WO2007026707A1

WO2007026707A1 - Crosslinked nitrile copolymer rubber, nitrile copolymer rubber composition, and process for producing the composition

Info

Publication number: WO2007026707A1
Application number: PCT/JP2006/316999
Authority: WO
Inventors: Akira Imada; Yoshiyuki Odagawa
Original assignee: Zeon Corporation
Priority date: 2005-08-31
Filing date: 2006-08-29
Publication date: 2007-03-08
Also published as: JPWO2007026707A1

Abstract

A crosslinked nitrile copolymer rubber which comprises 100 parts by weight of a nitrile copolymer rubber (A) having 55-80 wt.% units of an α,β-ethylenically unsaturated nitrile monomer and 0.1-100 parts by weight of a plasticizer (B) incorporated therein, and has a brittle temperature of -50 to -5°C. Preferably, the crosslinked rubber has a gasoline permeability coefficient, in terms of permeability to a gasohol consisting of isooctane, toluene, and ethanol in a proportion of 40/40/20 by weight, of 200 g·mm/m2·day or lower. The plasticizer (B) preferably is an ester of a specific dicarboxylic acid compound with an alcohol having an ether bond. The crosslinked nitrile copolymer rubber can have a low brittle temperature (excellent cold resistance) and low permeability to gasoline (excellent gasoline impermeability) despite the exceedingly high content of unsaturated nitrile monomer units.

Description

Nitrile copolymer rubber cross-linked product, nitrile copolymer rubber composition, and method for producing the composition

Technical field

[0001] In the present invention, although the content of unsaturated-tolyl monomer units is extremely high, 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.

Background art

[0002] Conventionally, 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. In such a -tolyl copolymer rubber, generally, if the content of α, j8-ethylenically unsaturated-tolyl monomer unit (abbreviated as “nitrile content”) is increased, Phosphorus permeability is lowered, but on the other hand, the brittle temperature rises and rubber elasticity is lowered. Therefore, the nitrile content force 3-50 wt ^_0/0 ultrahigh - tolyl - tolyl copolymer rubber, often used by軟I spoon by blending a plasticizer, Ru.

[0003] Recently, efforts to reduce the evaporation of gasoline and other fuels into the atmosphere have progressed due to the increase in global environmental protection activities. For example, NOX emissions are regulated in Japan and Europe, and in accordance with this, reduction of fuel transpiration is required. In Japan, there is a growing demand for even lower gasoline permeability in applications such as fuel hoses, seals, and knocks. On the other hand, regulations on fuel gas concentration in exhaust gas have been gradually strengthened in California in the US in 2004 (LEVII).

[0004] For such a situation, 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). On the other hand, there has been proposed 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. But the market Therefore, it is desirable to further reduce gasoline permeability even on the premise of using a rubber having a high -tolyl content.

[0005] In 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.

[0006] Also, in 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.

[0007] Therefore, it is desired to develop a cross-linked product using a super-high-tolyl-tolyl copolymer rubber which does not contain a large amount of halogen compound and has a brittle temperature of at least -5 ° C or lower. ing. 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

Disclosure of the invention

Problems to be solved by the invention

[0008] 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.

Means for solving the problem

[0009] 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.

[0010] Forcibly, according to 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.

[0011] 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. Preferably, 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). .

HOOCRCOOH (1)

(In the formula, R represents an alkylene group having 2 to 10 carbon atoms, and COOH represents a carboxy group.)

[0012] Furthermore, the cross-linked product is preferably the α, j8-ethylenically unsaturated-tolyl monomer unit force acrylonitrile unit and Z or meta-tally-tolyl unit. Preferably, 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. Preferably, the plasticizer (B) is dibutoxetyl adipate and Z or di (butoxyethoxyethyl) adipate.

[0013] According to another aspect of the present invention, a, j8-ethylenically unsaturated nitrile monomer unit 55 to 80 wt% -tolyl copolymer rubber (A) (B) 0.1-: A tolyl copolymer rubber composition containing a L00 weight part and giving a cross-linked product having an embrittlement temperature of 50 to 15 ° C. is provided.

[0014] According to another aspect of the present invention, there is provided a method for producing the above-tolyl copolymer rubber composition, comprising a, j8-ethylenically unsaturated-tolyl monomer unit 55 to 80% by weight. A step of preparing a mixed liquid of the latex of the tolyl copolymer rubber (A) and the emulsion of the plasticizer (B), coagulating the mixed liquid, and then drying to obtain a solid mixture; And a kneading step of the mixture and a rubber compounding agent. A method for producing a nitrile copolymer rubber composition is provided. In the production method, the plasticizer (B) force is preferably the ester compound (b).

[0015] According to still another aspect of the present invention, 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. It also has the strength of rubber cross-links and has a thickness of 0.1 ~: LOmm (I) and α, j8-ethylenically unsaturated- A nitrile copolymer rubber having a tolyl monomer unit of 5 wt% or more and less than 55 wt% (L) 100 parts by weight of plasticizer (M) O˜: LOO parts by weight A layered product obtained by laminating a layer (-) having a thickness of 0.1 to LOmm is provided, which is a cross-linked tolyl copolymer rubber having a temperature of −70 to −10 ° C.

The invention's effect

[0016] According to the present invention, even if the unsaturated-tolyl monomer unit content is a so-called ultra-high level, the gasoline permeability is low and the brittle temperature is low and the brittle temperature is low. Things are provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] 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 On the other hand, it is 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.

[0018] The nitrile copolymer rubber (A) has an α, β-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.

[0019] The α, j8-ethylenically unsaturated nitrile monomer forming the a, j8-ethylenically unsaturated-tolyl monomer unit is an a, β-ethylenically unsaturated compound having a nitrile group. If there is no limit. Examples of such compounds include: acrylonitrile; _α- 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.

[0020] The nitrile copolymer rubber (A) usually also has a gen monomer unit or an α-olefin monomer unit because the cross-linked product has rubber elasticity. [0021] 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.

[0022] As the 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.

[0023] 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.

[0024] The nitrile copolymer rubber (A) can be copolymerized in addition to the α, β-ethylenically unsaturated-tolyl monomer unit, the gen monomer unit or the _α- 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.

[0025] 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, β-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. ], (Meth) acrylic acid ethyl ester, (meth) acrylic acid butyl, (meth) acrylic acid 2-ethylhexyl and other α, j8-ethylenically unsaturated carboxylic acid alkyl ester; maleic acid mono (di) ethyl ester [Meaning of monoethyl maleate and jetyl maleate. The same applies to mono (di) butyl maleate. ], Mono (di) butyl maleate, mono (di) ethyl fumarate, mono (di) butyl fumarate, mono (di) cyclohexyl fumarate, mono (di) ethyl itaconate, mono (di) itaconate ) Mono (di) of α, β-ethylenically unsaturated polyvalent carboxylic acids such as butyl Steal; Alkoxyalkyl esters of α, β ethylenically unsaturated carboxylic acids such as methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, butoxychetyl (meth) acrylate; 2-methacrylic acid (meth) acrylic acid Ethyl, hydroxyalkyl esters of α, β ethylenically unsaturated carboxylic acids such as hydroxypropyl (meth) acrylate; heterocyclic aromatic butyl monomers such as bilyridine; Ν— (4-Linolehue -L) Acrylic amide, Ν— (4—linophenol) Methacrylamide, Ν— (4—linophenol) cinnamamide, Ν— (4—linophenol) crotonamide, Ν— Co-polymerizable anti-aging agents such as FE-LUE 4- (3-Bulbenoxy) -line, ルー -FUEL- 4- (4-Bulbenzyloxy) -line, etc. It is.

[0026] Mu-one viscosity of nitrile copolymer rubber (Α) (hereinafter sometimes referred to as “polymer-one viscosity”) (ML

4, 100 ° C) is preferably 15-200, more preferably 30

1+ to 120, particularly preferably 45 to L00. If 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.

[0027] The method for producing the nitrile copolymer rubber (A) is not particularly limited. In general, α, β-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. As 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.

[0028] 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.

[0029] 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.

[0030] That is, first, α, β-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. On the other hand, if 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.

[0031] After the first stage polymerization is started, the remainder of the monomer is fed. The remainder of the monomer may be supplied continuously or divided and supplied in multiple stages.

When 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. In this second stage polymerization, the monomer added in the second stage polymerization (m

When 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. Monomer (m

2) and all may be monomer (m2). If the amount of monomer (m2) used is less than 50% by weight, the monomer (m2) may disappear before the predetermined polymerization conversion rate is reached, and the polymerization may stop.

[0032] Alternatively, in the case where 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 When 10 to 30% by weight is reached, 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. In the case of four-stage polymerization, for example, 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. At that time, 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. In addition, it is possible to carry out further multi-stage polymerization. In order to control the content, it is preferable to carry out multistage polymerization.

[0033] In the above multi-stage polymerization !, the monomer supplied at each stage after the second stage is the monomer (ml) and monomer (m2) to be added at each stage. When 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.

[0034] 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.

[0035] As the plasticizer (B), those conventionally used as a plasticizer for blending rubber can be used without limitation.

Examples of such plasticizers include the following.

That is, 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).

HOOCRCOOH (1)

(In the formula, R represents an alkylene group having 2 to 10 carbon atoms, and COOH represents a carboxy group.

)

Furthermore, in addition to the above ester compound (b), 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 phthalate, dicyclohexyl phthalate Which phthalates: isophthalates such as di (2-ethylhexyl) isophthalate and diisooctylisophthalate; di (2-ethylhexyl) tetrahydrophthalate, di n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate Tetrahydrophthalic acid esters such as tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyltri And trimellitic acid derivatives such as meritate and triisonol trimellitate.

Of these, the above ester compound (b) is preferred.

[0036] 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.

[0037] Further, 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. Specific examples of 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

Three

O-C H O-CH OH) and other alcohols with 4 carbon atoms and 2 ether bonds; methoxy

2 4 2

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

3 2 4 2 4

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),

3 2 4 4 8 Carbon number, such as toxipropoxypropyl alcohol (CH 2 O—C 3 H 2 O 4 C 7 OH) 7

3 3 6 3 6

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

4 9 2 4 2 4

Nore, ethoxypropoxypropinoreanoreconole (C H O-C H O-C H OH), Provo

2 5 3 6 3 6

Xylethoxypropinoreanolenoconole (C H O—C H O—C H OH), methoxybutoxyp

3 7 2 4 3 6

Mouth pill alcohol (CH O-C H O-C H OH), diethoxybutyl alcohol, etc.

3 4 8 3 6

And alcohols having 8 carbon atoms and 2 ether bonds.

[0038] As the ester compound (b), a compound obtained by arbitrarily combining the compound (bl) and the alcohol (b2) can be used. In general, a monoester compound and a diester compound are preferably used. A diester compound is preferable. Specific examples of preferable diester compounds include dibutoxy acetyl adipate and di (butoxyethoxyethyl) adipate, and di (butoxyethoxyethyl) adipate is particularly preferable.

[0039] As a method for preparing the -tolyl copolymer rubber composition of the present invention, a step of preparing a mixed liquid of a latex of a nitrile copolymer rubber (A) and an emulsion of a plasticizer (B); A method comprising solidifying the mixed solution and then drying it to form a solid mixture, and kneading the solid mixture and the compounding agent for rubber is preferable.

[0040] 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.

[0042] 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.

Examples of 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.

[0043] 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.

[0044] After thoroughly mixing the latex of the nitrile copolymer rubber (A) and the emulsion of the plasticizer (B), the obtained mixed solution is coagulated. Although there is no limitation on the coagulation method, 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.

[0045] 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

Contains a 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.

[0046] 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.

[0047] When a sulfur-based crosslinking agent is used, 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.

[0048] 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.

[0049] When an organic peroxide crosslinking agent is used, 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). [0050] 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.

[0051] 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.

[0052] As the anti-aging agent, an anti-aging agent such as phenol, amine, benzimidazole or phosphoric acid can be used. In phenolic systems, such as 2,2'-methylenebis (4-methyl 6-t-butylphenol) In amine systems, 4,4'-bis (α, a-dimethylbenzyl) diphenylamine is used in benzimidazole systems. Examples include 2-mercaptobenzimidazole. These may be used alone or in combination of two or more.

[0053] As the filler, 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.

[0054] 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. When these rubbers are blended, other than the above-mentioned 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.

[0055] In order to prepare a nitrile copolymer rubber composition containing the above-described components other than the plasticizer, the -tolyl copolymer rubber (A) and the plasticizer (B) are also used. In general, 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.

[0056] 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

1+ 4

0.

[0057] The -tolyl copolymer rubber crosslinked product of the present invention is obtained by crosslinking the -tolyl copolymer rubber composition prepared as described above. In order to crosslink the nitrile copolymer rubber composition, 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.

[0058] Further, depending on the shape, size, etc. of the above crosslinked product, even if the surface is crosslinked, it may be sufficiently crosslinked to the inside. Mocho ヽ

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.

[0060] Further, 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.

[0061] Since the -tolyl copolymer rubber cross-linked product of the present invention has low gasoline permeability, the laminate having at least the layer (I) made of the cross-linked product is suitably used as a fuel hose or the like. [0062] The following are preferred as the other layer (Π) that is laminated together with the layer (I) comprising the crosslinked product and constitutes the laminate.

That is, as the layer (Π), (X, | 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. The copolymer rubber (L) and the plasticizer (M) 0 to: 100 parts by weight of the rubber (L): LOO parts by weight, preferably 4 to 90 parts by weight. — 70 to −10 ° C, preferably —60 to — 14 ° C, more preferably —50 to —18 ° C. 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).

Here, the thickness of 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 (Π). It is.

Instead of the thick rubber material, which is the only material of layer (I), the total thickness of the layer (I) and layer (Π) 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 (層) 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.

[0064] 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.).

Example

[0065] The present invention will be specifically described below with reference to Examples and Comparative Examples. In the following, “parts” are based on weight unless otherwise specified. The test and evaluation were as follows.

[0066] (1) Content of acrylonitrile monomer unit

Measured by Kjeldahl method according to JIS K6384-Nitrogen in tolyl copolymer rubber The content (% by weight) of the acrylonitrile monomer unit was determined by calculation from the elementary content.

[0067] (2) Mu-one viscosity (ML, 100 ° C)

1+ 4

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.

[0068] (3) Normal state properties (tensile strength, elongation, 100% tensile stress)

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.

[0069] (4) Normal physical properties (hardness)

About the sheet-like rubber cross-linked product obtained in the same manner as (3) above, the hardness of the cross-linked product was measured using a durometer hardness tester type A according to JIS K6253.

[0070] (5) Heat aging resistance (air heat aging test)

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.

[0071] (6) Oil resistance (immersion test)

In accordance with JIS K6258, in fuel oil C (isooctane and toluene mixed at a volume ratio of 1: 1) and fuel oil CE-20 (gasohol with a weight ratio of isooctane Z toluene Z ethanol of 40 Z40Z20), respectively. The sample was immersed for 48 hours at 40 ° C, and the volume change rate (unit:%) before and after immersion was measured.

[0072] (7) Gasoline permeability

For fuel oil C and fuel oil CE-20, gasoline permeability was measured by the aluminum cup method. In 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 smaller the gasoline permeation, the lower the gasoline permeability, and the better the gasoline resistance.

[0073] (8) Brittle temperature

According to JIS K6301, the embrittlement temperature (° C) was measured.

(Production Example 1) Production of latex of nitrile copolymer rubber (A1)

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. As 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. When the polymerization conversion reached 28%, 47%, 61% and 72% by weight, 6.9 parts, 6.3 parts, and 5. 5 parts and 4.7 parts were added and the second, third, fourth and fifth stage polymerization reactions were carried out. Thereafter, when the polymerization conversion rate reached 80% by weight, 0.3 part of hydroxylamine sulfate and 0.2 part of potassium hydroxide were added to terminate the polymerization. The contents of the reaction vessel was heated to 70 ° C, latte box of nitrile copolymer rubber to recover the unreacted monomer (A1) by steam distillation under reduced pressure (solids 26 wt ⁰ / ₀ ). The content of the acrylonitrile monomer unit in the nitrile copolymer rubber (A1) is 58.6% by weight with respect to 100% by weight of all the monomers, and the polymer one-one viscosity is 97. It was 7.

[0075] (Production Example 2) Production of latex of nitrile copolymer rubber (A2)

In the first stage reaction of Production Example 1, emulsion polymerization was carried out in the same manner as in Production Example 1, except that the amounts of acrylonitrile and 1,3-butadiene were 71.6 parts and 6.2 parts, respectively. Eye reaction started. When the polymerization conversion reached 19%, 38%, 51% and 62% by weight, 7.0 parts, 5.5 parts and 5. 1 part and 4.7 parts were added and the second, third, fourth and fifth stage polymerization reactions were carried out. Thereafter, when the polymerization conversion rate reached 70% by weight, 0.3 part of hydroxylamine sulfate and 0.2 part of potassium hydroxide were added to terminate the polymerization. Steam-distillation was performed to obtain a latex of the tolyl copolymer rubber (A2) (solid content: 24% by weight). The content of the acrylo-tolyl monomer unit in the nitrile copolymer rubber (A2) was 60.0% by weight, and the polymer one-viscosity was 77.6.

(Comparative Production Example 1) Production of latex of nitrile copolymer rubber (A3)

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. Then, 0.3 parts of hydroxylamine sulfate and 0.2 part of potassium hydroxide were added to the reaction vessel to stop the polymerization. Thereafter, steam distillation was carried out in the same manner as in Production Example 1 to obtain a latex of nitrile copolymer rubber (A 3). The nitrile copolymer rubber (A3) had an acrylonitrile monomer unit content of 49% by weight and a polymer-one viscosity of 90.0.

(Preparation Example 1) Preparation of a finer emulsion

Di (butoxyethoxyethyl) adipate (plasticizer) Prepared by mixing 50% by weight aqueous emulsion with potassium oleate as an emulsifier and 2.0% by weight of the same plasticizer under strong stirring. did.

[0078] Example 1

While stirring the latex of nitrile copolymer rubber (A1) in a container, 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.

[0079] Next, using a Banbury mixer, 100 parts of -tolyl copolymer rubber (A1) in the mixture was mixed with FEF carbon black (product name "SEAST SO", manufactured by Tokai Carbon Co., Ltd., filler) 20 parts, 1 part of stearic acid, 5 parts of acid and zinc are mixed and mixed at 50 ° C. Then, this mixture is transferred to a roll and tetramethylthiuram disulfide (product name `` Noxeller TT '', Ouchi Shinsei Co., Ltd., cross-linking accelerator) 1.5 parts, Ν-Cyclohexyl-2-benzothiazolylsulfenamide (Product name “Noxeller CZ”, Ouchi Shinsei Co., Ltd., cross-linking accelerator) 1.5 parts Then, 0.5 part of 325 mesh sulfur was added and kneaded at 50 ° C. to prepare a nitrile copolymer rubber composition.

Compound-one-viscosity of the obtained tolyl copolymer rubber composition and the cross-linked product obtained by crosslinking the composition with normal properties, air heat aging test (heat aging resistance), immersion test, gasoline permeation Table 1 shows the results of tests and evaluations on the property and brittle temperature.

[0080] Jewelery 12

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.

[0081] Comparative 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).

[0082] Using a Banbury mixer, add 100 parts of nitrile copolymer rubber (A1) to 20 parts of FEF carbon black, 1 part of stearic acid and 5 parts of zinc oxide and mix at 50 ° C. did. Next, this mixture was transferred to a roll, and 15 parts of di (butoxyethoxyethyl) adipate was added to the kneaded kneading force. mouth Since there was a large amount of unmixed plasticizer on the surface of the tool, this kneaded product was transferred to another roll and 1.5 parts of tetramethylthiuram disulfide, N cyclohexyl 2 benzothiazolylsulfenamide 1 Then, 5 parts and 0.5 part of 325 mesh sulfur were added and kneaded at 50 ° C. to prepare a nitrile copolymer rubber composition. Table 1 shows the results of tests and evaluations for the same items as in Example 1.

[0083] Comparative Examples 2 and 3

In 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.

[0084] [Table 1]

As shown in Table 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). [0086] On the other hand, the cross-linked product obtained by blending a plasticizer with a roll and having a brittle temperature, which has a large plasticizer bleed during roll kneading and poor workability, has a high strength ( Comparative example 1).

When the plasticizer was not added, the gasoline permeability of the crosslinked product was lower than that of the examples of the present invention, but the brittle temperature where the swelling in the immersion test was large was high (Comparative Example 2).

In addition, in the case of the tolyl copolymer rubber having no predetermined tolyl content according to the present invention without adding a plasticizer, in addition to the high brittle temperature, swelling in the immersion test is large. Gasoline permeability increased (Comparative Example 3).

[0087] Example 3

In a Banbury mixer, 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.

[0088] Using the -tolyl copolymer rubber composition obtained in the same manner as in Example 1 and the above-obtained high-tolyl rubber composition, each was first kneaded separately with a roll, and separately sheeted. As a result, sheet-like materials each having a thickness of 1.2 mm were produced. Next, both sheet-like materials were stacked and subjected to press crosslinking at 160 ° C. for 20 minutes at a press pressure of 1 OMPa to obtain a laminate having a total thickness of 2 mm. Table 2 shows the results of tests and evaluations on the same items as in Example 1 for the obtained laminate.

[0089] Comparative Example 4

Using the -tolyl copolymer rubber composition obtained in the same manner as in Comparative Example 3 and the high-tolyl rubber composition obtained in the same manner as in Example 3, press crosslinking was carried out in the same steps as in Example 3, and the total A laminate having a thickness of 2 mm was obtained. Table 2 shows the results of testing and evaluating the same items as in Example 1 for the obtained laminate.

[0090] [Table 2] Examples Comparative examples

3 4 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 (Π) 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).

On the other hand, the laminate using the tolyl copolymer rubber having no predetermined tolyl content of the present invention had high gasoline permeability and gave a crosslinked product (Comparative Example 4).

Claims

The scope of the claims

[1] α, j8-ethylenically unsaturated-tolyl monomer unit 55 to 80 wt% -tolyl copolymer rubber (A) 100 parts by weight of plasticizer (B) 0.1 to L00 weight A tolyl copolymer rubber cross-linked product having a brittle temperature of 50 to 15 ° C.

[2] Gasoline permeability coefficient force for gasohol with isooctane Z toluene Z ethanol weight ratio 0 係数 40Ζ20 200 ₈ '1111117111 ² ' (1-or less -tolyl copolymer rubber cross-linked product according to claim 1 which is 1 _& .

[3] The plasticizer (Β) 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): Or a crosslinked nitrile copolymer rubber as described in 2 above.

HOOCRCOOH (1)

[4] The -tolyl copolymer rubber cross-linked product according to any one of claims 1 to 3, wherein the OL, β-ethylenically unsaturated-tolyl monomer unit force is an acrylonitrile unit and a Ζ or meta-tally-tolyl unit.

[5] The -tolyl copolymer rubber (Α) according to any one of claims 1 to 4, further comprising a gen monomer unit and 20 to 45% by weight of Ζ or a-olefin monomer unit. Nitryl copolymer rubber cross-linked product.

[6] The -tolyl copolymer rubber cross-linked product according to any one of [3] to [5], wherein the plasticizer (B) is dibutoxychetyl adipate and Z or di (butoxyshetyl) yl adipate.

[7] a, j8—ethylenically unsaturated-tolyl monomer unit having 55-80 wt% -tolyl copolymer rubber (A) 100 parts by weight of plasticizer (B) 0.1-: L00 weight A tolyl copolymer rubber composition containing a polymer and giving a cross-linked product having an embrittlement temperature of 50 to 15 ° C.

[8] A method for producing the nitrile copolymer rubber composition according to claim 7,

α, β Ethylenically unsaturated-Tolyl monomer unit having 55 to 80 wt%-Tolyl copolymer rubber (Α) Latex and plasticizer (Β) emulsion When, Solidifying the mixture and then drying to form a solid mixture;

Kneading the mixture and a rubber compounding agent;

A method for producing a nitrile copolymer rubber composition, comprising:

[9] 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). 9. The method for producing a nitrile copolymer rubber composition according to 8.

HOOCRCOOH (1)

[10] A laminate having at least the layer (I) having the cross-linked strength of the nitrile copolymer rubber according to any one of claims 1 to 6.

[11] Cross-linked tolyl copolymer rubber according to any one of claims 1 to 6, and a layer (I) having a thickness of 0.1 to 10 mm,

α, β Ethylenically unsaturated nitrile monomer unit 5% by weight or more and less than 55% by weight -Tolyl copolymer rubber (L) 100 parts by weight of plasticizer (Μ) 0 ～： L00 It contains a part by weight, and the brittle temperature is -70 to -10 ° C-tolyl copolymer rubber cross-linking force, thickness 0.1 to: L 0 mm layer (Π),

A laminate formed by laminating layers.