolyl
weight
plasticizer
cross
Prior art date
Application number
PCT/JP2006/316999
Other languages
English (en)
Japanese (ja)
Inventor
Akira Imada
Yoshiyuki Odagawa
Original Assignee
Zeon Corporation
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 Zeon Corporation filed Critical Zeon Corporation
Priority to JP2007533262A priority Critical patent/JPWO2007026707A1/ja
Publication of WO2007026707A1 publication Critical patent/WO2007026707A1/fr

Links

Classifications

    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—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

Definitions

  • Nitrile copolymer rubber cross-linked product Nitrile copolymer rubber cross-linked product, nitrile copolymer rubber composition, and method for producing the composition
  • the brittle temperature is low (excellent in cold resistance) and the gasoline permeability is low (gasoline permeability resistance). It relates to a crosslinked nitrile copolymer rubber.
  • a rubber nitrile copolymer rubber containing a, j8-ethylenically unsaturated-tolyl monomer unit and a conjugated diene monomer unit or olefin monomer unit has been used. It is known as rubber with excellent oil resistance, and its cross-linked products are mainly used as materials for rubber products around various oils of automobiles such as fuel hoses, gaskets, packings and oil seals.
  • nitrile content ⁇ , j8-ethylenically unsaturated-tolyl monomer unit
  • Patent Document 1 discloses an extremely high-tolyl-tolyl copolymer rubber having a nitrile content of 45% by weight or more (in the examples, -tolyl content is 48% by weight).
  • a rubber hose for fuel equipped with a cross-linked layer in which the blending amount of the cold-resistant plasticizer is increased so that the gasoline permeability and the brittle temperature are not more than specific numbers, respectively.
  • the market it is desirable to further reduce gasoline permeability even on the premise of using a rubber having a high -tolyl content.
  • Patent Document 2 a rubber for a fuel hose comprising a blend of a nitrile copolymer rubber having a nitrile content of 43 to 50% by weight and a vinyl chloride resin having a specific solubility parameter and molecular weight. Compositions have been proposed. However, in recent years when environmental problems have become stricter, rubber cross-linked products containing a large amount of halogen are desired.
  • Patent Document 3 the ultra-high height-tolyl used for the glass transition temperature of 15-30 ° C and the glass transition temperature extrapolation end temperature of 70 ° C or less (super-high-tolyl is the nitrile content. It means a very high tolyl content of 55-80% by weight.) -Tolyl copolymer rubbers have been proposed. However, since the rubber of Patent Document 3 has a high brittle temperature of -3 to 12 ° C, the operating temperature environment is limited, and the plasticizer tends to bleed.
  • Patent Document 1 Japanese Patent Laid-Open No. 11-304058
  • Patent Document 2 JP 2001-72804 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-206011
  • the object of the present invention is to provide an unsaturated nitrile monomer unit content of! /, A very low level of gasoline, low gasoline permeability, low brittleness and low brittle temperature. It is to provide a crosslinked polymer rubber.
  • the present inventors have found that the problems result of intensive studies to solve, for example, nitrile content 55 to 80 wt 0/0 of ultra high - tolyl - latex tolyl copolymer rubber, plastic It was found that the above-mentioned object was achieved by mixing a solid mixture obtained by mixing with an emulsion of an agent and then coagulating and drying, thereby completing the present invention.
  • a, j8-ethylenically unsaturated-tolyl monomer unit having 55 to 80 wt% -tolyl copolymer rubber (A) Agent (B) Ol: LO There is provided a cross-linked tolyl copolymer rubber containing 0 part by weight and having an embrittlement temperature of ⁇ 50 to ⁇ 5 ° C.
  • the cross-linked product preferably has a gasoline permeability coefficient force of 200 g'mmZm 2 'day or less with respect to gasohol in which the weight ratio of isooctane Ztoluene Zethanol is 40Z40Z20.
  • the plasticizer (B) is an ester compound (b) of a compound (bl) having a chemical structure represented by the following general formula (1) and an ether bond-containing alcohol (b2). .
  • R represents an alkylene group having 2 to 10 carbon atoms, and COOH represents a carboxy group.
  • the cross-linked product is preferably the ⁇ , j8-ethylenically unsaturated-tolyl monomer unit force acrylonitrile unit and Z or meta-tally-tolyl unit.
  • the -tolyl copolymer rubber (A) further comprises 20 to 45% by weight of a gen monomer unit and a Z or a-olefin monomer unit.
  • the plasticizer (B) is dibutoxetyl adipate and Z or di (butoxyethoxyethyl) adipate.
  • a method for producing the above-tolyl copolymer rubber composition comprising a, j8-ethylenically unsaturated-tolyl monomer unit 55 to 80% by weight.
  • a method for producing a nitrile copolymer rubber composition is provided.
  • the plasticizer (B) force is preferably the ester compound (b).
  • a laminate having at least a layer (I) comprising any of the above-mentioned tolyl copolymer rubber cross-linked products, preferably any of the above-mentioned tolyl copolymers.
  • the gasoline permeability is low and the brittle temperature is low and the brittle temperature is low. Things are provided.
  • the -tolyl copolymer rubber cross-linked product of the present invention comprises: a, j8-ethylenically unsaturated-tolyl monomer unit 55 to 80 wt% -tolyl copolymer rubber (A) in 100 parts by weight
  • A a, j8-ethylenically unsaturated-tolyl monomer unit 55 to 80 wt% -tolyl copolymer rubber
  • A a bridge that contains 0.1 to 100 parts by weight of plasticizer (B) and has an embrittlement temperature in the range of -50 to -5 ° C.
  • the nitrile copolymer rubber (A) has an ⁇ , ⁇ -ethylenically unsaturated-tolyl monomer unit in an amount of 55 to 80% by weight, preferably 56%, based on 100% by weight of all monomer units. -76 wt%, more preferably 57-72 wt%. If the a, j8-ethylenically unsaturated-tolyl monomer unit content is too low, the oil resistance of the cross-linked product may deteriorate and the gasoline permeability may increase. On the other hand, if the content of 0L, j8-ethylenically unsaturated-tolyl monomer unit is too large, the brittle temperature may increase.
  • the ⁇ , j8-ethylenically unsaturated nitrile monomer forming the a, j8-ethylenically unsaturated-tolyl monomer unit is an a, ⁇ -ethylenically unsaturated compound having a nitrile group. If there is no limit. Examples of such compounds include: acrylonitrile; ⁇ - chloroacrylonitrile; a-halogenoacrylo-tolyl such as a-bromoacrylonitrile; and (X-alkylacrylonitrile; such as meta-tali-tolyl. Among these, acrylonitrile and And Z or meta-tally-tolyl are preferred, j8-ethylenically unsaturated-tolyl monomer may be used in combination of two or more of these.
  • the nitrile copolymer rubber (A) usually also has a gen monomer unit or an ⁇ -olefin monomer unit because the cross-linked product has rubber elasticity.
  • the gen monomer forming the gen monomer unit is preferably a conjugated gen unit such as 1,3 butadiene, isoprene, 2,3 dimethyl-1,3 butadiene, 1,3 pentagen, etc. And a non-conjugated diene monomer having 5 to 12 carbon atoms, such as 1,4 pentagen and 1,4 monohexagen. Of these, 1,3 butadiene is preferred, with conjugated diene monomers being preferred.
  • a-olefin monomer forming the a-olefin monomer unit ethylene, propylene, 1-butene, 4-methyl 1-pentene, 1 to 1, which preferably have 2 to 12 carbon atoms are preferred. Examples include xenene and 1-otaten.
  • the content of the gen monomer unit or a-olefin monomer unit in the nitrile copolymer rubber (A) is 45 to 20% by weight, preferably 100 to 20% by weight, preferably 100% by weight of the total monomer units. 4 4 to less than 24% by weight, more preferably 43 to 28% by weight. If these monomer units are too small, the rubber elasticity of the crosslinked product may be lowered. On the other hand, if it is too much, heat aging resistance and chemical stability may be impaired.
  • the nitrile copolymer rubber (A) can be copolymerized in addition to the ⁇ , ⁇ -ethylenically unsaturated-tolyl monomer unit, the gen monomer unit or the ⁇ - olefin monomer unit.
  • Other monomer units may be contained in an amount of preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less based on 100% by weight of the total monomer units.
  • Other strong copolymerizable monomers include, for example, aromatic bur compounds such as styrene, a-methylstyrene, butyltoluene; acrylic acid, methacrylic acid, maleic acid, anhydrous maleic acid, itaconic acid, A, ⁇ -ethylenically unsaturated carboxylic acid and its anhydride such as itaconic anhydride, fumaric acid, fumaric anhydride; methyl (meth) acrylate [means methyl acrylate and methyl methacrylate. The same applies to ethyl (meth) acrylate.
  • 100 ° C) is preferably 15-200, more preferably 30
  • the mu-one viscosity of the nitrile copolymer rubber (A) is too low, the strength characteristics of the crosslinked product may be deteriorated. Conversely, if it is too high, the processability of the nitrile copolymer rubber composition may be reduced.
  • the method for producing the nitrile copolymer rubber (A) is not particularly limited. In general, ⁇ , ⁇ -ethylenically unsaturated-tolyl monomer, gen monomer or a-olefin monomer, and other copolymerizable with these that can be prepared as required A method of copolymerizing monomers is convenient and preferable.
  • the polymerization method deviations from the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used, but the ease of control of the polymerization reaction can be improved with the plasticizer (B) described later.
  • An emulsion polymerization method using a force-on surfactant such as stool for mixing is preferable.
  • the nitrile copolymer rubber (A) is obtained by hydrogenating (hydrogenation reaction) an unsaturated bond portion in a gen monomer unit of a copolymer obtained by copolymerization as described above. Even so.
  • the method for hydrogenation is not particularly limited, and a known method may be employed.
  • the polymerization method of the nitrile copolymer rubber (A) is not limited! For example, the following method can be employed as an example of the polymerization method.
  • ⁇ ⁇ -ethylenically unsaturated-tolyl monomer (ml) used for polymerization and Of the total 100% by weight of conjugation monomer (m2), 60-85% by weight of monomer (ml) in the initial (first stage) polymerization, and 3-15% by weight of monomer ( Use m2). If the amount of monomer (ml) used exceeds 85% by weight, or if the amount of monomer (m2) used is less than 3% by weight, the monomer (m2 ) May disappear and polymerization may stop.
  • the amount of monomer (ml) used is less than 60% by weight, or if the amount of monomer (m2) used exceeds 15% by weight, the total amount of nitrile copolymer rubber produced will increase. There is a possibility that the content of the monomer (ml) unit with respect to 100% by weight of the monomer unit is less than 55% by weight.
  • the remainder of the monomer is fed.
  • the remainder of the monomer may be supplied continuously or divided and supplied in multiple stages.
  • the second stage of polymerization is carried out by continuously supplying the remainder of the monomer, usually all of the remainder of the monomer is fed over 1 hour and the polymerization conversion rate is 50-80. The polymerization is stopped when the weight percentage is reached.
  • the monomer added in the second stage polymerization m
  • the total ratio of 1) and the monomer (m2) is 100% by weight, the following is preferable. That is, less than 50% by weight monomer (ml) and more than 50% by weight monomer (m2), preferably 20-40% by weight monomer (ml) and 60-80% by weight.
  • the monomer (m2) may disappear before the predetermined polymerization conversion rate is reached, and the polymerization may stop.
  • the second and subsequent polymerizations are performed by supplying the remainder of the monomer in multiple stages, that is, when the polymerization is performed in three stages, for example, the first stage polymerization conversion rate
  • a part of the remainder of the monomer is supplied at a time to perform the second stage polymerization, and when the polymerization conversion rate reaches 30 to 50% by weight.
  • the remainder of the monomer is supplied at a time to carry out the third stage polymerization, and the polymerization is usually stopped when the polymerization conversion rate reaches 50 to 80% by weight.
  • the first, second, and third stage polymerization conversion rates reached 10 to 30% by weight, 30 to 50% by weight, and 50 to 65% by weight, respectively.
  • the remainder of the monomer is sequentially fed to polymerize, and the polymerization is stopped when the polymerization conversion rate reaches 65 to 85% by weight.
  • the monomer supplied at each stage after the second stage is the monomer (ml) and monomer (m2) to be added at each stage.
  • the total ratio is 100% by weight, the following is preferable. That is, less than 50% by weight of monomer (ml) and 50% by weight or more of monomer (m2), preferably 20-40% by weight of monomer (ml) and 60-80% by weight of single monomer It may be a body (m2), or all may be a monomer (m2). If the monomer (m2) is less than 50% by weight, the monomer (m2) may disappear before the predetermined polymerization conversion rate is reached, and the polymerization may be stopped.
  • nitrile copolymer rubber cross-linked product of the present invention Before the nitrile copolymer rubber cross-linked product of the present invention is obtained, a -tolyl copolymer rubber composition containing nitrile copolymer rubber (A) and plasticizer (B) is prepared. There is a need.
  • plasticizer (B) those conventionally used as a plasticizer for blending rubber can be used without limitation.
  • plasticizers examples include the following.
  • a compound (bl) having a chemical structure represented by the following general formula (1) such as dibutoxy shechinolea dipate, di (butoxy shech chechinole) adipate, an ether bond-containing alcohol (b2), Of the ester compound (b).
  • R represents an alkylene group having 2 to 10 carbon atoms
  • COOH represents a carboxy group
  • dialkyl esters of adipic acid such as di (2-ethylhexyl) adipate, disodecyl adipate, diisonol adipate, etc .; di (2-ethylhexyl) azelate, diisooctyl Azelaic acid esters such as azelate, di-n-hexyl azelate; sebacate esters such as di-n-butyl sebacate, di (2-ethylhexyl) sebacate; dibutyl phthalate, di (2-ethyl) Xylyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, diunedecyl phthalate, butyl benzyl phthalate, dinor
  • Compound (bl) represented by the above general formula (1) which is one raw material component of the ester compound (b) [hereinafter sometimes referred to as the compound (bl).
  • the alkylene group R is preferably a straight chain.
  • the carbon number is preferably 2 to 10 and more preferably 4 to 8.
  • Specific examples of the compound (bl) include succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like.
  • an ether bond-containing alcohol (b2) which is the other raw material component of the ester compound (b) [hereinafter sometimes referred to as an alcohol (b2). ] Is preferably monohydric alcohol.
  • the carbon number is preferably 4 to 10, and more preferably 6 to 8.
  • the number of ether bonds contained in the molecule of alcohol (b2) is preferably 1 to 4, more preferably 1 to 2.
  • preferable alcohol (b2) include alcohols having 4 carbon atoms and 1 ether bond such as methoxypropyl alcohol, ethoxyethyl alcohol, propoxymethyl alcohol; dimethoxyethyl alcohol, methoxyethoxymethyl alcohol (CH
  • Alcohols with 5 carbon atoms and 1 ether bond such as butyl alcohol, ethoxypropyl alcohol, propoxyethyl alcohol, etc .; dimethoxypropyl alcohol, methoxyethoxyethyl alcohol (CH 2 O—C H O—C H OH), diethoxymethyl alcohol
  • Alcohol having 5 carbon atoms and 2 ether bonds such as alcohol; Butoxyethyl alcohol, propoxypropyl alcohol, ethoxybutyl alcohol, methoxypentyl alcohol and other 6 carbon ethers having 1 ether bond; dimethoxybutyl alcohol, methoxy Ethoxypropinoreanoreconole (CH OC H OC H OH), Jetki Shech Alcohol having 6 carbon atoms and 2 ether linkages such as alcohol, butoxypropyl alcohol, propoxybutyl alcohol, ethoxypentyl alcohol, methoxyhexyl alcohol, etc. 7 alcohols having 1 ether bond; dimethoxypentyl alcohol , Methoxyethoxybutyl alcohol (CH OC H OC H OH),
  • An alcohol having 2 ether linkages an alcohol having 8 ether linkages such as pentoxypropyl alcohol, butoxybutyranolol, propoxypentinoreanolol, ethoxyhexenoreanolol and methoxyheptyl alcohol; Butokishetoki Siethyl Alcohol (CH OC H OC H OH), Dipropoxychetyl alcohol
  • Mouth pill alcohol (CH O-C H O-C H OH), diethoxybutyl alcohol, etc.
  • ester compound (b) a compound obtained by arbitrarily combining the compound (bl) and the alcohol (b2) can be used.
  • a monoester compound and a diester compound are preferably used.
  • a diester compound is preferable.
  • preferable diester compounds include dibutoxy acetyl adipate and di (butoxyethoxyethyl) adipate, and di (butoxyethoxyethyl) adipate is particularly preferable.
  • the mixing ratio of the nitrile copolymer rubber (A) and the plasticizer (B) is such that the plasticizer (B) in the emulsion is 100 parts by weight of the -tolyl copolymer rubber (A) in the latex. 0.1-: LOO parts by weight, preferably 3-50 parts by weight, more preferably 5-20 parts by weight. If the amount of the plasticizer (B) is too small, the brittle temperature of the resulting crosslinked product may be increased. Conversely, if the amount is too large, bleeding of the plasticizer may occur. [0041] Nitrile copolymer rubber (A) the concentration of the latex, more preferably preferably fixture 10 to 50 wt% 5-60 wt 0/0. Further, it is preferable that the nitrile copolymer rubber (A) is produced by emulsion polymerization and used after completion of the polymerization reaction.
  • emulsion of plasticizer (B) is preferably one of the concentration of 10 to 70% by weight of a medium of water, more preferably from 20 to 60 weight 0/0.
  • the method for preparing the emulsion is not limited, but preferably 1 to 20% by weight, more preferably 1.5 to 15% by weight of the emulsifier is dissolved in water with respect to the plasticizer (B), and then stirred vigorously.
  • the method of introducing the plasticizer (B) under the shearing force of is preferred.
  • emulsifiers include key-on surfactants such as potassium rosinate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate; polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, etc.
  • Nonionic surfactants Cationic surfactants such as didecyldimethylammonum chloride and stearyl trimethylammonumum chloride, and the same emulsifier used for emulsion polymerization of nitrile copolymer rubber (A) Things can be used.
  • the mixing method of the latex of the nitrile copolymer rubber (A) and the emulsion of the plasticizer (B) is not limited as long as they can be mixed sufficiently uniformly. Either continuous type may be used.
  • the obtained mixed solution is coagulated.
  • a method of adding a coagulant such as salt calcium, barium sulfate, aluminum sulfate to the mixed solution under stirring is usually employed.
  • the solidified product is filtered and then dried at 40 to: LOO ° C., preferably 50 to 90 ° C., to obtain a solid product.
  • the water content of the solid is preferably 0.05 to 5% by weight, more preferably 0.1 to 1.0% by weight.
  • the -tolyl copolymer rubber composition of the present invention usually contains a mixture for rubber other than the mixture of the -tolyl copolymer rubber (A) and the plasticizer (B) obtained as described above. Containing agents, for example
  • cross-linking agent for forming a cross-linked product.
  • the crosslinking agent is not limited as long as it is normally used as a crosslinking agent for nitrile group-containing copolymer rubber.
  • Preferred crosslinker Examples thereof include a sulfur-based crosslinking agent or an organic peroxide crosslinking agent, and among them, a sulfur-based crosslinking agent is more preferable.
  • Sulfur-based crosslinking agents include powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface treatment sulfur and insoluble sulfur, and the like; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzo Sulfur-containing compounds such as thiazyl disulfide, N, N, monodithiobis (hexahydro-2H-azenopine-2), phosphorus-containing polysulfide and polymer polysulfide; tetramethylthiuramdis And sulfur-donating compounds such as rufide, selenium dimethyldithiocarbamate, and 2- (4 'morpholinodithio) benzothiazole.
  • a crosslinking assistant such as zinc white or stearic acid; guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea
  • Crosslinking accelerators such as systems can be used.
  • the amount of these crosslinking aids and crosslinking accelerators is not particularly limited, and is usually used in the range of 0.1 to 5 parts by weight per 100 parts by weight of the nitrile copolymer rubber (A). Can do.
  • Examples of the organic peroxide crosslinking agent include dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, tamen hydroperoxide, paramentane hydroperoxide, 1, 3 and 1, 4 bis (t-butylperoxyisopropyl) benzene, 1,1-di-t-butylperoxy-3,3 trimethylcyclohexane, 4,4 bis- (t-butylperoxy) -n-butylvalerate, 2,5 Dimethyl-2,5 Di-t-butylperoxyhexane, 2,5-Dimethyl-2,5-di-t-butylperoxyhexyne-3, 1,1-di-t-butylperoxy 3,5,5 Trimethylcyclohexane, p Examples include ruperoxide, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate and the like.
  • a polyfunctional monomer such as trimethylolpropane trimetatalylate, dibutenebenzene, ethylene dimetatalylate, or triallyl isocyanurate is used as a crosslinking aid. It is done.
  • the amount of these crosslinking aids is not particularly limited, but it can be generally used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the nitrile copolymer rubber (A).
  • the content of the crosslinking agent in the nitrile copolymer rubber composition is not limited, but is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the nitrile copolymer rubber (A). More preferably, it is 0.2 to 5 parts by weight.
  • the nitrile copolymer rubber composition may contain other crosslinking retarders, anti-aging agents, fillers, reinforcing agents, lubricants, adhesives, lubricants, flame retardants, antifungal agents, and antistatic agents as necessary. You may contain additives, such as a coloring agent and a coloring agent.
  • an anti-aging agent such as phenol, amine, benzimidazole or phosphoric acid can be used.
  • phenolic systems such as 2,2'-methylenebis (4-methyl 6-t-butylphenol)
  • amine systems 4,4'-bis ( ⁇ , a-dimethylbenzyl) diphenylamine is used in benzimidazole systems.
  • Examples include 2-mercaptobenzimidazole. These may be used alone or in combination of two or more.
  • carbon black, silica, calcium carbonate, magnesium carbonate, tar, clay and the like can be used. These can be obtained by adding a silane coupling agent or the like.
  • the nitrile copolymer rubber composition may be blended with a rubber other than the nitrile copolymer rubber (A) as long as the effects of the present invention are not impaired.
  • the rubber other than the nitrile copolymer rubber (A) is not particularly limited. Examples thereof include attalinole rubber, fluoro rubber, styrene butadiene copolymer rubber, ethylene propylene terpolymer rubber, natural rubber, polyisoprene rubber and the like.
  • crosslinking agents for example, metal soap Z sulfur vulcanizing agent, triazine Z dithiocarbamate compound, polycarboxylic acid Z-form salt compound, polyamine System compounds (hexamethylenediamine, triethylenediamine, triethylenetetramine, hexamethylenediamine rubamate, ethylenediamine amine rubamate, etc.) can be used in combination as necessary.
  • metal soap Z sulfur vulcanizing agent triazine Z dithiocarbamate compound
  • polycarboxylic acid Z-form salt compound polyamine System compounds (hexamethylenediamine, triethylenediamine, triethylenetetramine, hexamethylenediamine rubamate, ethylenediamine amine rubamate, etc.) can be used in combination as necessary.
  • the -tolyl copolymer rubber (A) and the plasticizer (B) are also used.
  • anti-aging agents, supplements, etc., excluding cross-linking agents and heat-labile cross-linking aids are added to solid mixtures.
  • Components such as strong agents are primarily kneaded with a mixer such as a Banbury mixer, intermixer, kneader, etc., then transferred to a roll or the like and added with a crosslinking agent, etc., followed by secondary kneading.
  • Mu-one viscosity of the nitrile copolymer rubber composition (hereinafter referred to as "compound dome viscosity") (ML, 100 ° C) is preferably 20 to 200, More preferably 30-15
  • the -tolyl copolymer rubber crosslinked product of the present invention is obtained by crosslinking the -tolyl copolymer rubber composition prepared as described above.
  • molding is performed with a molding machine corresponding to the shape of the cross-linked product to be obtained, for example, an extruder, an injection molding machine, a compressor, a roll, and the like.
  • the shape of the cross-linked product is fixed by reaction.
  • Crosslinking may be performed after molding in advance, or may be performed simultaneously with molding.
  • the molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C.
  • the crosslinking temperature is usually 100 to 200 ° C, preferably 130 to 190 ° C, and the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 1 hour.
  • the cross-linked tolyl copolymer rubber of the present invention has a brittle temperature according to JIS K6301 of ⁇ 50 to ⁇ 5 ° C., preferably ⁇ 35 to ⁇ 5 ° C., more preferably ⁇ 25 to ⁇ 7. ° C. If the embrittlement temperature is too low, the gasoline permeability of the cross-linked product may be high. Conversely, if the brittle temperature is too high, use in a low temperature environment becomes difficult.
  • the -tolyl copolymer rubber cross-linked product of the present invention is an aluminum cup method (test of examples described later) using gasohol (mixture of gasoline and alcohol) in which the weight ratio of isooctane Z toluene Z ethanol is 40Z40Z20.
  • gasoline permeability measured by law reference is, 200g'mm / m 2 'day is preferably less tool 180g'mm / m 2' day or less, more preferably tool 16 0g'mmZm 2 'day or less are particularly preferred . If the gasoline permeability is too high, it is not suitable as a low gasoline permeability material required for fuel hoses.
  • the laminate having at least the layer (I) made of the cross-linked product is suitably used as a fuel hose or the like.
  • 8-ethylenically unsaturated-tolyl monomer unit is 5 wt% or more and less than 55 wt%, preferably 18 wt% or more and 45 wt% or less.
  • Laminar strength is preferred due to low gasoline permeability.
  • the rubber (L) has the same monomer units as the nitrile copolymer rubber (A) except that the content of a, j8-ethylenically unsaturated-tolyl monomer units is different.
  • the plasticizer (M) is the same as the plasticizer (B).
  • each layer is preferably 0.1 to LOmm, more preferably 0.2 to 5 mm for layer (I), and preferably 0.1 to LOmm, more preferably 0.2 to 5 mm for layer ( ⁇ ). It is.
  • the total thickness of the layer (I) and layer ( ⁇ ) is the same as that of layer (I).
  • the low gasoline permeability possessed by the layer and the low brittleness temperature characteristics possessed by the layer ( ⁇ ) can be highly balanced.
  • a multilayer hose having two or more layers having at least the layer (I) as an inner layer, which also has such a laminate strength, can be used as a fuel hose.
  • the crosslinked nitrile copolymer rubber of the present invention has low gasoline permeability even at a so-called ultra-high level where the unsaturated nitrile monomer unit content is 55 to 80 wt%. Brittleness has the advantage of low temperature. Therefore, for example, it is useful as a fuel hose having a single layer of the cross-linked product, and as a fuel hose having a multilayer structure having the cross-linked product as an inner layer. Furthermore, the -tolyl copolymer rubber cross-linked product of the present invention can be suitably used for sealing purposes (packing, gasket, diaphragm, etc.).
  • the mu-one viscosity of the “nitrile copolymer rubber” (Polymer-one) and the mu-one viscosity of the “-Tolyl copolymer rubber composition” (Compound-one) are JIS K6300 ⁇ Therefore, measure 7.
  • the nitrile copolymer rubber composition was put into a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and press-molded at 160 ° C. for 20 minutes with pressure to obtain a sheet-like crosslinked product.
  • the obtained sheet-like cross-linked product was punched with a JIS No. 3 dumbbell to prepare a test piece. Using the obtained test piece, the tensile strength, elongation and 100% tensile stress of the crosslinked product were measured according to JIS K6251.
  • the hardness of the cross-linked product was measured using a durometer hardness tester type A according to JIS K6253.
  • the specimen obtained in the same manner as in (3) above was placed at 100 ° C for 70 hours in accordance with the normal oven method of JIS K6257, then taken out and measured for tensile strength and elongation as in (3) above. With respect to the obtained tensile strength and elongation, the rate of change (%) of each of the normal properties of (3) above was determined. Further, the hardness was measured in the same manner as in the above (4), and the change (point) from the normal physical property value in the above (4) was determined for the obtained hardness.
  • gasoline permeability was measured by the aluminum cup method.
  • the aluminum cup method first, put 50 ml of fuel oil C or fuel oil CE-20 into a 100 ml capacity aluminum cup, cover it with the above test piece, and tighten it. Adjust the test piece so that the area separating the inside and outside of the aluminum cup is 25.50 cm 2 , leave the aluminum cup in a thermostat at 23 ° C, and then measure the weight every 24 hours. The oil permeation amount is measured every 24 hours, and the maximum amount is taken as the permeation amount (single ⁇ : g'mmz m 'day ⁇
  • the embrittlement temperature (° C) was measured.
  • a reaction vessel was charged with 240 parts of water, 68.2 parts of acrylonitrile, 8.4 parts of 1,3-butadiene and 2.5 parts of sodium dodecylbenzenesulfonate (emulsifier), and the temperature was adjusted to 5 ° C. Next, the gas phase was depressurized and sufficiently degassed.
  • a radical initiator 0.06 part of paramentane hydroperoxide, 0.02 part of sodium ethylenediamine tetraacetate, 0.06 part of ferrous sulfate (7 water salt) And 0.06 part of sodium formaldehyde sulfoxylate and 1 part of dodecyl mercabtan (chain transfer agent) were added to initiate the first stage reaction of the emulsion polymerization.
  • a reaction vessel was charged with 250 parts of water, 60 parts of acrylonitrile, 20 parts of 1,3-butadiene, 2.5 parts of sodium dodecylbenzene sulfonate, 1 part of tododecyl mercaptan and 0.008 part of ferrous sulfate. After fully degassing the phase by reducing the pressure, 0.03 part of paramentane hydroperoxide was charged, and emulsion polymerization was started at 10 ° C. When the polymerization conversion ratio to the charged monomer reached 42 and 60% by weight, 10 parts of 1,3-butadiene was added respectively, and the polymerization conversion ratio to the charged monomer reached 74% by weight.
  • nitrile copolymer rubber (A3) had an acrylonitrile monomer unit content of 49% by weight and a polymer-one viscosity of 90.0.
  • Di (butoxyethoxyethyl) adipate plasticizer
  • the di (butoxyethoxyethyl) adipate prepared above was added to 100 parts by weight of the solid content (polymer) of the latex.
  • a mixed solution was obtained by covering 30 parts by weight of emulsion. Thereafter, this mixture is mixed with 4% by weight of salty calcium (coagulant) based on the solid content of the latex.
  • the polymer was coagulated by pouring into an aqueous solution containing. This was filtered to collect the crumb, washed with water, and dried under reduced pressure at 60 ° C. to obtain a solid mixture of nitrile copolymer rubber (A1) and a plasticizer.
  • this mixture is transferred to a roll and tetramethylthiuram disulfide (product name ⁇ Noxeller TT '', Ouchi Shinsei Co., Ltd., cross-linking accelerator) 1.5 parts, ⁇ -Cyclohexyl-2-benzothiazolylsulfenamide (Product name “Noxeller CZ”, Ouchi Shinsei Co., Ltd., cross-linking accelerator) 1.5 parts
  • 0.5 part of 325 mesh sulfur was added and kneaded at 50 ° C. to prepare a nitrile copolymer rubber composition.
  • Example 1 The same procedure as in Example 1 was conducted except that the latex of the tolyl copolymer rubber (A2) was used in place of the latex of the nitrile copolymer rubber (A1) in Example 1. A composition was prepared. Table 1 shows the results of tests and evaluations for the same items as in Example 1.
  • the latex of the nitrile copolymer rubber (A1) is poured into an aqueous solution containing 4% by weight of salty calcium (coagulant) with respect to the solid content of the latex under stirring, and polymer is obtained. Solidified. The coagulated product was separated by filtration, and crumbs were collected, washed with water, and then dried under reduced pressure at 60 ° C. to obtain a tolyl copolymer rubber (A1).
  • Comparative Example 2 the -tolyl copolymer rubber (A1) obtained in Comparative Example 1 was obtained by coagulation and drying in the same manner as in Comparative Example 1 in Comparative Example 3.
  • -Tolyl copolymer rubber (A3) was used in the same manner as in Comparative Example 1 except that di (butoxyethoxyethyl) adipate was not added during kneading with a roll.
  • a copolymer rubber composition was prepared. Table 1 shows the results of tests and evaluations for the same items as in Example 1.
  • the nitrile copolymer rubber cross-linked product of the present invention has sufficient normal properties and heat aging resistance, and furthermore, gasoline with less oil penetration in oil immersion tests.
  • the embrittlement temperature with low permeability was sufficiently low (Examples 1 and 2).
  • high-tolyl rubber (DN4050, manufactured by Nippon Zeon Co., Ltd., acrylonitrile monomer unit content 40 wt%, polymer Mooney viscosity 50.0, brittle temperature 20.2 ° C) 60 parts of black, 1 part of stearic acid, 5 parts of zinc oxide and 5 parts of di (butoxyethoxyethyl) adipate were added and mixed at 50 ° C. The mixture is then transferred to a roll and 1.5 parts of tetramethylthiuram disulfide, 1.5 parts of N cyclohexyl 2 benzothiazolylsulfenamide, and 0.5 parts of 325 mesh sulfur are added and added.
  • a high-tolyl rubber composition was prepared by kneading at ° C.
  • Test oil C (g-mm / m'-day) 20 59 Test force 'Soline permeability
  • Fuel oil CE— 20 (g-mm / m 2 -day) 99 310 Evaluation Embrittlement temperature (.c) -17.4 17.2 Value As shown in Table 2, the -tolyl copolymer rubber cross-linked product of the present invention was used. Layer (I) and a layer ( ⁇ ) using a tolyl copolymer rubber having a tolyl content of 40% by weight has a low gasoline permeability (layer (I) In addition, the brittle temperature was sufficiently low (Example 3).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un caoutchouc de copolymère de nitrile réticulé qui comprend 100 parties en poids d'un caoutchouc de copolymère de nitrile (A) ayant de 55 à 80 % en poids de motifs d'un monomère nitrile α,β-éthyléniquement insaturé et de 0,1 à 100 parties en poids d'un plastifiant (B) incorporé dans celui-ci, et a une température de fragilité allant de -50 à -5 °C. De préférence, le caoutchouc réticulé a un coefficient de perméabilité à l’essence inférieur ou égal à 200 g.mm/m2.jour, en termes de perméabilité à une essence-alcool constituée par l’isooctane, le toluène et l’éthanol dans une proportion de 40/40/20 en poids. Le plastifiant (B) est de préférence un ester d'un composé acide dicarboxylique spécifique avec un alcool ayant une liaison éther. Le caoutchouc de copolymère de nitrile réticulé peut avoir une faible température de fragilité (une excellente résistance au froid) et une faible perméabilité à l'essence (une excellente imperméabilité envers l’essence) en dépit de la teneur excessivement élevée en motifs de monomère nitrile insaturé.
PCT/JP2006/316999 2005-08-31 2006-08-29 Caoutchouc de copolymère de nitrile réticulé, composition de caoutchouc de copolymère de nitrile et procédé pour produire la composition WO2007026707A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007533262A JPWO2007026707A1 (ja) 2005-08-31 2006-08-29 ニトリル共重合体ゴム架橋物、ニトリル共重合体ゴム組成物および該組成物の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005251362 2005-08-31
JP2005-251362 2005-08-31

Publications (1)

Publication Number Publication Date
WO2007026707A1 true WO2007026707A1 (fr) 2007-03-08

Family

ID=37808794

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/316999 WO2007026707A1 (fr) 2005-08-31 2006-08-29 Caoutchouc de copolymère de nitrile réticulé, composition de caoutchouc de copolymère de nitrile et procédé pour produire la composition

Country Status (2)

Country Link
JP (1) JPWO2007026707A1 (fr)
WO (1) WO2007026707A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008123405A1 (fr) * 2007-03-29 2008-10-16 Zeon Corporation Composition de caoutchouc copolymère nitrile et composition de latex copolymère nitrile
EP2028021A1 (fr) * 2007-08-16 2009-02-25 The Goodyear Tire & Rubber Company Pneu avec composant disposant d'une combinaison de plastifiants
WO2009096456A1 (fr) * 2008-01-30 2009-08-06 Zeon Corporation Composition de latex de copolymère de nitrile et composition de caoutchouc de copolymère de nitrile
CN105330913A (zh) * 2015-11-24 2016-02-17 中国航空工业集团公司沈阳飞机设计研究所 一种混炼胶
JP2020050722A (ja) * 2018-09-26 2020-04-02 日本ゼオン株式会社 ゴム混合液、ニトリル基含有共重合体ゴム組成物、架橋性ゴム組成物およびゴム架橋物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03749A (ja) * 1988-08-18 1991-01-07 Lexington Precision Corp 耐燃料性エラストマー組成物およびシール部材
JPH03181507A (ja) * 1989-11-27 1991-08-07 Stamicarbon Bv 結合アクリロニトリル分の高い選択された最終組成を有するアクリロニトリルブタジエンゴムコポリマー及びその連続的重合法
WO2000026292A1 (fr) * 1998-11-04 2000-05-11 Nippon Zeon Co., Ltd. Composition polyblend, article reticule, et tuyau d'amenee de carburant
JP2001072804A (ja) * 1999-06-28 2001-03-21 Tokai Rubber Ind Ltd ゴム組成物及び自動車用燃料輸送ホース
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
JP2002206011A (ja) * 2000-11-13 2002-07-26 Jsr Corp 不飽和ニトリル−共役ジエン系ゴム及びゴム組成物並びにこれらの製造方法
JP2004059695A (ja) * 2002-07-26 2004-02-26 Nippon Zeon Co Ltd ポリマーアロイ、架橋物および燃料ホース

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03749A (ja) * 1988-08-18 1991-01-07 Lexington Precision Corp 耐燃料性エラストマー組成物およびシール部材
JPH03181507A (ja) * 1989-11-27 1991-08-07 Stamicarbon Bv 結合アクリロニトリル分の高い選択された最終組成を有するアクリロニトリルブタジエンゴムコポリマー及びその連続的重合法
WO2000026292A1 (fr) * 1998-11-04 2000-05-11 Nippon Zeon Co., Ltd. Composition polyblend, article reticule, et tuyau d'amenee de carburant
JP2001072804A (ja) * 1999-06-28 2001-03-21 Tokai Rubber Ind Ltd ゴム組成物及び自動車用燃料輸送ホース
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
JP2002206011A (ja) * 2000-11-13 2002-07-26 Jsr Corp 不飽和ニトリル−共役ジエン系ゴム及びゴム組成物並びにこれらの製造方法
JP2004059695A (ja) * 2002-07-26 2004-02-26 Nippon Zeon Co Ltd ポリマーアロイ、架橋物および燃料ホース

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5338658B2 (ja) * 2007-03-29 2013-11-13 日本ゼオン株式会社 ニトリル共重合体ゴム組成物
CN101652424B (zh) * 2007-03-29 2011-12-28 日本瑞翁株式会社 腈共聚物橡胶组合物及腈共聚物胶乳组合物
US8563644B2 (en) 2007-03-29 2013-10-22 Zeon Corporation Nitrile copolymer rubber composition and nitrile copolymer latex composition
WO2008123405A1 (fr) * 2007-03-29 2008-10-16 Zeon Corporation Composition de caoutchouc copolymère nitrile et composition de latex copolymère nitrile
KR101475092B1 (ko) * 2007-03-29 2014-12-22 제온 코포레이션 니트릴 공중합체 고무 조성물 및 니트릴 공중합체 라텍스 조성물
EP2028021A1 (fr) * 2007-08-16 2009-02-25 The Goodyear Tire & Rubber Company Pneu avec composant disposant d'une combinaison de plastifiants
WO2009096456A1 (fr) * 2008-01-30 2009-08-06 Zeon Corporation Composition de latex de copolymère de nitrile et composition de caoutchouc de copolymère de nitrile
CN101932649B (zh) * 2008-01-30 2013-04-24 日本瑞翁株式会社 腈共聚物胶乳组合物及腈共聚物橡胶组合物
US8648137B2 (en) 2008-01-30 2014-02-11 Zeon Corporation Nitrile copolymer latex composition and nitrile copolymer rubber composition
US8927640B2 (en) 2008-01-30 2015-01-06 Zeon Corporation Nitrile copolymer latex composition and nitrile copolymer rubber composition
CN105330913A (zh) * 2015-11-24 2016-02-17 中国航空工业集团公司沈阳飞机设计研究所 一种混炼胶
JP2020050722A (ja) * 2018-09-26 2020-04-02 日本ゼオン株式会社 ゴム混合液、ニトリル基含有共重合体ゴム組成物、架橋性ゴム組成物およびゴム架橋物
JP7200569B2 (ja) 2018-09-26 2023-01-10 日本ゼオン株式会社 ゴム混合液、ニトリル基含有共重合体ゴム組成物、架橋性ゴム組成物およびゴム架橋物

Also Published As

Publication number Publication date
JPWO2007026707A1 (ja) 2009-03-12

Similar Documents

Publication Publication Date Title
JP5338658B2 (ja) ニトリル共重合体ゴム組成物
JP5617638B2 (ja) 燃料ホース用の架橋性ニトリル共重合体ゴム組成物の製造方法および燃料ホース用のゴム架橋物
JP5655784B2 (ja) ニトリルゴム組成物、架橋性ニトリルゴム組成物、ゴム架橋物、及びニトリルゴム組成物の製造方法
JP5347770B2 (ja) ニトリルゴム組成物および架橋性ゴム組成物、並びにゴム架橋物
JP5803943B2 (ja) ニトリルゴム組成物および架橋性ニトリルゴム組成物、並びにゴム架橋物
JP5417730B2 (ja) ニトリル共重合体ラテックス組成物およびニトリル共重合体ゴム組成物
JP5742836B2 (ja) ホース用ニトリル共重合体ゴム組成物および架橋物
JP5892171B2 (ja) ニトリル共重合体ゴム組成物及びゴム架橋物
JP2007277341A (ja) 加硫性ニトリル共重合体ゴム組成物およびその加硫物
JP5482385B2 (ja) ニトリル共重合体ゴム組成物
WO2007026707A1 (fr) Caoutchouc de copolymère de nitrile réticulé, composition de caoutchouc de copolymère de nitrile et procédé pour produire la composition
JP5381088B2 (ja) ニトリル共重合体ゴム組成物
JPWO2013133358A1 (ja) ニトリル共重合体ゴム組成物の製造方法
JP5391553B2 (ja) ニトリル共重合体ラテックス組成物およびニトリル共重合体ゴム組成物
WO2003055925A1 (fr) Caoutchouc acrylique, procede de production, compositions de caoutchouc, compositions de caoutchouc resistantes a l'huile et aux intemperies, et des caoutchoucs resistants a l'huile et aux intemperies contenant ces compositions
JP2007224161A (ja) 加硫性ニトリル共重合体ゴム組成物およびその加硫物
JP6852728B2 (ja) ニトリル共重合体ゴム組成物、架橋性ゴム組成物およびゴム架橋物
JP2009221371A (ja) ニトリル共重合体ゴム組成物の製造方法
WO2019163482A1 (fr) Composition de caoutchouc de copolymère de nitrile, composition de caoutchouc réticulable, produit réticulé en caoutchouc, et tuyau souple
JP5803914B2 (ja) ニトリル共重合体ゴム組成物
JPWO2005000550A1 (ja) ポリマーアロイ、架橋物および燃料ホース
JP2000290430A (ja) 架橋性フッ素ゴム組成物、架橋物、ゴム積層体およびゴム積層体の製造方法
JP2007099844A (ja) 架橋性ゴム組成物及び架橋物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2007533262

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06796976

Country of ref document: EP

Kind code of ref document: A1