WO2010050552A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2010050552A1 WO2010050552A1 PCT/JP2009/068582 JP2009068582W WO2010050552A1 WO 2010050552 A1 WO2010050552 A1 WO 2010050552A1 JP 2009068582 W JP2009068582 W JP 2009068582W WO 2010050552 A1 WO2010050552 A1 WO 2010050552A1
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- 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
- C08K7/00—Use of ingredients characterised by shape
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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
- C08L9/04—Latex
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
Definitions
- the present invention relates to a rubber composition that gives a crosslinked nitrile copolymer rubber having low gasoline permeability and excellent sour gasoline resistance and cold resistance, and a latex composition that gives the rubber composition.
- a rubber (nitrile copolymer rubber) containing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a conjugated diene monomer unit or an olefin monomer unit is a rubber having excellent oil resistance.
- the crosslinked product is mainly used as a material for rubber products around various oils for automobiles such as fuel hoses, gaskets, packings and oil seals.
- Patent Document 1 discloses a very high nitrile having a glass transition temperature of -15 to 30 ° C. and a nitrile content of 55 to 80% by weight (an extremely high nitrile is a very high nitrile content of 55 to 80% by weight).
- a nitrile copolymer rubber having a nitrile content has been proposed.
- the plasticizer tends to bleed and is inferior in cold resistance.
- EP1205499A2 Japanese Patent Application Laid-Open No. 2002-206011
- the present invention has been made in view of the above circumstances, and provides a rubber composition that provides a crosslinked nitrile copolymer rubber having low gasoline permeability and excellent sour gasoline resistance and cold resistance, and latex that provides the rubber composition.
- An object is to provide a composition.
- the latex of a nitrile copolymer rubber having a predetermined amount of an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is made into a slurry using a swelling power against water and an aqueous medium. It has been found that the above object can be achieved by a nitrile copolymer latex composition obtained by adding a platy filler having a thixotropic index (TI value) in a predetermined range, and the present invention has been completed. It was.
- TI value thixotropic index
- the present invention contains a latex of a nitrile copolymer rubber (A) having 20 to 70% by weight of an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a plate-like filler (B).
- the thixotropic index (TI value) is 1 to 6 when mixed into a slurry, and the ratio of the plate filler (B) to 100 parts by weight of the nitrile copolymer rubber (A) is 1 A nitrile copolymer latex composition that is ⁇ 200 parts by weight is provided.
- the nitrile copolymer rubber (A) further has a cationic monomer unit and / or a monomer unit capable of forming a cation, and in the nitrile copolymer rubber (A), The content ratio of the cationic monomer unit and / or the monomer unit capable of forming a cation is 0.1 to 20% by weight.
- the nitrile copolymer rubber (A) further has a conjugated diene monomer unit, and the content ratio of the conjugated diene monomer unit in the nitrile copolymer rubber (A) is 10 ⁇ 79.9% by weight.
- the plate-like filler (B) has an aspect ratio of 30 to 2,000.
- the plate-like filler (B) is a smectite.
- the nitrile copolymer latex composition further contains a plasticizer (C).
- the nitrile copolymer rubber (A) is a hydrogenated nitrile copolymer rubber in which at least a part of the carbon-carbon unsaturated bond portion is hydrogenated.
- the nitrile copolymer latex composition further contains 10 to 150 parts by weight of a vinyl chloride resin and / or an acrylic resin with respect to 100 parts by weight of the nitrile copolymer rubber (A).
- a nitrile copolymer rubber composition obtained by coagulating any of the above nitrile copolymer latex compositions.
- the nitrile copolymer rubber composition is used in an amount of 10 to 150 parts by weight of vinyl chloride resin and / or 100 parts by weight of the nitrile copolymer rubber (A) in the nitrile copolymer rubber composition.
- a crosslinkable nitrile copolymer rubber composition obtained by adding a crosslinking agent to any of the above nitrile copolymer rubber compositions.
- a crosslinked rubber product obtained by crosslinking the crosslinkable nitrile copolymer rubber composition.
- the rubber cross-linked product is a hose.
- a rubber composition that gives a crosslinked nitrile copolymer rubber having low gasoline permeability and excellent sour gasoline resistance and cold resistance, and a latex composition that gives the rubber composition.
- the nitrile copolymer latex composition of the present invention has a latex of nitrile copolymer rubber (A) having 20 to 70% by weight of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units and a swelling power to water of 15
- the ratio of the plate filler (B) to 100 parts by weight of the nitrile copolymer rubber (A) is 1 to 200 parts by weight.
- Nitrile copolymer rubber (A) First, the nitrile copolymer rubber (A) constituting the latex of the nitrile copolymer rubber (A) used in the present invention will be described.
- the nitrile copolymer rubber (A) is a rubber having at least 20 to 70% by weight of an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit.
- the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is 20 to 70% by weight, preferably 25 to 65% by weight, more preferably 30 to 60% by weight based on the total monomer units. %.
- the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is too low, the oil resistance of the resulting rubber cross-linked product is deteriorated and the gasoline permeability is increased.
- the content is too high, the resulting rubber cross-linked product is inferior in cold resistance, and the embrittlement temperature is increased.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
- the nitrile copolymer rubber (A) used in the present invention is a monomer capable of forming a cationic monomer unit and / or a cation in addition to the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit. It is preferable to further have a unit.
- the content ratio of the cationic monomer unit and / or the monomer unit capable of forming a cation is preferably 0.1 to 20% by weight, more preferably 0.3%, based on the total monomer units. -15% by weight, more preferably 0.5-10% by weight.
- the content ratio of the cationic monomer unit and / or the monomer unit capable of forming a cation is too low, the gasoline permeability of the resulting rubber cross-linked product tends to increase.
- the content ratio is too high, the cold resistance of the resulting rubber cross-linked product tends to deteriorate.
- a monomer that forms a cationic monomer unit and / or a monomer unit capable of forming a cation is a monomer that is positively charged when the resulting polymer contacts water or an aqueous acid solution.
- the monomer is not particularly limited as long as it is a monomer that forms a unit.
- a monomer containing a quaternary ammonium base is preferred as a cationic monomer.
- a monomer capable of forming a cation it is cationized to an ammonium salt (for example, amine hydrochloride or amine sulfate) when coming into contact with an aqueous acid solution such as hydrochloric acid and sulfuric acid such as a tertiary amino group.
- an ammonium salt for example, amine hydrochloride or amine sulfate
- aqueous acid solution such as hydrochloric acid and sulfuric acid such as a tertiary amino group.
- a monomer having a precursor portion (substituent) is preferred.
- cationic monomer examples include (meth) acryloyloxytrimethylammonium chloride [acryloyloxytrimethylammonium chloride and / or methacryloyloxytrimethylammonium chloride. The same applies hereinafter.
- Quaternary ammonium bases such as (meth) acryloyloxyhydroxypropyltrimethylammonium chloride, (meth) acryloyloxytriethylammonium chloride, (meth) acryloyloxydimethylbenzylammonium chloride, (meth) acryloyloxytrimethylammonium methyl sulfate (Meth) acrylic acid ester monomers; (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidepropyldimethylbenzylammonium chloride and other (meth) acrylamide monomers containing quaternary ammonium bases; It is done.
- the monomer capable of forming a cation include vinyl group-containing cyclic amine monomers such as 2-vinylpyridine and 4-vinylpyridine; tertiary amino groups such as dimethylaminoethyl (meth) acrylate.
- (Meth) acrylic acid ester monomer (meth) acrylamide-containing (meth) acrylamide monomer such as (meth) acrylamide dimethylaminoethyl and N, N-dimethylaminopropylacrylamide; N- (4-anilinophenyl) ) Acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) ) Aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
- acrylamide-containing (meth) acrylamide monomer such as (meth) acrylamide dimethylaminoethyl and N, N-dimethylaminopropylacrylamide
- N- (4-anilinophenyl) ) Acrylamide N- (4-an
- a vinyl group-containing cyclic amine monomer, a tertiary amino group-containing (meth) acrylic Acid ester monomers and tertiary amino group-containing (meth) acrylamide monomers are preferred, vinyl group-containing cyclic amine monomers and tertiary amino group-containing acrylamide monomers are more preferred, vinyl group-containing cyclic amines Monomers are particularly preferred. These can be used individually by 1 type or in combination of multiple types.
- the nitrile copolymer rubber (A) used in the present invention preferably also contains a conjugated diene monomer unit so that the resulting rubber cross-linked product has rubber elasticity.
- the conjugated diene monomer forming the conjugated diene monomer unit is preferably a conjugated diene having 4 or more carbon atoms, such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1 , 3-pentadiene. Of these, 1,3-butadiene is preferred. These can be used individually by 1 type or in combination of multiple types.
- the content ratio of the conjugated diene monomer unit in the nitrile copolymer rubber (A) is preferably 10 to 79.9% by weight, more preferably 20 to 74.7% by weight based on the total monomer units. %, More preferably 30 to 69.5% by weight.
- the content rate of a conjugated diene monomer unit is too low, there exists a possibility that the rubber elasticity of the rubber crosslinked material obtained may fall. On the other hand, if the amount is too large, the heat aging resistance and chemical stability of the resulting rubber cross-linked product may be impaired.
- the nitrile copolymer rubber (A) used in the present invention is the above ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, cationic monomer unit and / or monomer unit capable of forming a cation,
- other monomer units copolymerizable with the monomers forming these monomer units may be contained.
- the content ratio of such other monomer units is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less based on the total monomer units.
- Examples of such other copolymerizable monomers include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene; fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethyl styrene, pentafluoro Fluorine-containing vinyl compounds such as vinyl benzoate, difluoroethylene, and tetrafluoroethylene; non-conjugated diene compounds such as 1,4-pentadiene, 1,4-hexadiene, vinylnorbornene, and dicyclopentadiene; ethylene; propylene, 1-butene, ⁇ -olefin compounds such as 4-methyl-1-pentene, 1-hexene, 1-octene; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, fumaric anhydride, etc.
- aromatic vinyl compounds
- ⁇ , ⁇ -Ethylene Saturated carboxylic acids and their anhydrides ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Esters: monoethyl maleate, diethyl maleate, monobutyl maleate, dibutyl maleate, monoethyl fumarate, diethyl fumarate, monobutyl fumarate, dibutyl fumarate, monocyclohexyl fumarate, dicyclohexyl fumarate, monoethyl itaconate, diethyl itaconate , Monoesters and diesters of ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acids such as monobutyl itaconate, dibutyl itaconate; methoxyeth
- the Mooney viscosity of the nitrile copolymer rubber (A) (hereinafter sometimes referred to as “polymer Mooney viscosity”) (ML 1 + 4 , 100 ° C.) is preferably 3 to 250, more preferably 10 to 230, A preferred range is 20 to 200. If the polymer Mooney viscosity of the nitrile copolymer rubber (A) is too low, the strength characteristics of the resulting rubber cross-linked product may be lowered. On the other hand, when too high, workability in the case of using a nitrile copolymer latex composition may be deteriorated.
- the method for producing latex of nitrile copolymer rubber (A) is not particularly limited, and each monomer constituting the nitrile copolymer rubber (A) described above Any method can be used as long as it can be copolymerized, for example, an emulsion polymerization method for obtaining a latex of a copolymer having an average particle size of about 50 to 1,000 nm using an emulsifier such as sodium dodecylbenzenesulfonate, A suspension polymerization method (including a fine suspension polymerization method) for obtaining a latex of a copolymer having an average particle size of about 0.2 to 200 ⁇ m using a dispersant such as alcohol can be suitably used.
- the emulsion polymerization method is more preferable because the polymerization reaction can be easily controlled.
- the emulsion polymerization method is preferably performed according to the following procedure.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is referred to as “monomer (m1)”
- the conjugated diene monomer is referred to as “monomer (m2)”
- a cationic monomer The monomer capable of forming a body and / or cation is referred to as “monomer (m3)”.
- 100 parts by weight of the monomer mixture (however, the total amount of the monomer (m1), the monomer (m2) and the monomer (m3) is 100 parts by weight) is emulsion-polymerized, and the polymerization conversion rate is Preferably, a method of removing the unreacted monomer as desired after stopping the polymerization reaction at a point of 50 to 95% by weight is preferable.
- the polymerization reaction may be started using the total amount of the monomers (m1) to (m3) used in the emulsion polymerization, but the composition distribution of each monomer unit of the copolymer to be produced is controlled. From the viewpoint of obtaining a rubber cross-linked product rich in rubber elasticity, a part of the total amount of the monomers (m1) to (m3) used for the emulsion polymerization is used to start the polymerization reaction, and then the emulsion polymerization is performed. The remainder of the monomers (m1) to (m3) to be used is preferably added to the reactor for polymerization.
- the monomer (m1) used for the polymerization is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, particularly preferably 30 to 100% by weight, preferably the monomer (m2) used for the polymerization. Is from 5 to 90% by weight, more preferably from 10 to 80% by weight, particularly preferably from 15 to 70% by weight, and preferably from 0 to 100% by weight, more preferably from 30 to 70% by weight of the monomer (m3) used in the polymerization.
- a monomer mixture comprising 100% by weight, particularly preferably 70 to 100% by weight is charged into the reactor, and after the polymerization reaction is started, the polymerization conversion rate with respect to the monomer mixture charged into the reactor is preferably 5 to 80%. It is preferable to continue the polymerization reaction by adding the remaining monomer to the reactor in the range of% by weight.
- the method for adding the remaining monomer is not particularly limited, but it may be added all at once, dividedly, or continuously.
- the remaining monomer is preferably added in portions, particularly preferably added in portions 1 to 6 times. preferable.
- the amount of monomer to be added in a divided manner and the timing of the divided addition may be adjusted so as to obtain a desired copolymer in accordance with the progress of the polymerization reaction.
- a latex of the nitrile copolymer rubber (A) can be obtained by removing unreacted monomers using a known method such as heating distillation, vacuum distillation, steam distillation or the like.
- the latex solid content concentration of the nitrile copolymer rubber (A) obtained by the emulsion polymerization method is preferably 5 to 70% by weight, more preferably 10 to 60% by weight.
- the nitrile copolymer rubber (A) used in the present invention is such that at least a part of the unsaturated bond portion in the conjugated diene monomer unit portion of the copolymer obtained by copolymerization as described above is hydrogen.
- Hydrogenated nitrile copolymer rubber may be used (hydrogenation reaction).
- the method for hydrogenation is not particularly limited, and a known method may be employed.
- the nitrile copolymer rubber (A) is a hydrogenated nitrile copolymer rubber, the iodine value is 120 or less, preferably 80 or less, more preferably 40 or less.
- Nitrile Copolymer Latex Composition The nitrile copolymer latex composition of the present invention has a swellability with respect to water of 15 to 55 (ml / 2 g) in the latex of the nitrile copolymer rubber (A) described above, and A plate-like filler (B) having a thixotropic index (TI value) of 1 to 6 in a slurry mixed with an aqueous medium at a concentration of 5% by weight is added. In addition, ion-exchange water is used as an aqueous medium.
- TI value thixotropic index
- the plate filler (B) has a swelling power to water of 15 to 55 (ml / 2g), preferably 20 to 53 (ml / 2g), more preferably 24 to 51 (ml / 2g). is there.
- the plate-like filler (B) has a TI value of 1 to 6, preferably 1 to 5, more preferably, when mixed at a concentration of 5% by weight with respect to the aqueous medium to form a slurry. 2-5.
- the swelling power with respect to the water of a plate-shaped filler (B) is measured with the following method. That is, first, 100 ml of ion-exchanged water is put into a graduated cylinder, and then 2 g of plate-like filler (B) in a sufficiently dried state is added in about 10 times so as not to adhere to the inner wall of the graduated cylinder. Then, after standing for 24 hours, the volume (ml) of the deposit (plate filler (B) swollen with water) deposited at the bottom of the graduated cylinder was measured, and this was measured with the water of the plate filler (B). Swelling force (unit: ml / 2g).
- the swelling power of the plate-like filler (B) with respect to water tends to change depending on the kind and content of the cation contained in the plate-like filler (B), for example, the kind of cation And can be controlled by selecting the content. Specifically, by increasing the content of K + ions among divalent cations such as Ca 2+ ions and Mg 2+ ions and monovalent cations as cations, The swelling power of the filler (B) with respect to water can be reduced.
- the content of divalent cations and K + ions is decreased, and instead of the content of monovalent cations other than K + ions, such as Na + ions and Li + ions, By increasing it, the swelling power of the plate-like filler (B) with respect to water can be increased.
- the TI value is measured by the following method. That is, first, a plate-like filler (B) is added to ion-exchanged water so as to have a concentration of 5% by weight and stirred vigorously, and left at room temperature for 24 hours, whereby a slurry of the plate-like filler (B) is obtained. Prepare. Then, the B-type viscosity value measured at a rotor rotation speed of 6 rpm and the B-type viscosity value measured at a rotor rotation speed of 60 rpm were determined for the prepared slurry, and the ratio of these values (viscosity at 6 rpm / viscosity at 60 rpm) was obtained. ).
- the TI value is a general index indicating the thixotropy of the slurry. For example, at a rotation speed of 6 rpm (quiet stirring state), the slurry swollen with water is soft jelly and the viscosity increases. At several 60 rpm (violent stirring state), the soft jelly state is destroyed, so that the viscosity is lowered. Note that the thixotropy increases as the TI value increases.
- the TI value of the platy filler (B) tends to be lower as the aspect ratio of the platy filler (B) is smaller, and the cohesive force between the platy fillers (B) is further reduced.
- the smaller the value the lower the tendency. Therefore, for example, delamination in the plate-like filler (B) is suppressed by a method such as increasing the content of divalent cations in the plate-like filler (B).
- the aspect ratio of (B) By making the aspect ratio of (B) small, it becomes possible to lower the TI value of the plate-like filler (B).
- the TI value of the plate-like filler (B) tends to increase as the aspect ratio of the plate-like filler (B) increases, and the cohesive force between the plate-like fillers (B) increases. It tends to be higher. For this reason, for example, delamination in the plate-like filler (B) is easily caused by reducing the content of divalent cations in the plate-like filler (B).
- the TI value of the plate filler (B) can be increased.
- the TI of the plate-like filler (B) can also be increased by increasing the cohesive force between the plate-like fillers (B), for example, by adjusting the plate-like filler (B) by silane treatment. The value can be increased.
- the plate-like filler (B) is not particularly limited as long as it has a plate-like or flat shape, but preferably has an aspect ratio of 30 to 2,000, more preferably 35 to 1,800, More preferably, it is 40 to 1,600.
- the gasoline permeation blocking effect (gasoline permeation resistance) of the resulting rubber cross-linked product can be improved.
- the aspect ratio of the plate-like filler (B) is too small, there is a possibility that the gasoline permeation resistance of the resulting crosslinked product is deteriorated.
- distribution in a nitrile copolymer rubber (A) will become difficult, and there exists a possibility that the mechanical strength of the rubber crosslinked material obtained may fall.
- the aspect ratio of the plate-like filler (B) is a ratio between the surface average diameter and the average thickness of the plate-like filler (B).
- the surface average diameter and the average thickness are calculated as the arithmetic average value by measuring the surface diameter and thickness of 100 plate-like fillers (B) randomly selected with an atomic force microscope. Number average value.
- the plate-like filler (B) is not particularly limited, and examples thereof include plate-like or flat-like inorganic fillers, and those obtained by subjecting natural products to processing such as purification even if they are derived from natural products. Or a synthetic product. Specific examples include: kaolinites such as kaolinite and halosite; montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, mica and other smectites; and vermiculites; chlorite; talc, etc. Among them, smectites are preferable, and montmorillonite, mica, and saponite are particularly preferable. These can be used individually by 1 type or in combination of multiple types.
- montmorillonite as the plate-like filler (B) is contained as a main component in bentonite. Therefore, as the montmorillonite, one obtained by purifying bentonite or the like is used. Can do. Or when using montmorillonite as a plate-shaped filler (B), you may add in the nitrile copolymer latex composition of this invention as bentonite.
- montmorillonite, mica, saponite is used as the plate-like filler (B), these are dispersed in water, and each layer constituting montmorillonite, mica, saponite, which is a compound having a multilayer structure, is used. It is preferable to use one obtained by separation. By performing such an aqueous dispersion treatment, a composition having good dispersibility can be obtained.
- the nitrile copolymer rubber (A) can form a cationic monomer unit and / or a cation. When it has a body unit, it can be preferably used because it is more excellent in dispersibility in the monomer unit. In particular, by increasing the dispersibility of the nitrile copolymer rubber (A) and the plate-like filler (B), the gasoline permeability can be made smaller and the embrittlement temperature can be made lower.
- the average particle size of the plate-like filler (B) is preferably 0.001 to 20 ⁇ m, more preferably 0.005 to 15 ⁇ m, and particularly preferably 0.01 to 10 ⁇ m.
- the average particle diameter of the plate-like filler (B) is defined as a 50% volume cumulative diameter obtained by measuring the particle size distribution by the X-ray transmission method. If the particle size of the plate-like filler (B) is too small, the elongation of the resulting rubber cross-linked product may be reduced. Conversely, if it is too large, a stable latex composition may not be prepared.
- the content of the plate filler (B) in the nitrile copolymer latex composition of the present invention is 1 to 200 parts by weight, preferably 2 to 200 parts by weight with respect to 100 parts by weight of the nitrile copolymer rubber (A). 120 parts by weight, more preferably 5 to 60 parts by weight.
- a plate-shaped filler (B) When there is too little usage-amount of a plate-shaped filler (B), there exists a possibility that the gasoline permeability resistance of the rubber crosslinked material obtained may fall, or sour gasoline resistance may become inadequate. On the other hand, when there is too much usage-amount, there exists a possibility that elongation may fall.
- the nitrile copolymer latex composition of the present invention preferably contains a plasticizer (C) in addition to the nitrile copolymer rubber (A) and the plate-like filler (B).
- a plasticizer (C) those conventionally used as a plasticizer (C) for rubber compounding can be used, and are not particularly limited, but the SP value (solubility parameter) by the HOY method is 8 to 10.2 ( The plasticizer (C) which is cal / cm 3 ) 1/2 is preferably used.
- the SP value of the plasticizer (C) is too large, the resulting rubber cross-linked product tends to be inferior in cold resistance. On the other hand, if it is too small, the gasoline permeation resistance of the resulting rubber cross-linked product tends to deteriorate.
- plasticizer (C) examples include, for example, dibutoxyethyl adipate (SP value: 8.8), adipic acid Ester compound of adipic acid such as di (butoxyethoxyethyl) (SP value: 9.2) and ether bond-containing alcohol; azelaic acid such as dibutoxyethyl azelate, azelaic acid di (butoxyethoxyethyl) and ether bond Ester compounds with alcohols; ester compounds of sebacic acid and ether-bonded alcohols such as dibutoxyethyl sebacate and di (butoxyethoxyethyl) sebacate; dibutoxyethyl phthalate, di (butoxyethoxyethyl) phthalate, etc.
- Ester compound of phthalic acid and ether bond-containing alcohol; isophthalic acid Ester compounds of isophthalic acid such as dibutoxyethyl and di (butoxyethoxyethyl) isophthalate and alcohols containing ether bonds; di- (2-ethylhexyl) adipate (SP value: 8.5), diisodecyl adipate (SP value) 8.3), diisononyl adipate, dialkyl esters of adipate such as dibutyl adipate (SP value: 8.9); di- (2-ethylhexyl) azelate (SP value: 8.5), diisooctyl azelate Dialkyl esters of azelaic acid such as di-n-hexyl azelaic acid; di-n-butyl sebacate (SP value: 8.7), di- (2-ethylhexyl) sebacate (SP value: 8.4), etc.
- Dialkyl esters of sebacic acid dibutyl phthalate (SP value: 9.4), di- (2-ethylhexyl phthalate) (SP value: 9.0), di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate (SP value: 9.0), diisodecyl phthalate (SP value: 8.5), diundecyl phthalate (SP value: 8.5), dialkyl phthalates such as diisononyl phthalate (SP value: 8.9); dicycloalkyl phthalates such as dicyclohexyl phthalate; diphenyl phthalate, butylbenzyl phthalate ( Phthalic acid aryl esters such as SP value 10.2); diphthalic acid dialkyl esters such as di- (2-ethylhexyl) isophthalate and diisooctyl isophthalate; di- (2-ethylhexyl)
- dibasic acids such as adipic acid, azelaic acid, sebacic acid and phthalic acid, and an ether bond are contained.
- An ester compound with an alcohol is preferable, an ester compound with an adipic acid and an ether bond-containing alcohol is more preferable, and di (butoxyethoxyethyl) adipate is particularly preferable.
- the content of the plasticizer (C) in the nitrile copolymer latex composition of the present invention is preferably 0.1 to 200 parts by weight, more preferably 100 parts by weight of the nitrile copolymer rubber (A). 1 to 150 parts by weight, more preferably 2 to 100 parts by weight.
- the content of the plasticizer (C) is in the above range, in addition to preventing bleeding, the effect of the present invention becomes even more remarkable.
- the nitrile copolymer latex composition of the present invention may further contain a particulate filler (D) having an aspect ratio of 1 or more and less than 30.
- a particulate filler (D) having an aspect ratio of 1 or more and less than 30.
- the aspect ratio of the particulate filler (D) is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.
- the aspect ratio of the particulate filler (D) can be calculated by determining the ratio between the average major axis diameter of the particulate filler (D) and the 50% volume cumulative diameter.
- the average major axis diameter is a number average major axis diameter calculated as an arithmetic average value obtained by measuring the major axis diameters of 100 fillers randomly selected from an optical micrograph.
- the particulate filler (D) having an aspect ratio of 1 or more and less than 30 is not particularly limited.
- examples include barium acid, alumina, antimony oxide, red phosphorus, various metal powders, clay, various ferrites, and hydrotalcite. These can be used individually by 1 type or in combination of multiple types.
- a metal compound containing an oxygen atom is preferable, an alkaline earth metal compound containing an oxygen atom is more preferable, and calcium carbonate is particularly preferable.
- the surface is treated with at least one organic substance selected from the group consisting of fatty acids, fatty acid salts, fatty acid esters, resin acids, resin acid salts and resin acid esters. Also good. Dispersibility in the nitrile copolymer rubber composition can be enhanced by using a surface-treated filler as the particulate filler (D).
- the average particle diameter of the particulate filler (D) is preferably 0.01 to 50 ⁇ m, more preferably 0.01 to 40 ⁇ m, and still more preferably 0.01 to 25 ⁇ m.
- the average particle diameter of the particulate filler (D) is defined as a 50% volume cumulative diameter determined by measuring the particle size distribution by the X-ray transmission method. If the average particle size of the particulate filler (D) is too small, the effect of improving crack growth resistance in the presence of a solvent may not be obtained. On the other hand, if the average particle size is too large, the effect of improving the extrusion processability may not be obtained.
- the specific surface area of the particulate filler (D) preferably 1 ⁇ 100,000m 2 / g, more preferably 1 ⁇ 6,000m 2 / g, more preferably 1 ⁇ 500m 2 / g, particularly preferably 1 to 55 m 2 / g. If the specific surface area of the particulate filler (D) is too small, the elongation of the resulting rubber cross-linked product tends to decrease. On the other hand, if the specific surface area is too large, the effect of improving crack growth resistance in the presence of a solvent may not be obtained.
- the content ratio of the plate filler (B) and the particulate filler (D) is preferably in a weight ratio when “plate filler (B) / particulate filler (D)”. Is from 0.01 to 30, more preferably from 0.1 to 10, particularly preferably from 0.5 to 5. If the content ratio of the particulate filler (D) to the platy filler (B) is too low (if the “plate filler (B) / particulate filler (D)” is too large), the nitrile copolymer In some cases, the extrusion processability in the case of the combined rubber composition and the crack growth resistance improvement effect in the presence of the solvent in the case of the rubber cross-linked product may not be obtained.
- the content ratio of the particulate filler (D) to the platy filler (B) is too high (if the “plate filler (B) / particulate filler (D)” is too small), the rubber obtained In some cases, the gasoline permeation resistance of the cross-linked product is lowered, or the effect of improving the crack growth resistance in the presence of a solvent cannot be obtained.
- the nitrile copolymer latex composition of the present invention comprises a cup in addition to the nitrile copolymer rubber (A), the plate-like filler (B), the plasticizer (C), and the particulate filler (D).
- a ring agent may be contained.
- the coupling agent include silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide.
- the method for adding the coupling agent is not particularly limited, and examples thereof include a method of adding the plate-like filler (B) to the plate-like filler (B) and mixing it, and then using the plate-like filler (B) as an aqueous dispersion.
- the content of the coupling agent in the nitrile copolymer latex composition of the present invention is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the nitrile copolymer rubber (A). It is.
- the nitrile copolymer latex composition of the present invention comprises an aqueous dispersion of a plate-like filler (B) and a plasticizer (C) added as necessary to the latex of the nitrile copolymer rubber (A).
- a method in which the aqueous dispersion is added with stirring is preferred. As a result, the latex composition is uniformly mixed and dispersed.
- the method for adjusting the aqueous dispersion of the plate-like filler (B) is not particularly limited, but it may be prepared by adding the plate-like filler (B) while strongly stirring an aqueous medium such as ion exchange water. .
- aqueous medium such as ion exchange water.
- the solid content concentration of the aqueous dispersion of the plate filler (B) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight.
- the plate filler (B) when preparing an aqueous dispersion of the plate filler (B), the plate filler (B) may be dispersed in water using a wet pulverizer.
- a wet pulverizer By dispersing using a wet pulverizer, when the plate-like filler (B) is secondary agglomerated, the secondary agglomeration of the plate-like filler (B) can be eliminated, and the resulting crosslinked product Can be made more excellent in gasoline permeability.
- Nasmizer manufactured by Yoshida Kikai Kogyo Co., Ltd.
- Super Wing Mill DM-200 manufactured by STEC Co., Ltd.
- Starburst manufactured by Sugino Machine Co., Ltd.
- Star Mill Acshizawa Fine
- LPN nanogenizer manufactured by Serendip AG
- the method for preparing the aqueous dispersion of the plasticizer (C) when the plasticizer (C) is used is not particularly limited, but the amount of the surface activity is 0.5 to 10% by weight of the plasticizer (C). It is preferable to prepare by adding the plasticizer (C) while vigorously stirring the aqueous medium containing the agent.
- surfactants include anionic surfactants such as potassium rosinate, sodium lauryl sulfate, potassium oleate, sodium dodecylbenzenesulfonate; polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl.
- Nonionic surfactants such as esters; cationic surfactants such as didecyldimethylammonium chloride and stearyltrimethylammonium chloride.
- concentration of the plasticizer (C) in the aqueous dispersion is preferably 5 to 70% by weight.
- the nitrile copolymer latex composition of the present invention preferably further contains an acrylic resin and / or a vinyl chloride resin.
- an acrylic resin and / or a vinyl chloride resin By containing an acrylic resin and / or a vinyl chloride resin, ozone resistance can be further improved when a rubber cross-linked product is formed.
- the content of the acrylic resin and / or vinyl chloride resin is preferably 10 to 150 parts by weight, more preferably 15 to 125 parts by weight, and still more preferably 20 to 120 parts by weight with respect to 100 parts by weight of the nitrile copolymer rubber (A). 100 parts by weight.
- A nitrile copolymer rubber
- the method for containing the acrylic resin and / or vinyl chloride resin is not particularly limited.
- an acrylic resin and / or vinyl chloride resin in a latex state produced by emulsion polymerization is mixed with the nitrile copolymer latex composition ( Latex blend).
- the main constituent monomer constituting the resin is vinyl chloride, and the content of the monomer unit is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, particularly preferably 70 to 100% by weight.
- the main constituent monomer constituting the resin is a (meth) acrylic acid alkyl ester, and the content of the monomer unit is preferably 50 to 100% by weight.
- the degree of polymerization or the molecular weight of the vinyl chloride resin and the acrylic resin is not particularly limited, but in the case of vinyl chloride resin, the average degree of polymerization according to the solution viscosity method defined in JIS K6721 is preferably 400 to 3,000, more preferably 600 to 2,000.
- the number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent is preferably 10,000 to 7,000,000, more preferably 100,000 to 2,000,000. It is.
- Nitrile copolymer rubber composition crosslinkable nitrile copolymer rubber composition
- the nitrile copolymer rubber composition of the present invention coagulates the above nitrile copolymer latex composition, and is washed and dried as necessary. Can be obtained.
- Coagulation of the nitrile copolymer latex composition is not particularly limited, but it is preferable to carry out salting out by adding the nitrile copolymer latex composition to an aqueous solution containing a coagulant.
- the coagulant include calcium chloride, sodium chloride, calcium hydroxide, aluminum sulfate, and aluminum hydroxide.
- the amount of the coagulant used is preferably 0.5 to 150% by weight, particularly preferably 0.5 to 20% by weight, based on the nitrile copolymer rubber (A).
- the nitrile copolymer rubber (A) contains a cationic monomer unit and / or a monomer unit capable of forming a cation
- the nitrile copolymer latex composition is subjected to salting out. It is preferable to add a dilute sulfuric acid aqueous solution or the like to control the pH of the coagulant aqueous solution below the isoelectric point of the latex composition of the nitrile copolymer (A).
- the zeta potential of the functional group possessed by the cationic monomer unit and the monomer unit capable of forming a cation contained in the nitrile copolymer rubber (A) is increased.
- the dispersibility of the plate-like filler (B) can be improved, and the crumb particle size obtained by solidification can be increased.
- the crumb particle size has a great influence on the degree of dehydration in the vibrating screen or squeezer following the coagulation and washing process, the crumb recovery rate, and the degree of drying in the drying process. For example, if the crumb particle size is too small, the crumb particle size will be too small to flow out of the screen, or the polymer will be insufficiently squeezed by the squeezer and the degree of dehydration will decrease. , Productivity deteriorates. Therefore, the average particle diameter of crumb is preferably 0.5 to 40 mm.
- the crumb washing, dehydration and drying methods can be the same as the washing / dehydration method and drying method in general rubber production.
- a washing / dehydrating method a crumb obtained by coagulation and water may be separated using a mesh filter, a centrifugal separator, etc., then washed, and the crumb may be dehydrated with a squeezer or the like.
- the nitrile copolymer rubber composition of the present invention is obtained by drying to a desired moisture content by a band dryer, a ventilated dryer, a twin screw extruder or the like generally used for rubber production. Can do. Moreover, you may perform coagulation
- nitrile copolymer rubber composition of the present invention in addition to the method described above, for example, a latex of nitrile copolymer rubber (A), a plate-like filler (B), and if necessary Added plasticizer (C), particulate filler (D) added if necessary, coupling agent added if necessary, and acrylic resin and / or added if necessary It can be obtained by adding all or a part of one or more components of vinyl chloride resin and then coagulating and drying, and kneading the remaining components with a kneader such as a roll or Banbury mixer. .
- a kneader such as a roll or Banbury mixer.
- a kneading machine such as a roll or a Banbury mixer.
- the Mooney viscosity of the nitrile copolymer rubber composition thus obtained is preferably 5 to 300, more preferably 10 to 250.
- the crosslinkable nitrile copolymer rubber composition of the present invention is obtained by adding a crosslinking agent to the nitrile copolymer rubber composition obtained by the above method.
- the crosslinking agent is not particularly limited as long as it is usually used as a crosslinking agent for nitrile group-containing copolymer rubber.
- a typical crosslinking agent includes a sulfur-based crosslinking agent or an organic peroxide crosslinking agent that bridges between unsaturated bonds of the nitrile copolymer rubber (A). These can be used individually by 1 type or in combination of multiple types. Among these, a sulfur type crosslinking agent is preferable.
- Sulfur-based crosslinking agents include powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, and other sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothiazyl disulfide, N, Sulfur-containing compounds such as N′-dithio-bis (hexahydro-2H-azenopine-2), phosphorus-containing polysulfides, polymer polysulfides; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, 2- (4′-morpholinodithio) And sulfur donating compounds such as benzothiazole; These can be used individually by 1 type or in combination of multiple types.
- organic peroxide crosslinking agents include dicumyl peroxide, cumene hydroperoxide, t-butylcumyl peroxide, paramentane hydroperoxide, di-t-butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,4-bis (t-butylperoxyisopropyl) benzene, 1,1-di-t-butylperoxy-3,3-trimethylcyclohexane, 4,4-bis- (t-butyl-peroxy) -n-butylvale 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, 1,1-di-t-butyl Peroxy-3,5,5-trimethylcyclohexane, p-chlorobenzoyl peroxide, t-butyl
- the content of the crosslinking agent in the crosslinkable nitrile copolymer rubber composition of the present invention is not particularly 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.
- a multifunctional monomer such as trimethylolpropane trimethacrylate, divinylbenzene, ethylene dimethacrylate, or triallyl isocyanurate can be used in combination as a crosslinking aid.
- the amount of these crosslinking aids is not particularly limited, but is preferably in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the nitrile copolymer rubber (A).
- crosslinking assistants such as zinc white and stearic acid
- crosslinking accelerators such as guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, and thiourea
- the amounts of these crosslinking aids and crosslinking accelerators are not particularly limited, and are preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the nitrile copolymer rubber (A).
- the nitrile copolymer rubber composition or the crosslinkable nitrile copolymer rubber composition of the present invention includes other compounding agents used for general rubber as necessary, for example, a crosslinking retarder, an antiaging agent. , Fillers other than plate filler (B) and particulate filler (D), reinforcing agents, lubricants, adhesives, lubricants, processing aids, flame retardants, antifungal agents, antistatic agents, colorants, etc. These additives may be blended.
- an anti-aging agent such as phenol, amine, benzimidazole or phosphoric acid
- an anti-aging agent such as phenol, amine, benzimidazole or phosphoric acid
- 2,2'-methylenebis (4-methyl-6-t-butylphenol) and the like are used for phenols, and 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine and N-isopropyl-N 'for amines.
- -Phenyl-p-phenylenediamine and the like, and benzimidazole type include 2-mercaptobenzimidazole and the like. These may be used alone or in combination of two or more.
- the nitrile copolymer latex composition, the nitrile copolymer rubber composition, and the crosslinkable nitrile copolymer rubber composition of the present invention include nitrile copolymer rubber (A You may contain rubbers other than.
- the rubber other than the nitrile copolymer rubber (A) is not particularly limited, but acrylic rubber, ethylene-acrylic acid copolymer rubber, fluorine rubber, styrene-butadiene copolymer rubber, ethylene-propylene copolymer rubber, Mention may be made of ethylene-propylene-diene terpolymer rubber, natural rubber and polyisoprene rubber, ethylene-vinyl acetate copolymer and the like.
- the blending amount is preferably 100 parts by weight or less, more preferably 50 parts by weight with respect to 100 parts by weight of nitrile copolymer rubber (A).
- it is particularly preferably 30 parts by weight or less.
- the crosslinkable nitrile copolymer rubber composition of the present invention has a Mooney viscosity (hereinafter sometimes referred to as “compound Mooney viscosity”) (ML 1 + 4 , 100 ° C.), preferably 5 to 250, more preferably 10 ⁇ 200.
- compound Mooney viscosity hereinafter sometimes referred to as “compound Mooney viscosity”
- Cross-linked rubber The cross-linked rubber of the present invention is formed by cross-linking the cross-linkable nitrile copolymer rubber composition.
- a molding machine corresponding to the shape of the molded product (rubber crosslinked product) to be produced, such as an extruder, an injection molding machine, a compressor, a roll, etc.
- the shape of the cross-linked product is fixed by carrying out a cross-linking reaction.
- the cross-linking may be performed after molding or may be performed simultaneously with the 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.
- the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 1 hour.
- the rubber cross-linked product even if the surface is cross-linked, it may not be sufficiently cross-linked to the inside, so it may be further heated to perform secondary cross-linking.
- the rubber cross-linked product of the present invention thus obtained has a small gasoline permeability and has excellent sour gasoline resistance and cold resistance. Therefore, it is suitably used as a hose comprising one layer or two or more layers in which the layer (I) comprising the rubber cross-linked product of the present invention is at least one layer, and particularly suitably used as a fuel hose.
- the layer (I) composed of the rubber cross-linked product of the present invention may be used for any of the inner layer, intermediate layer and outer layer.
- the layer (II) other than the layer (I) of the laminate preferably has an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit content of 5 to 55% by weight, more preferably 18 to 45% by weight.
- a phosnium salt, 1,8-diazabicyclo (5.4) is added to either or both of the layer (I) and the layer (II) in order to bond the layer (I) and the layer (II).
- 0.0) Undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt), etc. and may contain layer (I), layer (II)
- a new layer (III) may be used as an adhesive layer.
- the layer (III) the same resin or rubber composition as the resin or rubber composition constituting the layer (II) described above can be used.
- the resin or rubber composition constituting the layer (II) described above can be used singly or in combination, and a phosnium salt, 1,8-diazabicyclo (5.4.0) Undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt) and the like may be contained.
- a phosnium salt 1,8-diazabicyclo (5.4.0) Undecene-7 salt (DBU salt), 1,5-diazabicyclo (4.3.0) -nonene-5 salt (DBN salt) and the like may be contained.
- the thickness of the layer (I) is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm.
- the thickness of layers other than the layer (I) is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm.
- the hose of the present invention is formed by forming into a cylindrical shape using an extruder or the like and crosslinking it. Since the crosslinkable nitrile copolymer rubber composition of the present invention has the property that mandrel cracks are unlikely to occur, it can be produced using a mandrel.
- the cross-linkable nitrile copolymer rubber composition of the present invention is formed into a cylindrical shape, and the obtained cylindrical shape It can be produced by fixing the shape by inserting a mandrel into the molded body and crosslinking the crosslinkable nitrile copolymer rubber composition.
- the hose has a multilayer structure including the crosslinked product of the present invention, a layer other than the layer composed of the crosslinked nitrile copolymer rubber composition of the present invention and the crosslinked product of the present invention is formed.
- the resin or rubber composition to be formed is formed into a cylindrical shape while being laminated, and the shape is fixed by inserting a mandrel into the obtained cylindrical laminated molded body, and a crosslinkable nitrile copolymer rubber composition is obtained. It can be produced by crosslinking.
- the rubber cross-linked product of the present invention includes seal members such as packings, gaskets, O-rings and oil seals; hoses such as oil hoses, fuel hoses, inlet hoses, gas hoses, brake hoses, refrigerant hoses; It is suitable for.
- seal members such as packings, gaskets, O-rings and oil seals
- hoses such as oil hoses, fuel hoses, inlet hoses, gas hoses, brake hoses, refrigerant hoses
- gas of the gas hose include air, nitrogen, oxygen, hydrogen, carbon dioxide, carbon monoxide, methane, ethane, propane, dimethyl ether, and LPG.
- the nitrile copolymer latex composition of the present invention provides the nitrile copolymer rubber composition of the present invention and is itself useful as a latex composition for coating.
- cover when using as a latex composition for coating
- a mold made of porcelain, glass or metal is immersed in the latex composition of the present invention, and then Dip-molding method in which the surface adhesion layer is heated and fixed by pulling up; roll impregnation method in which the fiber is impregnated with the latex composition of the present invention, squeezed with a roll, etc., heated and fixed; sprayed with the latex composition of the present invention on the fiber Spray impregnation method by spraying and fixing with, and a coating method in which the latex composition of the present invention is applied to the surface of a rubber-coated object and heated and fixed.
- the solid content concentration is preferably 15 to 40% by weight, more preferably 25 to 35% by weight.
- the solid content concentration of the latex composition varies depending on the type of fiber and the target adhesion amount, but is preferably 5 to 30% by weight. More preferably, it is 10 to 30% by weight. Since the penetration of the latex composition into the fiber is affected by the surface tension of the latex composition, the surface tension is preferably adjusted to 20 to 50 mN / m. Examples of the method for adjusting the surface tension of the latex composition include a method of adding an anionic surfactant or a nonionic surfactant.
- the nitrile copolymer latex composition of the present invention when used in a coating method, for example, it is coated on a substrate such as paper using a coating machine, and thereafter is heated with a hot air dryer. Dry to form a coating layer on the substrate.
- a coating machine include a blade coater, a roll coater, a curtain coater, a rod coater, and an ener knife knife coater.
- the solid content concentration of the latex composition is not particularly limited and is generally 10 to 60% by weight although it varies depending on the coating machine used.
- the drying conditions after coating are generally about 100 to 170 ° C. and about several tens of seconds.
- Mooney viscosity Mooney viscosity (ML 1 + 4 , 100 ° C.) was measured according to JIS K6300.
- a crosslinkable nitrile copolymer rubber composition (crosslinkable hydrogenated nitrile copolymer rubber composition) is placed in a 15 cm long, 15 cm wide, 0.2 cm deep mold and press molded at 160 ° C. for 20 minutes while applying pressure.
- a sheet-like rubber cross-linked product was obtained.
- JIS K6251 using a test piece punched out in dumbbell shape No. 3, the tensile strength, elongation and 100% tensile stress of the rubber cross-linked product are obtained.
- JIS K6253 The hardness of the rubber cross-linked product was measured using a durometer hardness tester type A, respectively.
- Gasoline permeability coefficient Prepare the same sheet-like rubber cross-linked product used for evaluation of the above-mentioned normal physical properties, and use "mixture of isooctane, toluene and ethanol in a weight ratio of 2: 2: 1" as fuel oil.
- the gasoline permeability coefficient was measured by the aluminum cup method. Specifically, 50 ml of the above fuel oil is put into a 100 ml capacity aluminum cup, and a sheet-like rubber cross-linked product is placed on the cup, which is then covered with a fastener and a sheet-like rubber cross-linked product.
- the brittle temperature was measured in accordance with JIS K6261 using the same sheet-like rubber cross-linked product used for the evaluation of the normal state physical properties.
- Extrudable crosslinkable nitrile copolymer rubber composition (including the case of “crosslinkable hydrogenated nitrile copolymer rubber composition”) was placed in a screw-type extruder set at a cylinder temperature of 60 ° C. and a head temperature of 80 ° C.
- the extrusion processability was evaluated by supplying and evaluating the smoothness of the surface skin of the obtained rubber cross-linked product through a die defined in ASTM D2230, Method A.
- Sour Gasoline Resistance Test Prepare the same sheet-like rubber cross-linked product used for evaluation of the above-mentioned normal physical properties, and use it as a fuel oil "mixture of isooctane, toluene and ethanol in a weight ratio of 2: 2: 1".
- a test oil in which dilauroyl peroxide is dissolved at a concentration of 3% by weight, the sheet is heated at a temperature of 40 ° C. for 500 hours (the test oil is replaced with a new oil at a rate of twice per 168 hours).
- the rubber cross-linked product was immersed.
- a sample after 500 hours was subjected to a tensile test in accordance with JIS K6253, and the presence or absence of cracks was observed during elongation by the tensile test to evaluate the sour gasoline resistance.
- Production Example 1 (Production of latex of nitrile copolymer rubber (A1)) A reaction vessel was charged with 240 parts of water, 75.7 parts of acrylonitrile and 2.5 parts of sodium dodecylbenzenesulfonate (emulsifier), and the temperature was adjusted to 5 ° C.
- a third-stage polymerization reaction was performed. Thereafter, when the polymerization conversion rate with respect to all charged monomers reached 75% by weight, 0.3 part of hydroxylamine sulfate and 0.2 part of potassium hydroxide were added to terminate the polymerization reaction. After the reaction was stopped, the contents of the reaction vessel were heated to 70 ° C., and unreacted monomers were recovered by steam distillation under reduced pressure to obtain a latex of nitrile copolymer rubber (A1) (solid content: 24% by weight). )
- a part of the latex was sampled, coagulated with a large amount of methanol, filtered and dried to obtain a nitrile copolymer rubber (A1).
- the content ratio of each monomer unit constituting the obtained nitrile copolymer rubber (A1) was measured using an FT-NMR apparatus (JNM-EX400WB) manufactured by JEOL Ltd., and acrylonitrile monomer unit 50 % By weight and 50% by weight of 1,3-butadiene units.
- the Mooney viscosity (polymer Mooney viscosity) of the nitrile copolymer rubber (A1) was 75.
- Production Example 2 (Production of latex of nitrile copolymer rubber (A2))
- the monomer used in the first stage of the emulsion polymerization was used in addition to 2.2 parts of 2-vinylpyridine.
- a latex of nitrile copolymer rubber (A2) (solid content: 24% by weight) was obtained.
- the content ratio of each monomer unit constituting the obtained nitrile copolymer rubber (A2) was measured in the same manner as in Production Example 1. As a result, 50% by weight of acrylonitrile monomer unit and 2% by weight of 2-vinylpyridine were measured. %, And 1,3-butadiene unit was 48% by weight.
- the Mooney viscosity (polymer Mooney viscosity) of the nitrile copolymer rubber (A2) was 73.
- Production Example 3 (Production of latex of hydrogenated nitrile copolymer rubber (A3)) About the latex of the nitrile copolymer rubber (A1) obtained in Production Example 1, a palladium catalyst (1 wt% acetic acid was added to the reactor so that the palladium content was 1000 ppm with respect to the dry rubber weight contained in the latex. A solution obtained by mixing a palladium acetone solution and an equal weight of ion-exchange water) is added, and a hydrogenation reaction is performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a latex of hydrogenated nitrile copolymer rubber (A3). It was.
- the content ratio of each monomer unit constituting the obtained hydrogenated nitrile copolymer rubber (A3) was measured in the same manner as in Production Example 1. As a result, 50% by weight of acrylonitrile monomer unit, 1,3- The total amount of butadiene units and saturated butadiene units was 50% by weight.
- the hydrogenated nitrile copolymer rubber (A3) had a Mooney viscosity (polymer Mooney viscosity) of 155 and an iodine value of 20.
- Production Example 4 (Production of latex of hydrogenated nitrile copolymer rubber (A4)) About the latex of the nitrile copolymer rubber (A2) obtained in Production Example 2, a palladium catalyst (1 wt% acetic acid was added to the reactor so that the palladium content was 1000 ppm with respect to the weight of the dry rubber contained in the latex. A solution obtained by mixing a palladium acetone solution and an equal weight of ion-exchanged water) and carrying out a hydrogenation reaction at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a latex of hydrogenated nitrile copolymer rubber (A4). It was.
- the content ratio of each monomer unit constituting the obtained hydrogenated nitrile copolymer rubber (A4) was measured in the same manner as in Production Example 1. As a result, 50% by weight of acrylonitrile monomer unit, 2-vinylpyridine 2% by weight, a total of 48% by weight of 1,3-butadiene units and saturated butadiene units.
- the hydrogenated nitrile copolymer rubber (A4) had a Mooney viscosity (polymer Mooney viscosity) of 163 and an iodine value of 30.
- Production Example 5 (Production of vinyl chloride resin latex) A pressure-resistant reaction vessel was charged with 120 parts of water, 0.8 part of sodium lauryl sulfate and 0.06 part of potassium persulfate, and after repeated vacuum degassing twice, 100 parts of vinyl chloride was added and heated while stirring. The emulsion polymerization was carried out at 47 ° C. After the polymerization conversion reached 90%, it was cooled to room temperature to remove unreacted monomers. The concentration of the obtained vinyl chloride resin latex was 41% by weight. The average particle size of the vinyl chloride resin was 0.3 ⁇ m, the average degree of polymerization according to JIS K6721 was 1,300, and the glass transition temperature was 80 ° C.
- Production Example 6 (Production of latex of acrylic resin)
- 150 parts of ion exchange water, 2 parts of sodium octyl sulfate, 0.3 part of ammonium persulfate (polymerization initiator), 80 parts of methyl methacrylate, 20 parts of acrylonitrile and t-dodecyl mercaptan (Molecular weight adjusting agent) 0.05 part was added, emulsion polymerization was started at a temperature of 80 ° C. with stirring, and the reaction was stopped after 5 hours to obtain a latex.
- the resulting acrylic resin latex had a concentration of 39% by weight and a polymerization conversion rate of 98% by weight.
- the average particle diameter of the acrylic resin was 0.2 ⁇ m, the number average molecular weight was 600,000, and the glass transition temperature was 103 ° C.
- Example 1 As a plate-like filler (B), 100 parts of purified bentonite (trade name “Bengel”, manufactured by Hojun Co., Ltd., swelling power: 35, TI value in case of 5% slurry: 2.5) is added to 1995 parts of distilled water. In the presence of 5 parts of sodium polyacrylate, the mixture was vigorously stirred to obtain a plate-like filler aqueous dispersion having a solid content concentration of 5%.
- bentonite trade name “Bengel”, manufactured by Hojun Co., Ltd., swelling power: 35, TI value in case of 5% slurry: 2.5
- the plate-like filler aqueous dispersion prepared above was added and dispersed.
- the aqueous dispersion of the plate-like filler is 20 parts of the plate-like filler (B) with respect to 100 parts of the latex solid content (nitrile copolymer rubber amount) of the nitrile copolymer rubber (A1).
- a solid content (nitrile copolymer rubber and plate-like filler) concentration of 15% was obtained to obtain a nitrile copolymer latex composition.
- the obtained nitrile copolymer latex composition is an aqueous solution containing calcium chloride (coagulant) in an amount of 4% by weight with respect to the amount of nitrile copolymer rubber (A1) in the latex composition.
- coagulant calcium chloride
- 10% dilute sulfuric acid is added as needed so that the pH of the aqueous solution during coagulation becomes 2, and the pH is adjusted while pouring and stirring to solidify the nitrile copolymer rubber (A1), and plate filling
- a crumb consisting of a mixture of agent (B) was produced.
- the obtained crumb was separated by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain a nitrile copolymer rubber composition.
- the aspect ratio of the purified bentonite (trade name “Bengel”) was 280 as measured by an atomic force microscope.
- nitrile copolymer rubber (A1) in the nitrile copolymer rubber composition 100 parts of nitrile copolymer rubber (A1) in the nitrile copolymer rubber composition, 2 parts of FEF carbon black (Seast SO, manufactured by Tokai Carbon Co., Ltd.), as a crosslinking aid 5 parts of zinc white and 1 part of stearic acid were added and mixed at 50 ° C. Then, this mixture was transferred to a roll and 0.5 parts of 325 mesh sulfur as a crosslinking agent and 1.5 parts of tetramethylthiuram disulfide (trade name “Noxeller TT”, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and N-cyclohexyl were used.
- FEF carbon black Seast SO, manufactured by Tokai Carbon Co., Ltd.
- Example 2 Except for using purified bentonite (trade name “Bengelbright 23”, manufactured by Hojun Co., Ltd., swelling power: 27, TI value in case of 5% slurry: 2.3) as the plate-like filler (B).
- B purified bentonite
- Each composition was prepared in the same manner as in Example 1 and evaluated in the same manner.
- Example 3 Except for using purified bentonite (trade name “Bengel HVP”, manufactured by Hojun Co., Ltd., swelling power: 42, TI value in case of 5% slurry: 4.8) as the plate-like filler (B).
- B the plate-like filler
- Each composition was prepared in the same manner as 1 and evaluated in the same manner. In addition, it was 285 as a result of measuring the aspect-ratio of refined bentonite (brand name "Bengel HVP”) with the atomic force microscope. The results are shown in Table 1.
- Example 4 Example except that refined bentonite (trade name “Bengel HV”, manufactured by Hojun Co., Ltd., swelling power: 50, TI value in the case of 5% slurry: 4.0) was used as the plate-like filler (B). Each composition was prepared in the same manner as 1 and evaluated in the same manner. In addition, it was 295 as a result of measuring the aspect-ratio of refined bentonite (brand name "Bengel HV”) with the atomic force microscope. The results are shown in Table 1.
- refined bentonite trade name “Bengel HV”, manufactured by Hojun Co., Ltd., swelling power: 50, TI value in the case of 5% slurry: 4.0
- Example 5 Except that synthetic mica (trade name “DMA-350”, manufactured by Topy Industries, swelling power: 25, TI value in case of 5% slurry: 2.3) was used as the plate-like filler (B). Each composition was prepared in the same manner as in Example 1 and evaluated in the same manner. The aspect ratio of the synthetic mica (trade name “DMA-350”) measured with an atomic force microscope was 1000. The results are shown in Table 1.
- Example 6 Each composition was prepared in the same manner as in Example 1 except that the latex of the nitrile copolymer rubber (A2) produced in Production Example 2 was used instead of the latex of the nitrile copolymer rubber (A1). The evaluation was made in the same manner. The results are shown in Table 1.
- Example 7 When preparing the crosslinkable nitrile copolymer rubber composition, the latex of the vinyl chloride resin obtained in Production Example 5 (45 parts of vinyl chloride resin) was added to 100 parts of the nitrile copolymer rubber (A1). Further, a nitrile copolymer rubber composition was obtained in the same manner as in Example 1 except that 35 parts of di (butoxyethoxyethyl) adipate as a plasticizer (C) was further added. The obtained nitrile copolymer rubber composition was kneaded with a roll at 170 ° C. for 5 minutes, and then a crosslinkable nitrile copolymer rubber composition was prepared in the same manner as in Example 1 and evaluated in the same manner.
- di (butoxyethoxyethyl) adipate (trade name “Adekasizer RS-107”, manufactured by Asahi Denka Kogyo Co., Ltd.) is a 50 wt% aqueous emulsion of di (butoxyethoxyethyl) adipate. 2% by weight of potassium oleate as an emulsifier was added to di (butoxyethoxyethyl) adipate and mixed under strong stirring to prepare an aqueous dispersion and an aqueous dispersion. The results are shown in Table 1.
- Example 8 When preparing the crosslinkable nitrile copolymer rubber composition, the latex of the acrylic resin obtained in Production Example 6 (45 parts of acrylic resin) was further added to 100 parts of the nitrile copolymer rubber (A1). In the same manner as in Example 1 except that 35 parts of di (butoxyethoxyethyl) adipate (trade name “Adeka Sizer RS-107”, manufactured by Asahi Denka Kogyo Co., Ltd.) as a plasticizer (C) was further added. Each composition was prepared and evaluated in the same manner. Incidentally, di (butoxyethoxyethyl) adipate as the plasticizer (C) was added as an aqueous dispersion in the same manner as in Example 7. The results are shown in Table 1.
- Example 9 When preparing the nitrile copolymer rubber composition, 100 parts of the nitrile copolymer rubber (A1) is used with di (butoxyethoxyethyl) adipate as a plasticizer (C) (trade name “Adekaizer RS- 107 ”(manufactured by Asahi Denka Kogyo Co., Ltd.) Each composition was prepared and evaluated in the same manner as in Example 1 except that 10 parts were further added. Incidentally, di (butoxyethoxyethyl) adipate as the plasticizer (C) was added as an aqueous dispersion in the same manner as in Example 7. The results are shown in Table 1.
- Comparative Example 2 Example except that purified montmorillonite (trade name “Kunipia F”, manufactured by Kunimine Industries, swelling force: 65, TI value when 5% slurry was used: 5.4) was used as the plate-like filler (B). Each composition was prepared in the same manner as 1 and evaluated in the same manner. As a result of measuring the aspect ratio of the purified bentonite (trade name “Kunipia F”) with an atomic force microscope, it was 300. The results are shown in Table 1.
- Comparative Example 5 Each composition was prepared in the same manner as in Comparative Example 3 except that the latex of the nitrile copolymer rubber (A2) produced in Production Example 2 was used instead of the latex of the nitrile copolymer rubber (A1). The evaluation was made in the same manner. The results are shown in Table 1.
- Comparative Example 6 Example except that refined bentonite (trade name “Bengel A”, manufactured by Hojun Co., Ltd., swelling power: 42, TI value in the case of 5% slurry: 7.5) was used as the plate-like filler (B). Each composition was prepared in the same manner as 1 and evaluated in the same manner. The aspect ratio of the purified bentonite (trade name “Bengel A”) was 290 as measured by an atomic force microscope. The results are shown in Table 1.
- Example 10 Each composition was prepared in the same manner as in Example 1, except that the latex of hydrogenated nitrile copolymer rubber (A3) produced in Production Example 3 was used instead of the latex of nitrile copolymer rubber (A1). Prepared and evaluated in the same manner. The results are shown in Table 2.
- Example 11 Each composition was prepared in the same manner as in Example 1 except that the latex of hydrogenated nitrile copolymer rubber (A4) produced in Production Example 4 was used instead of the latex of nitrile copolymer rubber (A1). Prepared and evaluated in the same manner. The results are shown in Table 2.
- Example 12 In the same manner as in Example 6, a crumb comprising a mixture of the nitrile copolymer rubber (A2) and the plate-like filler (B) was obtained. The obtained crumb was separated by filtration, washed with water, and then reduced in pressure at 60 ° C.
- this mixture was transferred to a roll and 0.5 parts of 325 mesh sulfur as a cross-linking agent, 1.5 parts of tetramethylthiuram disulfide (trade name “Noxeller TT”, manufactured by Ouchi Shinsei Chemical Co., Ltd.), and N-cyclohexyl -2-Benzothiazolylsulfenamide (trade name “Noxeller CZ”, manufactured by Ouchi Shinsei Chemical Co., Ltd., crosslinking accelerator) 1.5 parts is added and kneaded at 50 ° C. to form a crosslinkable nitrile copolymer rubber.
- a composition was prepared.
- Example 13 As a particulate filler (D), instead of 15 parts of untreated calcium carbonate (Silver W), calcium carbonate having a surface treated with a fatty acid (trade name “Shiraka Hana CC”, manufactured by Shiraishi Kogyo Co., Ltd., aspect ratio 1.0 A crosslinkable nitrile copolymer rubber composition was prepared in the same manner as in Example 12 except that 20 parts of an average particle size of 0.05 ⁇ m and a specific surface area of 26 m 2 / g were used. Evaluation was performed. The results are shown in Table 3.
- Example 14 As a particulate filler (D), instead of 15 parts of untreated calcium carbonate (Silver W), calcium carbonate whose surface was treated with rosin acid (trade name “Shiraka Hana O”, manufactured by Shiraishi Kogyo Co., Ltd., aspect ratio 1. 0, average particle size 0.03 ⁇ m, specific surface area 51 m 2 / g) except that 20 parts were used, a crosslinkable nitrile copolymer rubber composition was prepared in the same manner as in Example 12, and the same as in Example 12. Evaluation was performed. The results are shown in Table 3.
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Abstract
Description
好ましくは、前記ニトリル共重合体ゴム(A)が、共役ジエン単量体単位をさらに有し、前記ニトリル共重合体ゴム(A)中における、前記共役ジエン単量体単位の含有割合が、10~79.9重量%である。
好ましくは、前記板状充填剤(B)のアスペクト比が30~2,000である。
好ましくは、前記板状充填剤(B)が、スメクタイト類である。
好ましくは、前記ニトリル共重合体ラテックス組成物は、可塑剤(C)をさらに含有する。
好ましくは、前記ニトリル共重合体ゴム(A)が、炭素-炭素不飽和結合部分のうち少なくとも一部が水素化された水素化ニトリル共重合体ゴムである。
好ましくは、前記ニトリル共重合体ラテックス組成物は、前記ニトリル共重合体ゴム(A)100重量部に対して、10~150重量部の塩化ビニル樹脂および/またはアクリル樹脂をさらに含有する。
好ましくは、前記ニトリル共重合体ゴム組成物は、該ニトリル共重合体ゴム組成物中のニトリル共重合体ゴム(A)100重量部に対して、10~150重量部の塩化ビニル樹脂および/またはアクリル樹脂をさらに含有する。
好ましくは、前記ニトリル共重合体ゴム組成物は、アスペクト比が1以上30未満である粒子状充填剤(D)をさらに含有し、前記板状充填剤(B)と前記粒子状充填剤(D)との含有比率が、重量比で、「前記板状充填剤(B)/前記粒子状充填剤(D)」=0.01~30である。
本発明によれば、上記いずれかのニトリル共重合体ゴム組成物に架橋剤を加えてなる架橋性ニトリル共重合体ゴム組成物が提供される。
本発明によれば、上記架橋性ニトリル共重合体ゴム組成物を架橋してなるゴム架橋物が提供される。
好ましくは、上記ゴム架橋物がホースである。
まず、本発明で用いるニトリル共重合体ゴム(A)のラテックスを構成する、ニトリル共重合体ゴム(A)について説明する。
ニトリル共重合体ゴム(A)は、少なくともα,β-エチレン性不飽和ニトリル単量体単位20~70重量%を有するゴムである。
ニトリル共重合体ゴム(A)のラテックスの製造方法としては、特に限定されず、上記したニトリル共重合体ゴム(A)を構成する各単量体を共重合できる方法であれば良いが、たとえば、ドデシルベンゼンスルホン酸ナトリウムなどの乳化剤を用いて約50~1,000nmの平均粒径を有する共重合体のラテックスを得る乳化重合法や、ポリビニルアルコールなどの分散剤を用いて約0.2~200μmの平均粒径を有する共重合体のラテックスを得る懸濁重合法(微細懸濁重合法も含む)などを好適に用いることができる。これらのなかでも、重合反応制御が容易なことから乳化重合法がより好ましい。
なお、以下において、適宜、α,β-エチレン性不飽和ニトリル単量体を「単量体(m1)」とし、共役ジエン単量体を「単量体(m2)」とし、カチオン性単量体および/またはカチオンを形成可能な単量体を「単量体(m3)」とする。
また、重合反応を停止する重合転化率が低すぎると、未反応の単量体の回収が非常に困難になる。一方、高すぎると、得られるゴム架橋物の常態物性が悪化する傾向がある。
本発明のニトリル共重合体ラテックス組成物は、上述のニトリル共重合体ゴム(A)のラテックスに、水に対する膨潤力が15~55(ml/2g)であり、かつ、水媒体に対して5重量%の濃度で混合してスラリーとした場合におけるチクソトロピックインデックス(TI値)が1~6である板状充填剤(B)を加えてなるものである。なお、水媒体としては、イオン交換水を用いる。
すなわち、まず、メスシリンダーにイオン交換水100mlを入れ、次いで十分に乾燥した状態の板状充填剤(B)2gを、メスシリンダーの内壁に付着しないように、約10回に分けて投入する。そして、24時間静置後、メスシリンダーの下部に堆積した堆積物(水で膨潤した板状充填剤(B))の容積(ml)を測定し、これを板状充填剤(B)の水に対する膨潤力(単位は、ml/2g)とすることができる。
すなわち、まず、イオン交換水中に板状充填剤(B)を5%重量濃度になるように添加して強攪拌し、24時間室温で放置することにより、板状充填剤(B)のスラリーを調製する。そして、調製したスラリーの、ローターの回転数6rpmで測定したB型粘度の値と、ローターの回転数60rpmで測定したB型粘度の値とを求め、これらの比(6rpmの粘度/60rpmの粘度)から求められる。なお、TI値は、スラリーのチクソトロピー性を示す一般的指標であり、たとえば、回転数6rpm(静かな攪拌状態)では、水で膨潤したスラリーが柔らかいゼリー状のため粘度が高くなる一方で、回転数60rpm(激しい攪拌状態)では、上記柔らかいゼリー状態が破壊されることにより、粘度が低下することとなる。なお、TI値が大きいほど、チクソトロピー性は大きくなる。
カップリング剤の添加方法は特に限定されないが、例えば、板状充填剤(B)に添加して混合した後に、該板状充填剤(B)を水性分散液とする方法などが挙げられる。
本発明のニトリル共重合体ラテックス組成物におけるカップリング剤の含有量は、ニトリル共重合体ゴム(A)100重量部に対して、好ましくは30重量部以下であり、より好ましくは20重量部以下である。
本発明に好適に用いられる塩化ビニル樹脂は、樹脂を構成する主構成単量体が塩化ビニルであって、該単量体単位の含有量が好ましくは50~100重量%、より好ましくは60~100重量%、特に好ましくは70~100重量%である。また、本発明に好適に用いられるアクリル樹脂は、樹脂を構成する主構成単量体が(メタ)アクリル酸アルキルエステルであって、該単量体単位の含有量が好ましくは50~100重量%、より好ましくは60~100重量%、特に好ましくは70~100重量%である。アルキル基の炭素数は、好ましくは1~20、より好ましくは1~18、特に好ましくは1~10である。
塩化ビニル樹脂とアクリル樹脂の重合度または分子量は、特に限定されないが、塩化ビニル樹脂では、JIS K6721に規定の溶液粘度法による平均重合度が、好ましくは400~3,000、より好ましくは600~2,000である。アクリル樹脂では、テトラヒドロフランを溶剤とするゲルパーミエーションクロマトグラフィ(GPC)による標準ポリスチレン換算の数平均分子量が、好ましくは10,000~7,000,000、より好ましくは100,000~2,000,000である。
本発明のニトリル共重合体ゴム組成物は、上記ニトリル共重合体ラテックス組成物を凝固し、必要に応じて水洗・乾燥することにより得ることができる。
また、粒子状充填剤(D)を配合する場合には、ニトリル共重合体ゴム(A)のラテックスに、粒子状充填剤(D)以外の成分(板状充填剤(B)、必要に応じて添加される可塑剤(C)、必要に応じて添加されるカップリング剤、必要に応じて添加されるアクリル樹脂および/または塩化ビニル樹脂)を含有させた後に凝固・乾燥し、次いで、粒子状充填剤(D)を配合して、ロールやバンバリーミキサー等の混錬機で混錬して得ることもできる。
架橋剤は、ニトリル基含有共重合体ゴムの架橋剤として通常使用されるものであればよく、特に限定されない。代表的な架橋剤としては、ニトリル共重合体ゴム(A)の不飽和結合間を架橋する硫黄系架橋剤または有機過酸化物架橋剤が挙げられる。これらは一種単独でまたは複数種併せて用いることができる。これらのなかでも、硫黄系架橋剤が好ましい。
本発明のゴム架橋物は、上記架橋性ニトリル共重合体ゴム組成物を架橋してなる。
本発明の架橋性ニトリル共重合体ゴム組成物を架橋する際には、製造する成形品(ゴム架橋物)の形状に対応した成形機、たとえば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、次いで架橋反応させることにより架橋物の形状を固定化する。架橋を行う際には、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10~200℃、好ましくは25~120℃である。架橋温度は、通常、100~200℃、好ましくは130~190℃であり、架橋時間は、通常、1分~24時間、好ましくは2分~1時間である。
すなわち、ホースを、本発明の架橋物のみからなる単層のものとする場合には、まず、本発明の架橋性ニトリル共重合体ゴム組成物を筒状に成形し、得られた筒状の成形体にマンドレルを挿入することにより形状を固定し、架橋性ニトリル共重合体ゴム組成物を架橋させることにより製造することができる。
あるいは、ホースを、本発明の架橋物を含む多層のものとする場合には、本発明の架橋性ニトリル共重合体ゴム組成物と、本発明の架橋物からなる層以外の層を形成することとなる樹脂又はゴム組成物と、を積層させながら筒状に成形し、得られた筒状の積層成形体にマンドレルを挿入することにより形状を固定し、架橋性ニトリル共重合体ゴム組成物を架橋させることにより製造することができる。
ムーニー粘度(ML1+4、100℃)は、JIS K6300に準拠して測定した。
架橋性ニトリル共重合体ゴム組成物(架橋性水素化ニトリル共重合体ゴム組成物)を縦15cm、横15cm、深さ0.2cmの金型に入れ、加圧しながら160℃で20分間プレス成形してシート状のゴム架橋物を得た。得られたシート状のゴム架橋物を用いてJIS K6251に従い、ダンベル状3号形で打ち抜いた試験片を用いてゴム架橋物の引張強さ、伸びおよび100%引張応力を、また、JIS K6253に従い、デュロメータ硬さ試験機タイプAを用いてゴム架橋物の硬さを、それぞれ測定した。
上記常態物性の評価に用いたシート状のゴム架橋物と同様のものを準備し、燃料油として「イソオクタンとトルエンとエタノールを重量比2:2:1で混合したもの」を使用して、アルミカップ法によりガソリン透過係数を測定した。具体的には、100ml容量のアルミニウム製のカップに、上記燃料油を50ml入れ、その上にシート状のゴム架橋物をのせ、これで蓋をして、締め具で、シート状のゴム架橋物によりアルミカップ内外を隔てる面積が25.50cm2になるように調整し、該アルミカップを23℃の恒温槽内にて、放置し、24時間毎に重量測定することにより24時間毎の油の透過量を測定し、その最大量をガソリン透過係数とするものである(単位:g・mm/m2・day)。
なお、ガソリン透過係数は低い程、好ましい。
上記常態物性の評価に用いたシート状のゴム架橋物と同様のものを用い、JIS K6261に従い、脆化温度を測定した。
押し出し加工性
架橋性ニトリル共重合体ゴム組成物(「架橋性水素化ニトリル共重合体ゴム組成物」の場合を含む)を、シリンダー温度60℃、ヘッド温度80℃に設定したスクリュー型押出機に供給し、ASTM D2230のA法に定められたダイを通し、得られたゴム架橋物の表面肌の平滑性を評価することにより、押し出し加工性の評価を行った。
上記常態物性の評価に用いたシート状のゴム架橋物と同様のものを準備し、燃料油としての「イソオクタンとトルエンとエタノールを重量比2:2:1で混合したもの」にジラウロイルペルオキシドを3重量%の濃度で溶解させた試験油中に、温度40℃、500時間(試験油は168時間当たり2回の割合で新規のものと交換した。)の条件にて、シート状のゴム架橋物を浸漬させた。そして、500時間経過後のサンプルについて、JIS K6253に準拠して、引張試験を行い、引張試験による伸長時にクラックの発生の有無を観察し、耐サワーガソリン性を評価した。
反応容器に、水240部、アクリロニトリル75.7部およびドデシルベンゼンスルホン酸ナトリウム(乳化剤)2.5部を仕込み、温度を5℃に調整した。次いで、気相を減圧して十分に脱気してから、1,3-ブタジエン22部、重合開始剤であるパラメンタンヒドロペルオキシド0.06部、エチレンジアミン四酢酸ナトリウム0.02部、硫酸第一鉄(7水塩)0.006部およびホルムアルデヒドスルホキシル酸ナトリウム0.06部、ならびに連鎖移動剤のt-ドデシルメルカプタン1部を添加して乳化重合の1段目の反応を開始した。反応開始後、仕込み単量体に対する重合転化率が、それぞれ42重量%、60重量%に達した時点で、反応容器に1,3-ブタジエンをそれぞれ12部、12部追加して2段目、3段目の重合反応を行った。その後、仕込み全単量体に対する重合転化率が75重量%に達した時点でヒドロキシルアミン硫酸塩0.3部および水酸化カリウム0.2部を添加して重合反応を停止させた。反応停止後、反応容器の内容物を70℃に加温し、減圧下に水蒸気蒸留により未反応の単量体を回収してニトリル共重合体ゴム(A1)のラテックス(固形分:24重量%)を得た。
製造例1において、乳化重合1段目の反応の仕込み単量体として、アクリロニトリル75.7部および1,3-ブタジエン22部に加えて、2-ビニルピリジン2.2部をさらに使用した以外は、製造例1と同様にして、ニトリル共重合体ゴム(A2)のラテックス(固形分:24重量%)を得た。
製造例1において得られたニトリル共重合体ゴム(A1)のラテックスについて、該ラテックスに含有される乾燥ゴム重量に対してパラジウム含有量が1000ppmになるように反応器にパラジウム触媒(1重量%酢酸パラジウムアセトン溶液と等重量のイオン交換水を混合した溶液)を添加して、水素圧3MPa、温度50℃で6時間水素添加反応を行い、水素化ニトリル共重合体ゴム(A3)のラテックスを得た。
製造例2において得られたニトリル共重合体ゴム(A2)のラテックスについて、該ラテックスに含有される乾燥ゴム重量に対してパラジウム含有量が1000ppmになるように反応器にパラジウム触媒(1重量%酢酸パラジウムアセトン溶液と等重量のイオン交換水を混合した溶液)を添加して、水素圧3MPa、温度50℃で6時間水素添加反応を行い、水素化ニトリル共重合体ゴム(A4)のラテックスを得た。
耐圧反応容器に、水120部、ラウリル硫酸ナトリウム0.8部および過硫酸カリウム0.06部を仕込んで、減圧脱気を2回くり返した後、塩化ビニルを100部仕込み、攪拌しつつ加温して47℃にて乳化重合を行った。重合転化率が90%に達した後、室温に冷却して未反応単量体を除去した。得られた塩化ビニル樹脂ラテックスの濃度は41重量%であった。塩化ビニル樹脂の平均粒径は0.3μmであり、JIS K6721による平均重合度は1,300、ガラス転移温度は80℃であった。
温度計、撹拌装置を備えた反応器に、イオン交換水150部、オクチル硫酸ナトリウム2部、過硫酸アンモニウム(重合開始剤)0.3部、メタクリル酸メチル80部、アクリロニトリル20部およびt-ドデシルメルカプタン(分子量調整剤)0.05部を入れ、攪拌しながら温度80℃にて乳化重合を開始し、5時間後に反応を停止してラテックスを得た。得られたアクリル樹脂ラテックスの濃度は39重量%で重合転化率は98重量%であった。アクリル樹脂の平均粒径は0.2μmであり、数平均分子量は600,000、ガラス転移温度は103℃であった。
板状充填剤(B)として精製ベントナイト(商品名「ベンゲル」、株式会社ホージュン製、膨潤力:35、5%スラリーとした場合のTI値:2.5)100部を、蒸留水1995部に、ポリアクリル酸ナトリウム5部の存在下に添加して強攪拌し、固形分濃度5%の板状充填剤水性分散液を得た。
そして、得られたクラムを濾別、水洗した後、60℃で減圧乾燥してニトリル共重合体ゴム組成物を得た。なお、精製ベントナイト(商品名「ベンゲル」)のアスペクト比を原子間力顕微鏡で測定した結果、280であった。
板状充填剤(B)として精製ベントナイト(商品名「ベンゲルブライト 23」、株式会社ホージュン製、膨潤力:27、5%スラリーとした場合のTI値:2.3)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、精製ベントナイト(商品名「ベンゲルブライト 23」)のアスペクト比を原子間力顕微鏡で測定した結果、260であった。結果を表1に示す。
板状充填剤(B)として精製ベントナイト(商品名「ベンゲル HVP」、株式会社ホージュン製、膨潤力:42、5%スラリーとした場合のTI値:4.8)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、精製ベントナイト(商品名「ベンゲル HVP」)のアスペクト比を原子間力顕微鏡で測定した結果、285であった。結果を表1に示す。
板状充填剤(B)として精製ベントナイト(商品名「ベンゲル HV」、株式会社ホージュン製、膨潤力:50、5%スラリーとした場合のTI値:4.0)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、精製ベントナイト(商品名「ベンゲル HV」)のアスペクト比を原子間力顕微鏡で測定した結果、295であった。結果を表1に示す。
板状充填剤(B)として合成マイカ(商品名「DMA-350」、トピー工業社製、膨潤力:25、5%スラリーとした場合のTI値:2.3)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、合成マイカ(商品名「DMA-350」)のアスペクト比を原子間力顕微鏡で測定した結果、1000であった。結果を表1に示す。
ニトリル共重合体ゴム(A1)のラテックスの代わりに、製造例2で製造したニトリル共重合体ゴム(A2)のラテックスを使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。結果を表1に示す。
架橋性ニトリル共重合体ゴム組成物を調製する際に、ニトリル共重合体ゴム(A1)100部に対して、製造例5で得られた塩化ビニル樹脂のラテックス(塩化ビニル樹脂は45部)をさらに添加し、可塑剤(C)としてのアジピン酸ジ(ブトキシエトキシエチル)35部をさらに加えた以外は、実施例1と同様にして、ニトリル共重合体ゴム組成物を得た。得られたニトリル共重合体ゴム組成物をロールで170℃で5分間混錬した後、実施例1と同様に架橋性ニトリル共重合体ゴム組成物を調製し、同様にして評価を行った。なお、可塑剤(C)としてのアジピン酸ジ(ブトキシエトキシエチル)(商品名「アデカサイザーRS-107」、旭電化工業社製)は、アジピン酸ジ(ブトキシエトキシエチル)の50重量%水性エマルジョンに、乳化剤としてのオレイン酸カリウムをアジピン酸ジ(ブトキシエトキシエチル)の2重量%添加し、強撹拌下で混合することにより水分散液とし、水分散液として添加した。結果を表1に示す。
架橋性ニトリル共重合体ゴム組成物を調製する際に、ニトリル共重合体ゴム(A1)100部に対して、製造例6で得られたアクリル樹脂のラテックス(アクリル樹脂は45部)をさらに添加し、可塑剤(C)としてのアジピン酸ジ(ブトキシエトキシエチル)(商品名「アデカサイザーRS-107」、旭電化工業社製)35部をさらに加えた以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、可塑剤(C)としてのアジピン酸ジ(ブトキシエトキシエチル)は、実施例7と同様に、水分散液として添加した。結果を表1に示す。
ニトリル共重合体ゴム組成物を調製する際に、ニトリル共重合体ゴム(A1)100部に対して、可塑剤(C)としてのアジピン酸ジ(ブトキシエトキシエチル)(商品名「アデカサイザーRS-107」、旭電化工業社製)10部をさらに添加した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、可塑剤(C)としてのアジピン酸ジ(ブトキシエトキシエチル)は、実施例7と同様に、水分散液として添加した。結果を表1に示す。
板状充填剤(B)として精製ベントナイト(商品名「ベンゲルブライト 11」、株式会社ホージュン製、膨潤力:6、5%スラリーとした場合のTI値:1.3)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、精製ベントナイト(商品名「ベンゲルブライト 11」)のアスペクト比を原子間力顕微鏡で測定した結果、35であった。結果を表1に示す。
板状充填剤(B)として精製モンモリロナイト(商品名「クニピアF」、クニミネ工業社製、膨潤力:65、5%スラリーとした場合のTI値:5.4)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、精製ベントナイト(商品名「クニピアF」)のアスペクト比を原子間力顕微鏡で測定した結果、300であった。結果を表1に示す。
板状充填剤(B)として精製ベントナイト(商品名「ベンゲル 2M」、株式会社ホージュン製、膨潤力:69、5%スラリーとした場合のTI値:5.5)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、精製ベントナイト(商品名「ベンゲル 2M」)のアスペクト比を原子間力顕微鏡で測定した結果、310であった。結果を表1に示す。
板状充填剤(B)としてベントナイト(商品名「赤城」、株式会社ホージュン製、膨潤力:5、5%スラリーとした場合のTI値:1.2)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、ベントナイト(商品名「赤城」)のアスペクト比を原子間力顕微鏡で測定した結果、30であった。結果を表1に示す。
ニトリル共重合体ゴム(A1)のラテックスの代わりに、製造例2で製造したニトリル共重合体ゴム(A2)のラテックスを使用した以外は、比較例3と同様にして、各組成物を調製し、同様にして評価を行った。結果を表1に示す。
板状充填剤(B)として精製ベントナイト(商品名「ベンゲルA」、株式会社ホージュン製、膨潤力:42、5%スラリーとした場合のTI値:7.5)を使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。なお、精製ベントナイト(商品名「ベンゲルA」)のアスペクト比を原子間力顕微鏡で測定した結果、290であった。結果を表1に示す。
ニトリル共重合体ゴム(A1)のラテックスの代わりに、製造例3で製造した水素化ニトリル共重合体ゴム(A3)のラテックスを使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。結果を表2に示す。
ニトリル共重合体ゴム(A1)のラテックスの代わりに、製造例4で製造した水素化ニトリル共重合体ゴム(A4)のラテックスを使用した以外は、実施例1と同様にして、各組成物を調製し、同様にして評価を行った。結果を表2に示す。
実施例6と同様にして、ニトリル共重合体ゴム(A2)、および板状充填剤(B)の混合物からなるクラムを得て、得られたクラムを濾別、水洗した後、60℃で減圧乾燥し、次いで、バンバリーミキサーを用いて、上記乾燥クラムに、該クラム中のニトリル共重合体ゴム(A2)100部に対して、粒子状充填剤(D)としての未処理の炭酸カルシウム(商品名「シルバーW」、白石工業社製、アスペクト比3.5、平均粒径3μm、比表面積5.5m2/g)20部、FEFカーボンブラック(商品名「シーストSO」、東海カーボン社製)2部、架橋助剤としての亜鉛華5部およびステアリン酸1部を添加して50℃にて混合した。そして、この混合物をロールに移して架橋剤である325メッシュ硫黄0.5部、テトラメチルチウラムジスルフィド(商品名「ノクセラーTT」、大内新興化学工業社製)1.5部、およびN-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド(商品名「ノクセラーCZ」、大内新興化学工業社製、架橋促進剤)1.5部を添加して50℃で混練し、架橋性ニトリル共重合体ゴム組成物を作製した。
粒子状充填剤(D)として、未処理の炭酸カルシウム(シルバーW)15部の代わりに、表面を脂肪酸で処理した炭酸カルシウム(商品名「白艶華CC」、白石工業社製、アスペクト比1.0、平均粒径0.05μm、比表面積26m2/g)20部を用いた以外は、実施例12と同様にして、架橋性ニトリル共重合体ゴム組成物を作製し、実施例12と同様に評価を行った。結果を表3に示す。
粒子状充填剤(D)として、未処理の炭酸カルシウム(シルバーW)15部の代わりに、表面をロジン酸で処理した炭酸カルシウム(商品名「白艶華O」、白石工業社製、アスペクト比1.0、平均粒径0.03μm、比表面積51m2/g)20部を用いた以外は、実施例12と同様にして架橋性ニトリル共重合体ゴム組成物を作製し、実施例12と同様に評価を行った。結果を表3に示す。
また、表3より、粒子状充填剤(D)をさらに配合した場合には、常態物性が良好で、ガソリン透過係数が小さく、脆化温度が低く、耐サワーガソリン性に優れたものとしながら、押し出し加工性を良好なものとすることが可能であった(実施例12~14)。
また、水に対する膨潤力が55(ml/2g)超である板状充填剤を用いた場合には、脆化温度が高くなり、耐寒性に劣る結果となった(比較例2,3,5)。
また、水に対する膨潤力が15~55(ml/2g)でも、5%スラリーとした場合におけるTI値が6を超える板状充填剤を用いた場合には、脆化温度が高くなり、耐寒性に劣る結果となった(比較例6)。
Claims (14)
- α,β-エチレン性不飽和ニトリル単量体単位20~70重量%を有するニトリル共重合体ゴム(A)のラテックスと、板状充填剤(B)とを含有するニトリル共重合体ラテックス組成物であって、
前記板状充填剤(B)は、水に対する膨潤力が15~55(ml/2g)であり、かつ、水媒体に対して5重量%の濃度で混合してスラリーとした場合におけるチクソトロピックインデックス(TI値)が1~6であり、
前記ニトリル共重合体ゴム(A)100重量部に対する、前記板状充填剤(B)の比率が、1~200重量部であるニトリル共重合体ラテックス組成物。 - 前記ニトリル共重合体ゴム(A)が、カチオン性単量体単位および/またはカチオンを形成可能な単量体単位をさらに有し、前記ニトリル共重合体ゴム(A)中における、前記カチオン性単量体単位および/またはカチオンを形成可能な単量体単位の含有割合が、0.1~20重量%である請求項1に記載のニトリル共重合体ラテックス組成物。
- 前記ニトリル共重合体ゴム(A)が、共役ジエン単量体単位をさらに有し、前記ニトリル共重合体ゴム(A)中における、前記共役ジエン単量体単位の含有割合が、10~79.9重量%である請求項1または2に記載のニトリル共重合体ラテックス組成物。
- 前記板状充填剤(B)のアスペクト比が30~2,000である請求項1~3のいずれかに記載のニトリル共重合体ラテックス組成物。
- 前記板状充填剤(B)が、スメクタイト類である請求項1~4のいずれかに記載のニトリル共重合体ラテックス組成物。
- 可塑剤(C)をさらに含有する請求項1~5のいずれかに記載のニトリル共重合体ラテックス組成物。
- 前記ニトリル共重合体ゴム(A)が、炭素-炭素不飽和結合部分のうち少なくとも一部が水素化された水素化ニトリル共重合体ゴムである請求項3~6のいずれかに記載のニトリル共重合体ラテックス組成物。
- 前記ニトリル共重合体ゴム(A)100重量部に対して、10~150重量部の塩化ビニル樹脂および/またはアクリル樹脂をさらに含有する請求項1~7のいずれかに記載のニトリル共重合体ラテックス組成物。
- 請求項1~8のいずれかに記載のニトリル共重合体ラテックス組成物を、凝固して得られるニトリル共重合体ゴム組成物。
- 前記ニトリル共重合体ゴム組成物中のニトリル共重合体ゴム(A)100重量部に対して、10~150重量部の塩化ビニル樹脂および/またはアクリル樹脂をさらに含有する請求項9に記載のニトリル共重合体ゴム組成物。
- 請求項9に記載のニトリル共重合体ゴム組成物に、アスペクト比が1以上30未満である粒子状充填剤(D)をさらに含有させてなるニトリル共重合体ゴム組成物であって、
前記板状充填剤(B)と前記粒子状充填剤(D)との含有比率が、重量比で、「前記板状充填剤(B)/前記粒子状充填剤(D)」=0.01~30であるニトリル共重合体ゴム組成物。 - 請求項9~11のいずれかに記載のニトリル共重合体ゴム組成物に架橋剤を加えてなる架橋性ニトリル共重合体ゴム組成物。
- 請求項12に記載の架橋性ニトリル共重合体ゴム組成物を架橋してなるゴム架橋物。
- ホースである請求項13に記載のゴム架橋物。
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