WO2005037914A1 - ポリマーアロイ、架橋物および工業部品 - Google Patents
ポリマーアロイ、架橋物および工業部品 Download PDFInfo
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- WO2005037914A1 WO2005037914A1 PCT/JP2004/015258 JP2004015258W WO2005037914A1 WO 2005037914 A1 WO2005037914 A1 WO 2005037914A1 JP 2004015258 W JP2004015258 W JP 2004015258W WO 2005037914 A1 WO2005037914 A1 WO 2005037914A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a polymer alloy suitable as a material for various industrial components, a crosslinked product of the polymer alloy, and an industrial component composed of the crosslinked product.
- Nitrile copolymer rubbers such as acrylonitrile-butadiene rubber (NBR) have excellent oil resistance and are therefore used for various applications including fuel hoses used for fuel system piping of automobiles.
- NBR acrylonitrile-butadiene rubber
- nitrile copolymer rubber is inferior in ozone resistance, so a polymer alloy improved in ozone resistance etc. by blending nitrile copolymer rubber with vinyl chloride resin has been proposed. Widely used.
- the salty butyl resin contained in the polymer alloy has a problem that chlorine atoms in the resin may cause environmental problems at the time of disposal treatment, so that halogens such as chlorine atoms are removed.
- New materials and materials that can improve ozone resistance without being included are required.
- Patent Document 1 Japanese Patent Publication No. 50-27486
- Patent Document 2 Japanese Patent Application Laid-Open No. 2001-226527
- An object of the present invention is to provide a polymer alloy having excellent oil resistance and ozone resistance and also having excellent solvent crack resistance, a crosslinked product of the polymer alloy, and an industrial part composed of the crosslinked product. .
- the inventors of the present invention use a polymer alloy having a specific composition comprising two specific ⁇ , ⁇ -ethylenically unsaturated nitriles-one conjugated gen copolymer rubbers and a specific acrylic copolymer. The inventors have found that the above objects can be achieved, and have completed the present invention.
- [0012] 1. ⁇ , —ethylenically unsaturated nitrile-one conjugated gen copolymer rubber having a number average molecular weight of 50,000 to 150,000 ( ⁇ ) 5-88 weight 0 /.
- A an acrylic copolymer (B) containing ethylenically unsaturated nitrile monomer units (B) 10 to 60% by weight, and a number average molecular weight of 1,000-20
- a polymer alloy that also has% power is provided.
- the invention's effect it is possible to provide a polymer alloy excellent in oil resistance and ozone resistance and also excellent in solvent cracking resistance, a crosslinked product of the polymer alloy, and an industrial part composed of the crosslinked product. it can.
- Porimaaroi of the present invention has a number average molecular weight 50, 000- 150, 000 of the alpha, one Echire emissions unsaturated nitrile one conjugated diene copolymer rubber (Alpha), alpha, one ethylenically unsaturated nitrile single And an ⁇ , ⁇ -ethylenically unsaturated nitrile-one conjugated copolymer rubber (C) having a number average molecular weight of from 1,000 to 20,000.
- a ⁇ -ethylenically unsaturated nitrile-conjugated gen copolymer rubber having a number average molecular weight of 50,000 to 150,000 ( ⁇ ) is referred to as a rubber ( ⁇ ⁇ ), and ⁇
- Acrylic copolymer ( ⁇ ) containing ⁇ -ethylenically unsaturated nitrile monomer unit is referred to as copolymer ( ⁇ ) and has a number average molecular weight of 1,000-20,000, / 3 _ ethylenic
- the unsaturated nitrile-conjugated gen copolymer rubber (C) will be described as rubber (C).
- the rubber ( ⁇ ) used in the present invention is obtained by copolymerizing a j3_ethylenically unsaturated nitrile monomer and a conjugated diene monomer, and has a large molecular weight, is there.
- the number average molecular weight of the rubber (A) is measured by gel 'permeation' chromatography; in terms of styrene, 50,000-150,000, preferably ⁇ 60,000-120, 000, more preferably 70,000-100,000. If the molecular weight is too small, the mechanical strength of the crosslinked product will be poor, and if it is too large, the polymer alloy will have poor processability as a molding material.
- the content of the ⁇ -ethylenically unsaturated nitrile monomer unit in the rubber (A) is preferably 25 to 80% by weight, more preferably 28 to 60% by weight, and particularly preferably 30 to 80% by weight. 55% by weight.
- the content of the conjugated diene monomer unit in the rubber (II) is preferably 20 to 75% by weight, more preferably 40 to 72% by weight, and particularly preferably 45 to 70% by weight. If the content of the a, -ethylenically unsaturated nitrile monomer unit is too small and the content of the conjugated diene monomer unit is too large, the oil resistance of the crosslinked product may be poor.
- Examples of the a, ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile and metal Ronitrile and the like are mentioned, and acrylonitrile is preferable.
- conjugated diene monomer examples include 1,3-butadiene, isoprene, and 2,3_dimethyl-
- Examples include 1,3-butadiene and 1,3_pentadiene, and 1,3_butadiene is preferred.
- the rubber (A) is selected from the group consisting of a, another monomer copolymerizable with a monoethylenically unsaturated nitrile monomer and a conjugated diene monomer as long as the effects of the present invention are not substantially impaired. It may be a copolymer of the body.
- Examples of such other monomers include non-conjugated diene monomers, olefins, aromatic vinyl monomers, ⁇ , _ ethylenically unsaturated monocarboxylic acids, ⁇ , Examples thereof include saturated polycarboxylic acids or anhydrides thereof, ⁇ , ethylenically unsaturated carboxylic acid ester monomers, and copolymerizable antioxidants.
- non-conjugated diene monomer examples include those having 5 to 12 carbon atoms, such as 1,4-pentagen, 1,4-hexadiene, byurnorbornene, and dicyclopentadiene.
- ⁇ -olefins having 2 to 12 carbon atoms are preferred, such as ethylene, propylene,
- aromatic vinyl monomer examples include styrene and ⁇ -methylstyrene.
- ⁇ , ⁇ to ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid and the like.
- ⁇ , —Ethylenically unsaturated polycarboxylic acids include itaconic acid, fumaric acid, maleic acid and the like.
- the anhydride of a, j3_ethylenically unsaturated polycarboxylic acid examples include itaconic anhydride and maleic anhydride.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester monomers include carbon atoms such as methyl acrylate, ethyl acrylate, ⁇ -dodecyl acrylate, methyl methacrylate, and ethyl methacrylate.
- Has a hydroxyalkyl group with 11 to 12 carbon atoms such as 2-hydroxyethylmetharylate (Meth) atalinolehydroxyanolequinoleestenole monomer; monoethylenole maleate, mono-n-butyl itaconate, etc .; ⁇ -ethylenic dicarboxylic acid monoalkyl ester monomer; dimethyl maleate, fumarate ⁇ -ethylenic dicarboxylic acid dialkyl ester monomers such as dimethyl dimethyl itanate, dimethyl itaconate, and getyl itaconate; ⁇ -ethylene containing amino groups such as dimethinoleaminomethyl acrylate Unsaturated carboxylic acid esters; and the like.
- Examples of copolymerizable antioxidants include ⁇ — (4-anilinophenyl) acrylamide, ⁇ _ (4_anilinophenyl) methacrylamide, ⁇ — (4-anilinophenyl) cinnamamide, ⁇ - (4-anilinophenyl) cinnamamide, Crotonamide, 4-phenyl-2- (3-bierbenzyloxy) aniline, 4-phenyl-4_ (4-vinylbenzyloxy) aniline and the like.
- the content of the other monomer units in the rubber ( ⁇ ) is usually 50% by weight or less, preferably 30-1% by weight.
- the rubber ( ⁇ ) used in the present invention preferably does not substantially contain a halogen atom.
- the halogen content is preferably 0.5% by weight or less, more preferably 0.1% by weight or less, and particularly preferably 0% by weight. The lower the halogen content, the lower the burden on the environment at the time of disposal.
- the rubber ( ⁇ ) used in the present invention preferably has a viscosity at ML (100 ° C.) of 10 to 10 ⁇ m.
- the mechanical properties of the crosslinked product may be inferior; if it is too high, the processability may be inferior.
- the method for producing the rubber (A) is not particularly limited, and a known method can be employed, and an emulsion polymerization method is preferably used.
- the rubber (A) is produced by the emulsion polymerization method, it is polymerized at 0-50 ° C in a reactor from which oxygen has been removed.
- the above monomers, emulsifiers, initiators, molecular weight regulators and the like are charged into the reactor and reacted.
- the monomers, emulsifiers and the like may be added in their entirety before the start of the reaction, or may be arbitrarily added in portions after the start of the reaction.
- a coagulant is added to the emulsion polymerization solution containing the rubber (A) to coagulate the rubber (A), and the rubber (A) is washed, dried and recovered.
- the copolymer (B) used in the present invention comprises ⁇ ,; 3-ethylenically unsaturated nitrile monomer units. And (meth) acrylate monomer units.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include the same ones as in the case of the rubber ( ⁇ ⁇ ) described above. Among them, (meth) acrylonitrile is preferable.
- the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is preferably 1 to 65% by weight, more preferably 10 to 60% by weight, particularly preferably 10 to 60% by weight of the whole copolymer ( ⁇ ). It is preferably 15-55% by weight.
- the oil resistance of the polymer alloy is improved. If the content of a, / 3_ ethylenically unsaturated nitrile monomer unit is too small, the oil resistance of the polymer alloy may decrease, and if it is too large, the processability may decrease.
- Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid.
- Examples include isobutyl, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate.
- the content of the (meth) acrylate monomer unit in the copolymer (B) is preferably 40 to 90% by weight.
- the copolymer (B) is obtained by copolymerizing another monomer copolymerizable with the ⁇ , -ethylenically unsaturated nitrile monomer and the (meth) acrylate monomer. There may be.
- the other monomer is not particularly limited, but a monomer that does not introduce an unsaturated bond into the main chain is preferable, and a monomer that does not introduce a crosslinkable group is preferable.
- a monomer that does not introduce an unsaturated bond into the main chain is preferable, and a monomer that does not introduce a crosslinkable group is preferable.
- examples of such a monomer include an aromatic vinyl monomer, a vinyl ester monomer, a vinyl ether monomer, and the like.
- the aromatic butyl monomer include styrene, butyltoluene, and polymethylstyrene.
- the vinyl ester monomer include vinyl acetate, vinyl propionate, and the like.
- the butyl ether monomer include methyl butyl ether, ethyl butyl ether, and hydroxybutyl vinyl ether.
- the copolymer (B) used in the present invention preferably does not substantially contain a halogen atom.
- the halogen content is preferably 0.5% by weight or less, more preferably 0.1% by weight or less, and particularly preferably 0% by weight. The lower the halogen content, the more the same advantages as in the case of the rubber (A) described above.
- the number average molecular weight (Mn) of the copolymer (B) used in the present invention is not particularly limited, but is preferably a value of 25,000- 2,000,000, more preferred ⁇ is 50,000-1,000,000, especially preferred ⁇ is 100,000-700,000. If the Mn is too small, the ozone resistance may be reduced, and if it is too large, the moldability may be poor.
- the glass transition temperature (Tg) of the copolymer (B) used in the present invention is not particularly limited, but is preferably 50 to 150 ° C, more preferably 30 to 120 ° C, and particularly preferably 30 to 120 ° C. Preferably 0-100. C. If the Tg of the copolymer (B) is too low, it tends to stick when kneading with the rubber (A) with a roll or a bumper, etc., and the workability is reduced, while if the Tg is too high, the rubber (A) Problems such as poor dispersibility in the inside occur.
- the method for producing the copolymer (B) used in the present invention is not particularly limited, but a method capable of obtaining a copolymer in a particle state such as emulsion polymerization or suspension polymerization can be preferably employed. In emulsion polymerization, suspension polymerization, and the like, seed polymerization may be performed.
- the average particle size of the copolymer (B) when obtained in the form of particles is not particularly limited.
- the average particle size of the copolymer ( ⁇ ) can be controlled by the polymerization conditions.
- the block copolymer ( ⁇ ) is pulverized by a pulverizer such as a jet air pulverizer, a mechanical collision pulverizer, a roll mill, a hammer mill, and an impeller breaker, and the obtained pulverized material is subjected to an air classifier.
- a pulverizer such as a jet air pulverizer, a mechanical collision pulverizer, a roll mill, a hammer mill, and an impeller breaker
- the average particle size can also be adjusted by introducing the particles into a classifier such as a sieve classifier to classify the particles.
- the rubber (C) used in the present invention is a rubber having a relatively low molecular weight obtained by copolymerizing a j3-ethylenically unsaturated nitrile monomer and a conjugated diene monomer. It is a rubber that is usually liquid at room temperature.
- the number average molecular weight of the rubber (C) is from 1,000 to 20,000, preferably ⁇ 2,000 to 10,000, in terms of positive styrene, as measured by gel permeation chromatography. Preferably, it is between 3,000 and 7,000. If the molecular weight of the rubber (C) is small, the mechanical strength of the crosslinked product is poor, and if it is large, the solvent cracking resistance of the crosslinked product is poor.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
- Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethinolene 1,3-butadiene, and 1,3-pentadiene.
- the content of the ⁇ -ethylenically unsaturated nitrile monomer unit in the rubber (C) is preferably 25 to 80% by weight / 0 . , More preferably 28-60% by weight, particularly preferably 30-55% by weight.
- the content of the conjugated diene monomer unit in the rubber (C) is preferably 20 to 75% by weight, more preferably 40 to 72% by weight, and particularly preferably 45 to 70% by weight. If the content of the a, / 3-ethylenically unsaturated nitrile monomer unit is too small and the content of the conjugated diene monomer unit is too large, the oil resistance and mechanical strength of the crosslinked product may be poor. Conversely, if the content of the ⁇ , ⁇ -ethylene unsaturated nitrile monomer unit is too large and the content of the conjugated diene monomer unit is too small, the mechanical strength of the crosslinked product at high temperatures is poor. There is.
- the rubber (C) may be any other monomer copolymerizable with the a, ⁇ -ethylenically unsaturated nitrile monomer and the conjugated diene monomer within a range that does not substantially impair the effects of the present invention. It may be a copolymer of a monomer. As such other monomers, those described as other monomers used for rubber (II) can be used.
- the method for producing the rubber (C) is not particularly limited, and a known method can be adopted, and an emulsion polymerization method can be preferably used.
- the rubber (C) is produced by the emulsion polymerization method, the same method as in the case of producing the rubber (II) by the emulsion polymerization method can be adopted, except for selecting the amount of the molecular weight modifier used for the polymerization.
- the content of the rubber (Alpha), rubber to the total amount of the copolymer (beta) and the rubber (C) ( ⁇ ) is 5 to 88 weight 0/0, preferably 10 75% by weight. If the content of the rubber ( ⁇ ) is too small, the mechanical strength of the crosslinked product is poor, and if it is too large, the ozone resistance is poor.
- the content of the copolymer ( ⁇ ) with respect to the total amount of the rubber ( ⁇ ), the copolymer ( ⁇ ) and the rubber (C) is 1
- the content of the rubber (Alpha), copolymer (beta) and rubber to the total amount of rubber (C) (C) are 2-50 weight 0/0, is preferably 5- 40 wt 0/0 . If the content of the rubber (C) is too small, the solvent crack resistance of the crosslinked product is poor, and if it is too large, the mechanical strength is poor.
- the polymer alloy according to the present invention includes, besides the rubber (A), the copolymer (B) and the rubber (C), as long as the effects and objects of the present invention are not impaired. Further, a rubber resin other than the copolymer (B) may be contained. The content of these rubbers or resins is usually 20% by weight or less, preferably 15% by weight or less. If the content of these rubbers and the like is too large, the ozone resistance and oil resistance of the polymer alloy may be poor.
- the polymer alloy according to the present invention includes a compounding agent used for a general rubber, for example, a reinforcing agent such as nylon black and silica; calcium carbonate, magnesium carbonate, clay, nylon, talc, fine powder and the like.
- Fillers such as talc, mai power, aluminum hydroxide, magnesium hydroxide, citric acid, magnesium silicate, aluminum silicate, calcium silicate; ⁇ , ⁇ -unsaturated carboxylic acid metal salts; pigments; You may make it contain.
- the polymer alloy according to the present invention is obtained by using a rubber (A), (C), a copolymer ( ⁇ ⁇ ), and the above-mentioned compounding agents and the like compounded as necessary, for example, using a mixer such as a roll or a Banbury. And can be prepared by a dry blending method of mixing under heating. Alternatively, it may be prepared by using a latex coprecipitation method in which the rubbers (A) and (C) and the copolymer ( ⁇ ) are mixed in a latex state and coagulated.
- the crosslinkable polymer alloy of the present invention is obtained by blending a crosslinker with the above polymer alloy.
- crosslinking agent examples include a sulfur-based crosslinking agent, an organic peroxide, and a polyamine-based crosslinking agent.
- sulfur-based crosslinking agent examples include sulfur such as powdered sulfur and precipitated sulfur; organic sulfur compounds such as 4,4'-dithiomorpholine; and the like.
- Examples of the organic peroxide include dialkyl peroxides, disilver oxides, and peroxyesters.
- dialkyl peroxides include dicumyl peroxide, di-t_butyl peroxide, 2,5-dimethinolee 2,5-di (t-butylperoxy) _3-hexine, and 2,5_dimethinoleate 2,5-di ( Examples include t-butylperoxy) hexane and 1,3-bis (t_butylperoxyisopropyl) benzene.
- peroxyesters include 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyisopropylcarbonate, and the like.
- a polyamine-based cross-linking agent is a compound having two or more amino groups, in which a plurality of hydrogens of an aliphatic hydrocarbon or an aromatic hydrocarbon is represented by an amino group or a hydrazide structure, that is, -CONHNH. It has been replaced with the following structure.
- a polyamine-based crosslinking agent fats
- Examples include aliphatic polyamines, aromatic polyamines, and compounds having two or more hydrazide structures.
- the aliphatic polyamines include hexamethylene diamine, hexamethylene diamine dirubamate, tetramethylene pentamine, hexamethylene diamine cinnamaldehyde adduct, hexamethylene diamine dibenzoate salt, and the like.
- Aromatic polyamines include 4,4-methylenedianiline, 4,4, oxydiphenylamine, m-phenylenediamine, p-phenylenediamine, and 4,4'-methylenebis (o-chloroamine). Diphosphorus) and the like.
- the compound having two or more hydrazide structures include isophthalic dihydrazide, adipic dihydrazide, and sebacic dihydrazide.
- the amount of the crosslinking agent varies depending on the type of the crosslinking agent.
- the total amount of the rubber (A) and the rubber (C) is 0.1 to 10 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight. It is 7 parts by weight, particularly preferably 0.5-5 parts by weight. If the amount of the crosslinking agent is too small, the compression set becomes large, and if it is too large, the bending fatigue resistance is poor.
- a crosslinking accelerator is usually used in combination.
- the crosslinking accelerator include zinc white, sulfenamide-based crosslinking accelerator, guanidine-based crosslinking accelerator, thiazole-based crosslinking accelerator, thiuram-based crosslinking accelerator, and dithioate-based crosslinking accelerator.
- the amount of the crosslinking accelerator used is not particularly limited, and may be determined according to the use of the crosslinked product, the required performance, the type of the sulfur crosslinking agent, the type of the crosslinking accelerator, and the like.
- a crosslinking aid is usually used in combination.
- the crosslinking aid include triallyl cyanurate, trimethylolpropane trimetatalate, N, N, _m-phenylene bismaleimide, and the like. These may be dispersed in clay, calcium carbonate, silica, or the like to use those having improved handling properties.
- the amount of the crosslinking aid used is not particularly limited and is determined according to the use of the crosslinked product, the required performance, the type of the crosslinking agent, the type of the crosslinking aid, and the like. Just do it.
- the method for preparing the crosslinkable polymer alloy according to the present invention is not particularly limited, and may be performed by a known method in which a crosslinking agent is blended into rubber.
- the compounding of the cross-linking agent is preferably carried out by a method that does not easily generate heat generated by shearing so that the cross-linking does not progress during mixing.
- the crosslinked product of the present invention is obtained by crosslinking the above crosslinkable polymer alloy.
- Cross-linking of the cross-linkable polymer alloy can be performed by heating the cross-linking agent contained in the polymer alloy to a temperature equal to or higher than the cross-linking initiation temperature.
- the crosslinking temperature is preferably 100 to 200 for a general crosslinking agent. C, more preferably 130-190. C, particularly preferably 140-180. C. If the temperature is too low, the crosslinking time may be too long or the crosslinking density may be too low. If the temperature is too high, molding failure may occur.
- the crosslinking time varies depending on the crosslinking method, crosslinking temperature, shape and the like, but is preferably in the range of 1 minute or more and 5 hours or less from the viewpoint of crosslinking density and production efficiency. Further, depending on the shape and size of the cross-linked product, the surface may be cross-linked, but the inside may not be sufficiently cross-linked, so that secondary cross-linking may be performed.
- the heating method for cross-linking may be appropriately selected from methods used for normal rubber cross-linking, such as press heating, steam heating, oven heating, and hot air heating.
- the crosslinked product of the present invention has excellent ozone resistance and oil resistance, and also has excellent solvent crack resistance. Therefore, it is suitably used as a constituent material of industrial parts such as hoses, belts, seals and rolls. Specifically, it is used as a material for industrial parts such as fuel hoses for automobiles such as filler hoses, other general fuel hoses, timing belts, packings, oil seals, rolls, automobile interior parts, fuel system seals and gaskets. It is suitable. Particularly, it is extremely suitable for rolls for printing, spinning, papermaking, dyeing, and iron making, etc., which require solvent resistance.
- rubber (A) was produced as follows. 100 parts of a monomer mixture (butadiene 55%, nitrile nitrile 45%), 270 parts of ion-exchanged water, 3 parts of potassium oleate (milk-forming agent), 0.1 part of sodium formaldehyde sulfoxylate, cumenehide Mouth peroxide (polymerization initiator) 0.01 parts and tert-dodecyl mercaptan (molecular weight regulator) 0.51 parts were charged into a nitrogen-replaced autoclave, and the monomer conversion was determined at a reaction temperature of 10 ° C. Was reached and the reaction was stopped by adding 0.1 part of hydroxylamine sulfate as a terminator.
- a monomer mixture butadiene 55%, nitrile nitrile 45%
- 270 parts of ion-exchanged water 3 parts of potassium oleate (milk-forming agent)
- a copolymer (B1) was produced as follows. 150 parts of ion-exchanged water in the reaction vessel
- the size of the acrylic copolymer particles was measured using a light scattering particle size analyzer (Model N4, manufactured by Coulter Inc.).
- the particles of the copolymer B1 were dissolved in tetrahydrofuran, and the number average molecular weight measured by gel permeation chromatography using polystyrene as a standard substance was about 660,000.
- the polymerization reaction solution was filtered to collect the particles of the copolymer B1, the collected particles were dispersed in pure water, and a washing step of filtering and collecting the particles again was performed twice, followed by drying and drying of the copolymer B1. Particles were obtained.
- the glass transition temperature of the particles was 21.0 ° C.
- the glass transition temperature was measured by a differential scanning calorimetry (DSC method).
- the particles of the copolymer B1 did not have a melting temperature.
- Copolymer B2 described below And so on.
- rubber (C1) was produced as follows. 100 parts of monomer mixture (butadiene 55%, Atari lonitrinole 45./.), 200 parts of ion-exchanged water, 2 parts of sodium dodecylbenzenesulfonate (emulsifier), 0.2 parts of sodium sulfate, ammonium persulfate (polymerization initiator ) Charge 0.3 parts and 10 parts of tert-dodecyl mercaptan (molecular weight regulator) into an autoclave purged with nitrogen, react at 35 ° C until the monomer conversion reaches 85%, and stop. The reaction was stopped by adding 0.5 part of hydroxynoreamine sulfate as an agent.
- the emulsion polymerization reaction solution was taken out, and steam at 100 ° C. was blown into it. 280 parts of the emulsion polymerization solution from which unreacted monomers had been removed were added to 1000 parts of a 0.5% aluminum sulfate aqueous solution to coagulate the copolymer rubber. The coagulated material is washed thoroughly with water and dried at about 80 ° C for 3 hours to obtain a liquid acrylonitrile-butadiene copolymer rubber having an acrylonitrile monomer unit amount of 43.3% and a number average molecular weight of 4030 (rubber). (C1)) was obtained.
- Oil resistance was determined according to JIS-K6258. Fuel oil C (isooctane and toluene mixed at a volume ratio of 1: 1 adjusted to 40 ° C: Fue) The crosslinked sheet was immersed in C), and the volume swelling (unit:%) after 48 hours had been obtained was evaluated. The smaller the volume swell, the better the oil resistance. The results are shown in Table 1.
- the ozone resistance (static ozone test) is based on JIS-K6259. evaluated. Later The less cracks that occur, the better the ozone resistance. The evaluation was indicated by the following abbreviations. NC: No cracks were observed. A1—3, B1—3, C1—3: The alphabet represents the number of cracks. B is greater than A. C is greater than B. The larger the number, the larger the crack. Cut: The crosslinked sheet has been cut. The results are shown in Table 1.
- the solvent cracking resistance (solvent crack growth test) was determined by drawing a mark at intervals of 20 mm at the center of a strip-shaped test piece having a width of 10 mm and a length of 100 mm. At the center, insert a 2mm wide razor in the direction parallel to the marked line so that it penetrates to the back. Next, this test piece is attached to a jig that can be stretched to an arbitrary length, and then stretched so that the stretch rate becomes 100%. The test piece in the stretched state was immersed in predetermined Fuel-C at 40 ° C, and the time until the specimen was broken was measured. The longer the time to rupture, the better the solvent crack resistance. The results are shown in Table 1.
- a polymer alloy and a 2 mm thick crosslinked sheet for testing were prepared in the same manner as in Example 1 except that rubber (A) was 40 parts, copolymer (B1) was 40 parts, and rubber (C1) was 20 parts. Oil resistance, ozone resistance and solvent crack resistance were evaluated. The results are shown in Table 1.
- a polymer alloy and a 2 mm thick crosslinked sheet for testing were prepared in the same manner as in Example 1 except that rubber (A) was 30 parts, copolymer (B1) was 50 parts, and rubber (C1) was 20 parts. Oil resistance, ozone resistance and solvent crack resistance were evaluated. The results are shown in Table 1.
- a copolymer (B2) was produced as follows. In the same manner as in Example 1 except that n-butyl acrylate was used instead of ethyl acrylate and the amount of acrylonitrile used was changed, the acrylonitrile monomer unit amount was 44.5%, and the average particle size was 47.5%.
- a rubber (C2) was produced as follows.
- the copolymer rubber was coagulated and dried in the same manner as in Example 1 except that the charged amount of tert-dodecyl mercaptan (molecular weight regulator) was changed to 6 parts.
- the obtained rubber was a liquid acrylonitrile-butadiene copolymer rubber (rubber (C2)) having an acrylonitrile monomer unit amount of 43.9% and a number average molecular weight of 6,500.
- 45 parts of the rubber (A) used in Example 1 40 parts of the copolymer (B2), and 15 parts of the rubber (C 2) were used.
- a polymer alloy and a crosslinked sheet having a thickness of 2 mm for a test were produced, and oil resistance, ozone resistance and solvent crack resistance were evaluated. The results are shown in Table 1.
- Rubber (C3) was produced as follows. The copolymer rubber was coagulated and dried in the same manner as in Example 1 except that 100 parts of a monomer mixture (butadiene 67%, atarilonitrile 33%) was used. The obtained rubber was a liquid acrylonitrile-butadiene copolymer rubber (rubber (C3)) having an acrylonitrile monomer unit amount of 31.8% and a number average molecular weight of 4,700.
- rubber (C3) liquid acrylonitrile-butadiene copolymer rubber having an acrylonitrile monomer unit amount of 31.8% and a number average molecular weight of 4,700.
- Table 1 shows the following.
- Comparative Example 1 contains too little rubber (A) and too much rubber (C1). Was difficult to mold due to its low viscosity and severe adhesion.
- the copolymer (B1) having a large amount of the rubber (A) and Comparative Example 2 having a small content of the rubber (C1) are inferior in both ozone resistance and solvent crack resistance.
- Comparative Example 3 in which the content of the copolymer (B1) is small, is very good in solvent cracking resistance, but inferior in ozone resistance.
- Comparative Example 4 containing no rubber (C1-C3) has good ozone resistance, but is inferior in solvent crack resistance.
- Example 117 which is within the scope of the present invention, favorable results were obtained in all of the oil resistance, the ozone resistance and the solvent cracking resistance, and the balance of these characteristics was obtained. It turns out that it is excellent.
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Abstract
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EP04792475A EP1674519A1 (en) | 2003-10-17 | 2004-10-15 | Polymer alloy, crosslinked object, and industrial part |
JP2005514795A JPWO2005037914A1 (ja) | 2003-10-17 | 2004-10-15 | ポリマーアロイ、架橋物および工業部品 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006348164A (ja) * | 2005-06-16 | 2006-12-28 | Jsr Corp | 耐油耐候性ゴム組成物及びその成形体 |
WO2011049055A1 (ja) * | 2009-10-19 | 2011-04-28 | 日本ゼオン株式会社 | 架橋性ニトリルゴム組成物およびその製造方法 |
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DE102008004952A1 (de) * | 2008-01-18 | 2009-07-23 | Continental Aktiengesellschaft | Kautschukmischung mit verbesserter Tieftemperaturflexibilität |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4654404A (en) * | 1984-11-21 | 1987-03-31 | Nippon Zeon Co., Ltd. | Oil-resistant rubber composition |
JPH09309975A (ja) * | 1996-05-21 | 1997-12-02 | Nippon Zeon Co Ltd | 半導電性ゴムロール |
JP2002047379A (ja) * | 2000-08-03 | 2002-02-12 | Nippon Zeon Co Ltd | ゴム配合材料、ゴム組成物、及びゴム架橋物 |
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2004
- 2004-10-15 CN CNA2004800304567A patent/CN1867627A/zh active Pending
- 2004-10-15 WO PCT/JP2004/015258 patent/WO2005037914A1/ja active Application Filing
- 2004-10-15 EP EP04792475A patent/EP1674519A1/en active Pending
- 2004-10-15 JP JP2005514795A patent/JPWO2005037914A1/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4654404A (en) * | 1984-11-21 | 1987-03-31 | Nippon Zeon Co., Ltd. | Oil-resistant rubber composition |
JPH09309975A (ja) * | 1996-05-21 | 1997-12-02 | Nippon Zeon Co Ltd | 半導電性ゴムロール |
JP2002047379A (ja) * | 2000-08-03 | 2002-02-12 | Nippon Zeon Co Ltd | ゴム配合材料、ゴム組成物、及びゴム架橋物 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006348164A (ja) * | 2005-06-16 | 2006-12-28 | Jsr Corp | 耐油耐候性ゴム組成物及びその成形体 |
WO2011049055A1 (ja) * | 2009-10-19 | 2011-04-28 | 日本ゼオン株式会社 | 架橋性ニトリルゴム組成物およびその製造方法 |
US9382391B2 (en) | 2009-10-19 | 2016-07-05 | Zeon Corporation | Cross-linkable nitrile rubber composition and method of production of same |
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JPWO2005037914A1 (ja) | 2006-12-28 |
CN1867627A (zh) | 2006-11-22 |
EP1674519A1 (en) | 2006-06-28 |
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