JP3513938B2 - Aqueous emulsion of nitrile group-containing highly saturated copolymer rubber and adhesive composition thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber and an adhesive composition thereof. More specifically, an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating an unsaturated nitrile-conjugated diene copolymer having an alkylthio group,
And an adhesive composition comprising an aqueous emulsion of the copolymer rubber and a resorcin-formaldehyde resin. Although the adhesive composition containing the aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber of the present invention can be widely used as an adhesive, it is particularly useful for vulcanizing adhesion between the highly saturated nitrile rubber and the fiber.

[0002]

2. Description of the Related Art Conventionally, an aqueous latex of acrylonitrile-butadiene copolymer rubber has been widely used as an adhesive because it has excellent adhesiveness to polar substances. As a nitrile rubber latex having excellent heat resistance, oil resistance, and weather resistance, the present inventors have proposed an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber represented by a hydride of an acrylonitrile-conjugated diene copolymer. It was reported (JP-A-62-201945). However, it has been difficult to say that the vulcanized product using this aqueous emulsion as an adhesive has sufficient adhesive strength and mechanical strength.

The inventors of the present invention further used, as a bonding agent, a highly saturated nitrile rubber similar to the highly saturated nitrile rubber when the highly saturated nitrile rubber and the fiber were vulcanized and bonded to form a composite. It has been reported that an adhesive composition, which is a mixture of an aqueous emulsion and a resorcinol formaldehyde resin, is useful (JP-A-63-248879 and JP-A-3-).
167239). However, when vulcanizing and bonding the adhesive composition as described above, a sulfur-based vulcanizing agent is often distributed, and in this case, both the nitrile rubber to be adhered and the nitrile rubber in the adhesive are highly saturated. Since it is a mold and has a low degree of unsaturation, vulcanization is difficult and insufficient, and it is difficult to obtain sufficient adhesive strength.

[0004]

In view of the above circumstances, an object of the present invention is to maintain good weather resistance, oil resistance and heat resistance generally possessed by a nitrile group-containing highly saturated copolymer rubber. In particular, it is an object of the present invention to provide an adhesive composition which is excellent in vulcanization adhesion suitability between a rubber compounded with a sulfur-based vulcanizing agent and a fiber and which can provide a vulcanized adhesive having good adhesive strength and mechanical strength. .

Another object of the present invention is to use a high nitrile group content which can be used as an adhesive having the above-mentioned characteristics and which is useful as a film, a binder and the like having good oil resistance, heat resistance and weather resistance. An object is to provide an aqueous emulsion of a saturated copolymer rubber.

[0006]

The above objects are achieved by the following (1) emulsion of a nitrile group-containing highly saturated copolymer rubber and (2) an adhesive composition containing the same. (1) A nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating a conjugated diene portion of an unsaturated nitrile-conjugated diene copolymer, comprising at least three tertiary carbon atoms and at least one of them. Having a C12 to C16 alkylthio group having a sulfur atom directly bonded to the tertiary carbon atom in the molecule and having a Mooney viscosity of 15 to 200,
Aqueous emulsion of nitrile group-containing highly saturated copolymer rubber having an iodine value of 80 or less.

(2) An aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber described in (1) above and resorcin-
An adhesive composition containing a formaldehyde resin.

Aqueous solution of highly saturated copolymer rubber containing nitrile group
Emulsion The aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber of the present invention has at least 3 tertiary carbon atoms and a sulfur atom directly bonded to at least 1 tertiary carbon atom therein. A particle size of a highly saturated copolymer rubber obtained by hydrogenating a conjugated diene portion of an unsaturated nitrile-conjugated diene copolymer having an alkylthio group having 12 to 16 carbon atoms in a molecule, which is obtained by emulsifying and dispersing in water, a particle size of 0. 005-0.5μ
m, and the solid content concentration is 5 to 80% by weight. The nitrile group-containing highly saturated copolymer rubber has a Mooney viscosity of 15
To 200, preferably 30 to 100, and the iodine value is 80 or less, preferably 40 or less. If the Mooney viscosity of this highly saturated copolymer rubber is less than 15, only a molded product having low strength can be obtained, and sufficient adhesive strength cannot be obtained when used as an adhesive between rubber and fiber, which is not preferable. .
When the Mooney viscosity exceeds 200, the viscosity increases, and it becomes difficult to uniformly disperse the adhesive on the fiber surface. The lower limit of the iodine value is at least 1. If the iodine value is too low, sulfur vulcanization becomes difficult.

The unsaturated nitrile-conjugated diene copolymer used for producing the nitrile group-containing highly saturated copolymer rubber used in the present invention preferably has a number average molecular weight of 35,000.
3 to 20% by weight of 0 or less components, more preferably 5 to 1
Contains 5% by weight. If the content of the component having a number average molecular weight of 35,000 or less is excessively high, the mechanical strength will decrease. If it is too low, the workability will be poor. By containing an appropriate amount of a component having a number average molecular weight of 35,000 or less, workability can be improved while maintaining good mechanical strength. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the unsaturated nitrile-conjugated diene copolymer is usually 2.3 to 5.
5, preferably 2.7-4. If Mw / Mn is excessively large, workability is poor even if an appropriate amount of a component having a number average molecular weight of 35,000 or less is contained.

The content of bonded unsaturated nitrile unit in the copolymer is 10 to 60% by weight, and particularly 20 to 50% by weight.
Is preferred. In addition, the composition distribution width of the unsaturated nitrile (ΔA
N) is usually 35 or less, preferably 3 to 20, and more preferably 5 to 15. When ΔAN is excessively large, the balance between oil resistance and cold resistance becomes poor.

The unsaturated nitrile-conjugated diene copolymer used in the present invention preferably contains substantially no halogen. Here, "substantially containing no halogen" means that the content of halogen in the copolymer is about 3 ppm or less. Substantially halogen-free is important, for example, to avoid metal corrosion problems when the copolymer is used as an adhesive component and contacted with the metal.

Specific examples of unsaturated nitriles include acrylonitrile, methacrylonitrile and α-chloroacrylonitrile. Specific examples of the conjugated diene include 1,3-butadiene, 2,3-dimethylbutadiene, isoprene and 1,3-pentadiene.

In addition to these monomers, a part of all the monomers may be replaced with another copolymerizable monomer, if necessary, within a range that does not impair the effects obtained by the present invention. It is possible. Other copolymerizable monomers include vinyl-based monomers such as styrene, α-methylstyrene and vinylpyridine; non-conjugated diene-based monomers such as vinylnorbornene, dicyclopentadiene and 1,4-hexadiene. Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isononyl acrylate, n-hexyl acrylate, 2-methyl-pentyl acrylate, n
-Acrylates and methacrylates having an alkyl group having about 1 to 18 carbon atoms such as octyl acrylate, 2-ethylhexyl acrylate, n-dotecil acrylate, methyl methacrylate, ethyl methacrylate; methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxy. An acrylate having an alkoxyalkyl group having a total carbon number of about 2 to 12, such as ethyl acrylate, ethoxypropyl acrylate, methoxyethoxy acrylate, and ethoxybutoxy acrylate; α and β-cyanoethyl acrylate, α, β and γ-cyanopropyl acrylate, cyanobutyl. 2 carbon atoms such as acrylate, cyanohexyl acrylate, cyanooctyl acrylate
An acrylate having about 12 cyanoalkyl groups;
Acrylate having a hydroxyalkyl group such as 2-hydroxyethyl acrylate and hydroxypropyl acrylate; monoethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, Dimethyl itaconate, diethyl itaconate, di-itaconate
Unsaturated dicarboxylic acid mono- and dialkyl esters such as n-butyl and di-2-ethylhexyl itaconate; further dimethylaminomethyl acrylate, diethylaminoethyl acrylate, 3- (diethylamino) -2-
Unsaturated carboxylic acid ester monomers such as hydroxypropyl acrylate and 2,3-bis (difluoroamino) propyl acrylate; trifluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, heptal orobutyl acrylate, octa Fluoropentyl acrylate, nonafluoropentyl acrylate, undecafluorohexyl acrylate, pentadecafluorooctyl acrylate, heptadecafluorononyl acrylate, heptadecafluorodecyl acrylate, nonadecafluorodecyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, octa Fluoropentyl methacrylate, dodecafluoroheptyl methacrylate Acrylates and methacrylates having fluoroalkyl groups such as pentadecafluorooctyl acrylate and hexadecafluorononyl methacrylate; fluorine-substituted benzyl acrylates and methacrylates such as fluorobenzyl acrylate, fluorobenzyl methacrylate and difluorobenzyl methacrylate; fluoroethyl vinyl ether, fluoropropyl vinyl ether, Fluoroalkyl vinyl ethers such as trifluoromethyl vinyl ether, trifluoroethyl vinyl ether, perfluoropropyl vinyl ether and perfluorohexyl vinyl ether, o- or p-trifluoromethylstyrene, vinyl pentafluorobenzoate, fluorine such as difluoroethylene and tetrafluoroethylene Inclusion Alkenyl-based monomers;
Furthermore, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate,
Examples thereof include epoxy (meth) acrylate and urethane (meth) acrylate. The amount of these monomers used is not particularly limited, but it is usually used in the range of 80% by weight or less in all the monomers, and particularly 10% by weight or less in applications where oil resistance and heat resistance are required. Used in the range of.

In particular, the unsaturated carboxylic acid ester type monomer, and if necessary, in combination with the fluorine-containing vinyl type monomer, are copolymerized with the unsaturated nitrile and the conjugated diene to obtain the nitrile of the present invention. The cold resistance can be improved without impairing the ozone resistance and heat resistance of the group-containing highly saturated copolymer rubber. Among them, unsaturated dicarboxylic acid dialkyl ester is preferable. The amount of the unsaturated carboxylic acid ester-based monomer or the fluorine-containing vinyl-based monomer used is 1 to 80% by weight, preferably 15 to 60% by weight, and more preferably 20 to 40% by weight based on the total amount of the monomers.
It can be used in the range of% by weight.

Among the copolymer rubbers of unsaturated nitrile and conjugated diene, acrylonitrile having a bound acrylonitrile content of 10 to 60% by weight, preferably 20 to 50% by weight.
Butadiene copolymer rubber (hereinafter referred to as NBR) is suitable, and commercially available ones having a low nitrile amount to an extremely high nitrile amount can be used, and the optimum bound acrylonitrile content is NBR is selected.

The unsaturated nitrile-conjugated diene copolymer used in the present invention has a direct bond to at least three tertiary carbon atoms in the molecule and at least one tertiary carbon atom therein. Examples of the alkylthio group having a sulfur atom having 12 to 16 carbon atoms include 1,1-di (2,2-dimethylpropyl) -1-ethylthio group and 1,1-di (2,2).
A 2-dimethylpropyl) -1- (2,2,4,4-tetramethylpentyl) -1-ethylthio group may be mentioned, and these may be contained alone or in combination with each other in one molecule. Of these, a 1,1-di (2,2-dimethylpropyl) -1-ethylthio group is particularly preferable.

In the molecule of the unsaturated nitrile-conjugated diene copolymer used in the present invention, the above-mentioned alkylthio group is 0.03 mol or more, preferably 0.1%, per 100 mol of the monomer unit constituting the molecule. It is present in an amount of 07 mol or more, more preferably 0.09 mol or more. The amount of the alkylthio group is usually 0.3 mol or less. When the amount of the alkylthio group is excessively low, high crosslinking efficiency cannot be obtained in high-temperature and short-time vulcanization such as injection molding, and therefore the tensile stress and impact resilience of the molded product are not improved and the desired high speed is achieved. Vulcanization is not achieved. Further, as the amount of the alkylthio group becomes higher, the scorch time (T ₅ ) becomes remarkably shortened, and further, the mold staining property is significantly improved,
Highly productive injection molding is possible. Particularly, when the amount is 0.09 mol or more, the crosslinking efficiency is greatly improved, and the maximum torque in the vulcanization curve measured by using the oscillating disc rheometer is dramatically increased.

The unsaturated nitrile-conjugated diene copolymer used in the present invention is, as a molecular weight modifier, directly attached to at least three tertiary carbon atoms and at least one tertiary carbon atom thereof. 12 to 12 carbon atoms having a bonded thiol group
It is produced by preparing a copolymer latex of an unsaturated nitrile and a conjugated diene by emulsion polymerization in the presence of a radical initiator using 16 alkylthiol compounds, and coagulating the latex.

The radical polymerization initiator used is not particularly limited, but organic peroxides, redox polymerization initiators, azo compounds, persulfates and the like are usually used. The amount of these polymerization initiators used is usually 100
It is 0.005 to 3 parts by weight per part by weight. The polymerization temperature is preferably in the range of 0 to 100 ° C.

Specific examples of the alkyl thiol compound used as a molecular weight adjusting agent in producing an unsaturated nitrile-conjugated diene copolymer include 2,2 ', 4,6,6'-
Pentamethylheptane-4-thiol and 2,2 ',
4,6,6 ', 8,8'-heptamethylnonane-4-thiol can be mentioned. Among them, 2, 2 ', 4, 6,
6'-Pentamethylheptane-4-thiol is particularly preferable, and the unsaturated nitrile-conjugated diene copolymer produced by using the thiol compound is hydrogenated to obtain a nitrile group-containing highly saturated copolymer rubber which has a high vulcanizability. Is very good.

The alkylthiol compounds used as a molecular weight modifier in the production of unsaturated nitrile-conjugated diene copolymers can be used alone or in combination. In addition, if necessary, it is also possible to use together with other compounds conventionally known as a molecular weight modifier in radical polymerization. In this case, the alkylthiol compound should be contained in at least 50% by weight, preferably 80% by weight or more, more preferably 95% by weight or more, based on the total weight of the molecular weight modifier used.

Other compounds known as molecular weight regulators in radical polymerization include 2,4,4-trimethylpentane-2-thiol, dodecane-12-thiol and 2,2,6,6-tetramethylheptane. Alkyl thiol compounds such as 4-methanethiol and 2,4,6-trimethylnonane-4-thiol; xanthogen disulfides such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide; tetramethylthiuram disulfide, tetraethylthiuram disulfide , Thiuram disulfides such as tetrabutyl thiuram disulfide; halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide; hydrocarbons such as pentaphenylethane; and acrolein, Takurorein, allyl alcohol,
2-ethylhexyl thioglycolate, terpinolene, α-terpinene, γ-terpinene, dipentene, α
-Methylstyrene dimer (2-4-diphenyl-4-
Methyl-1-pentene is preferably 50% by weight or more), 2,5-dihydrofuran, 3,6-dihydro-2.
H-pin, phthalane, 1,2-butadiene, 1,4-hexadiene and the like can be mentioned.

The amount of the molecular weight modifier used in the radical polymerization is usually the monomer mixture 1 used in the copolymerization.
The amount is 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight, relative to 00 parts by weight, and the amount used in this range is advantageous in controlling the molecular weight of the resulting copolymer. The molecular weight modifier is added by dividing it during the polymerization,
It is possible to obtain polymers containing 3 to 20% by weight of low-molecular-weight components of n <35,000, which polymers have good processability. Generally, the total amount of the molecular weight modifier used is 10 to 9
It is preferable that 5% by weight is contained in the monomer mixture before polymerization, and the remaining amount of the molecular weight modifier is added to the polymerization system when the polymerization conversion rate reaches 20 to 70% by weight. The number of times of addition is appropriately determined as needed.

As an alternative method, irrespective of the method in which the molecular weight modifier is dividedly added in the polymerization process, two or more kinds of copolymers having different molecular weights, which are separately produced using the above molecular weight modifier, are mixed and prepared. You can also do it.

In the production of the unsaturated nitrile-conjugated diene copolymer used in the present invention, by using such a specific alkylthiol compound as a molecular weight modifier, the polymerization conversion rate of radical polymerization is 75% or more, preferably A high conversion rate of 80% or more can be achieved, and as a result,
The nitrile rubber can be produced with high productivity.

Generally, in the radical polymerization of nitrile rubber, the branching reaction or gelation reaction increases as the polymerization conversion rate increases. As a result, when the obtained nitrile rubber is vulcanized with a vulcanizing agent, high crosslinking efficiency cannot be obtained, and vulcanization physical properties such as tensile stress and impact resilience are deteriorated. Conventionally, t-dodecyl mercaptan used as a general-purpose molecular weight modifier in radical polymerization of nitrile rubber is a mixture of isomers of an alkylthiol compound having 9 to 16 carbon atoms, and a mixture of such isomers. The nitrile rubber obtained by using as a molecular weight modifier does not have sufficient high-speed vulcanizability during vulcanization at high temperature in a short time such as injection molding.

On the other hand, according to the method for producing an unsaturated nitrile-conjugated diene copolymer used in the present invention, even if the polymerization conversion rate is set to a high value of 80% or more, for example, oscillating It is possible to obtain a nitrile rubber excellent in high-speed vulcanization such that the maximum torque in the vulcanization curve measured using a disc rheometer shows a high value.

The total amount of the monomers to be polymerized can be charged all at once. Alternatively, the polymerization is initiated in the presence of 30 to 90% by weight of the total amount of the monomers used, and A method in which the remaining amount of the monomer is added to the polymerization system when the polymerization conversion rate reaches 20 to 70% can be adopted. The unsaturated nitrile-conjugated diene copolymer rubber composition obtained by this monomer division addition method is characterized by having good and well-balanced oil resistance and cold resistance.

The kind and amount of the monomer to be added in portions are appropriately selected according to the target amount of the bound unsaturated nitrile and the composition distribution width (ΔAN) of the unsaturated nitrile. For example,
When the amount of the bound unsaturated nitrile is less than 37%, the unsaturated nitrile is generally added during the polymerization, and when the amount of the bound nitrile is 37% or more, the conjugated diene is generally added during the polymerization. The number of times of addition is appropriately determined as needed. The emulsifier used when the unsaturated nitrile-conjugated diene copolymer latex is prepared by emulsion polymerization is not particularly limited, and examples thereof include carboxylate-based, sulfonate-based, and inorganic polyphosphate-based emulsifiers. used. Among them, the copolymer obtained by using a carboxylic acid-based emulsifier as an emulsifier further improves the problem of mold contamination in high temperature short time vulcanization such as injection molding.

Examples of the carboxylic acid emulsifier used include fatty acid soap and rosin acid soap.
Specifically, fatty acid soap is a long-chain aliphatic carboxylic acid having 12 to 18 carbon atoms, for example, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, etc., and sodium of these mixed aliphatic carboxylic acids. It is selected from salts or potassium salts. Also, the rosin acid soap is selected from sodium salt or potassium salt of disproportionated or hydrogenated natural rosin such as gum rosin, wood rosin or tall oil rosin. These natural rosins are mainly composed of abietic acid, levopimaric acid, parastrinic acid, dehydroabietic acid, tetrahydroabietic acid, neoabietic acid and the like. The amount of the emulsifier used is not particularly limited, but is usually 0.05 to 10 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the monomer.

In the process of emulsion copolymerization of unsaturated nitrile and conjugated diene, hydroxylamine, sodium carbamate, etc. are added to terminate the polymerization when a predetermined conversion rate is reached. Then, the residual monomer is removed from the produced copolymer latex by heating, steam distillation or the like.

The method of coagulating the copolymer latex prepared as described above is not particularly limited, and it is used in usual emulsion polymerization of an inorganic coagulant, a polymer coagulant or a dry heat coagulant. A coagulant can be added to coagulate. However, in order to produce the preferred unsaturated nitrile-conjugated diene copolymer used in the present invention, a nonionic surfactant is added to the copolymer latex prepared as described above, and then the copolymer latex is added. Put in a coagulation bath in which metal salt is dissolved and heat to coagulate.
By adopting such a preferred latex coagulation method, a crumb having an appropriate size and porosity and good drying property can be easily produced, and the use of a metal salt can be achieved by adding a nonionic surfactant. The amount can be reduced.

In the above-mentioned preferred latex coagulation method, specific examples of the nonionic surfactant added to the latex include alkylene oxide adducts of alkylphenol formalin condensates (for example, oxyethylene-oxypropylene co-adducts) and polyoxy. Examples thereof include ethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block polymer, alkylsulfinyl alcohol, and fatty acid monoglyceride. These nonionic surfactants may be used alone or in combination of two or more, and are appropriately selected depending on the coagulation conditions.

Among the above nonionic surfactants, an oxyethylene-oxypropylene co-adduct of an alkylphenol formalin condensate is preferred. This co-adduct shows a good thermosensitive gel effect. Cloud point of co-adduct is 10 to 100 ° C
The range is preferable, and the range of 20 to 70 ° C. is more preferable.
If the cloud point is too low, the handleability is poor, while if it is too high, it becomes difficult to obtain the heat-sensitive gel effect. The amount of the nonionic surfactant added is 0.01 to 5 with respect to 100 parts by weight of the polymer.
Part by weight is preferable, and 0.05 to 2 parts by weight is more preferable. If the amount of addition is too small, the above-mentioned effect of addition is not observed, and even if the amount of addition exceeds 5 parts by weight, the effect is substantially unchanged.

As the metal salt which can be dissolved during solidification,
Usually, calcium sulfate, sodium chloride, and metal sulfate are used. In particular, when a halogen-free metal sulfate is used, it is possible to obtain a nitrile group-containing highly saturated copolymer rubber that does not cause the problem of metal corrosion. Specific examples of the metal sulfate include aluminum sulfate, magnesium sulfate, sodium sulfate and the like, among which aluminum sulfate and magnesium sulfate are preferable.

The amount of the metal salt used is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polymer. If the amount of the metal salt is less than 0.5 part by weight, the coagulation in the coagulation bath becomes insufficient or the crumbs become large.
On the other hand, if it exceeds 50 parts by weight, the solidification rate is dominated by the metal salt, and the crumb becomes poor in porosity.

When the coagulation bath containing the polymer latex is heated above the cloud point of the nonionic surfactant, the polymer in the system coagulates and separates. The cloud point of nonionic surfactant is 1
The range of 0 to 100 ° C. is preferable, and if the cloud point is too low, cooling is required to keep it below the cloud point, and conversely, if it is too high, high temperature heating is required to solidify. The solidified polymer is recovered, washed with water and dried, and then the obtained unsaturated nitrile-conjugated diene copolymer is hydrogenated to obtain the desired highly saturated nitrile group-containing copolymer rubber.

The method for hydrogenating the unsaturated nitrile-conjugated diene copolymer is not particularly limited, and it can be hydrogenated according to a conventional method. Examples of the catalyst used in the hydrogenation include palladium / silica and palladium complex (JP-A-3-252405). Furthermore, JP-A-62-125858, JP-A-62-42937, JP-A-1-45402, JP-A-1-45403, JP-A-1-45404, and JP-A-1-45404.
It is also possible to use rhodium or ruthenium compounds such as those described in US Pat. The amount of the catalyst used is not particularly limited, but is usually 5 to 10,000 ppm based on the weight of the copolymer.

The method for preparing the aqueous emulsion of the nitrile group-containing highly saturated copolymer of the present invention is not particularly limited,
Usually, a phase inversion method or a method of directly hydrogenating a latex of an unsaturated nitrile-conjugated diene copolymer is adopted.
Hereinafter, these aqueous emulsion preparation methods will be described in detail.

The phase inversion method is a method in which a solution of a nitrile group-containing highly saturated copolymer rubber and an emulsifier aqueous solution are mixed, the rubber is emulsified and dispersed as fine particles in water by vigorous stirring, and the solvent is further removed. By this method, an aqueous dispersion of a nitrile group-containing highly saturated copolymer rubber is obtained. As the nitrile group-containing highly saturated copolymer rubber solution in that case, the solution at the end of the polymerization and the hydrogenation reaction may be used as it is, or may be concentrated or diluted, or the solid rubber may be used as a solvent. It can also be dissolved in and used. As the solvent, the rubber-soluble aromatic solvents such as benzene, toluene and xylene, halogenated hydrocarbon solvents such as dichloroethane and chloroform, ketones such as methyl ethyl ketone, acetone and tetrahydrofuran may be used alone or in combination. . The concentration of the nitrile group-containing highly saturated copolymer rubber in the solution is appropriately 1 to 25% by weight.

Examples of emulsifiers used in the preparation of the aqueous emulsifier solution include fatty acids such as oleic acid and stearic acid, potassium salts such as rosin acid, alkylbenzene sulfonic acid and alkyl sulfates, sodium salts, and polyoxyethylene-based nonionic emulsifiers. Commonly known ones are used alone or as a mixture. The volume ratio with the nitrile group-containing highly saturated copolymer rubber solution is 3: 1 to 1: 2.
0 is suitable. As a stirrer when emulsifying and dispersing,
Various homomixers and ultrasonic emulsifiers are used.
Removal of the solvent from the emulsion is performed by a known method such as a steam stripping method. When provided as a product, the proportion of the total solid content in the nitrile group-containing highly saturated copolymer rubber aqueous dispersion is appropriately 1 to 70% by weight.

As a method for direct hydrogenation, a method using a palladium-based catalyst (for example, JP-A-2-17) is used.
8305) and a method using a rhodium-based catalyst (for example, JP-A-59-115303 and JP-A-56-133).
219, U.S. Pat. No. 3,898,208), and a method using a ruthenium-based catalyst (for example, JP-A-6-
184223, JP-A-6-192323) and the like, but are not limited thereto. As a specific example, for example, when using a palladium-based catalyst,
As described in JP-A-2-178305, an organic solvent that dissolves or swells the nitrile group-containing unsaturated copolymer is added to the copolymer latex. According to this method, the nitrile group-containing unsaturated copolymer in the copolymer latex swells with an organic solvent, and the hydrogenation catalyst can be easily accessible to the double bond in the copolymer, so that the aqueous solution While maintaining the emulsion state,
The hydrogenation reaction can be performed efficiently.

Specific examples of the organic solvent include aromatic solvents such as benzene, toluene, xylene and ethylbenzene; halogenated hydrocarbon solvents such as dichloroethane, chloroform and chlorobenzene; carbon tetrachloride; methyl ethyl ketone, acetone, cyclohexanone, cyclo Ketones such as pentanone; Esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; Higher alcohols such as diacetone alcohol and benzen alcohol; Ethers such as dioxane and tetrahydrofuran; Acetonitrile, acrylonitrile, propio Examples thereof include nitriles such as nitrile, and these organic solvents can be used alone or in combination of two or more kinds.

The amount of the organic solvent used is the polymer latex /
The volume ratio of the organic solvent is in the range of 1/3 to 1/0. The hydrogenation reaction proceeds even if the amount exceeds this range, but if the amount of the solvent is too large, the emulsion is broken and the solvent phase and the aqueous phase are easily separated. Then, a new step for separating the aqueous phase and the solvent phase and a step for recovering the hydrogenated polymer from the solvent phase are required, which rather complicates the step. When the volume ratio of polymer latex / organic solvent is in the range of 1/3 to 1 / 1.5, the hydrogenation reaction can be carried out while maintaining the emulsion state, but the emulsion may be destroyed after the reaction. Therefore, when the emulsion state is maintained after the reaction, the volume ratio of polymer latex / organic solvent is 1 /
It is preferable to control in the range of 1 to 1/0.

Furthermore, when it is desired to suppress the increase of emulsion particles under the hydrogenation reaction condition and make the emulsion particle size after the hydrogenation reaction substantially the same as that before the hydrogenation reaction,
The amount of the organic solvent used is an aqueous emulsion / organic solvent volume ratio in the range of 1/1 to 1/0. If it exceeds this range, the emulsion particles are coalesced or destroyed during the hydrogenation reaction, and it is not possible to obtain a nitrile group-containing hydrogenated polymer aqueous emulsion in which the average particle diameter of the emulsion does not substantially change before and after the hydrogenation reaction.

The lower limit of the amount of the organic solvent added is not particularly limited, but in order to carry out the hydrogenation reaction uniformly and efficiently, the volume ratio of polymer latex / organic solvent is preferably 1/1 to 1/1 /.
It is desirable to add it in a ratio of 0.05.
The timing of adding the organic solvent is not particularly limited, and the organic solvent may be added before, after, or simultaneously with the addition of the hydrogenation catalyst. When the hydrogenation catalyst is dissolved in an organic solvent, it is preferable to add it as a solution of the hydrogenation catalyst in an organic solvent to the polymer latex in terms of efficiency and operation of the hydrogenation reaction.

The hydrogenation catalyst used is not particularly limited as long as it is a palladium compound. Specific examples of the palladium compound include, for example, palladium salts of carboxylic acids such as formic acid, acetic acid, propionic acid, lauric acid, succinic acid, stearic acid, oleic acid, phthalic acid and benzoic acid; palladium chloride, dichloro (cyclooctadiene). ) Palladium, chlorinated palladium such as dichloro (norbornadiene) palladium, dichloro (benzonitrile) palladium, dichlorobis (triphenylphosphine) palladium, ammonium tetrachloropalladium (II) acid, ammonium hexachloropalladium (IV) acid; palladium bromide Examples thereof include, but are not limited to, inorganic compounds and complex salts such as palladium iodide, palladium sulfate dihydrate, potassium tetracyanopalladium (II) trihydrate, and the like. Among them,
Particularly preferred are palladium salts of carboxylic acids, dichloro (norbornadiene) palladium, ammonium hexachloropalladate and the like. The amount of the catalyst used may be appropriately determined depending on the kind of the copolymer to be hydrogenated and the desired hydrogenation rate, but usually 5 to 6,000 pp per copolymer.
m, preferably 10 to 4,000 ppm. 6,0
You may use more than 00ppm, but it is not economical.

The hydrogenation reaction temperature is 0 to 300 ° C, preferably 20 to 150 ° C. Although there is no problem even if it exceeds 150 ° C., side reactions easily occur, which is not desirable in the selective hydrogenation reaction of carbon-carbon double bonds. The side reaction includes, for example, hydrogenation of an organic solvent and hydrogenation of an ethylenically unsaturated monomer unit in a copolymer, for example, a nitrile group of acrylonitrile.

Gaseous hydrogen or dissolved hydrogen is used as a hydrogen source and is brought into contact with the nitrile group-containing unsaturated copolymer. The hydrogen pressure is in the range of atmospheric pressure to 300 kg / cm ² , preferably 5 to 200 kg / cm ² . 300 kg /
High pressure of cm ² or more is acceptable, but the equipment cost is high,
However, there are many factors that hinder the practical use, such as being difficult to handle. Usually, it is used in the range of several atmospheres to several tens of atmospheres.

After the hydrogenation reaction is completed, a reaction system ion-exchange resin or the like is added to adsorb the catalyst, and then the catalyst can be removed by a usual catalyst removal method such as a centrifugation method or a filtration method. Further, the catalyst may be left as it is in the nitrile group-containing hydrogenated copolymer without being removed. In order to obtain an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber, the solvent added during the hydrogenation reaction may be removed by a known method such as an ordinary steam stripping method.

The aqueous emulsion of hydrogenated copolymer thus obtained is concentrated if necessary. Concentration is carried out by a conventional method such as a rotary evaporator and a high speed centrifuge so that the total solid content concentration is preferably in the range of 10 to 70% by weight.

According to the method as described above, the nitrile group-containing unsaturated polymer can be hydrogenated in the emulsion state. Therefore, after the nitrile group-containing unsaturated polymer is taken out from the polymerization system in a solid state, it is added to an organic solvent. The process can be greatly simplified as compared with the conventional method of dissolving and hydrogenating in a solution state.

Adhesive Composition The adhesive composition of the present invention contains the above-mentioned aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber and a resorcin-formaldehyde resin as essential components. As the resorcin-formaldehyde resin, conventionally known ones (for example, those disclosed in JP-A-55-142635) can be used and are not particularly limited. Further, 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or a similar compound which has been conventionally used for enhancing the adhesive strength, isocyanate, blocked isocyanate, ethylene urea, polyepoxide, modified Polyvinyl chloride resin or the like can be used in combination. In the adhesive composition of the present invention, the amount of resorcin-formaldehyde resin used (dry weight conversion) is usually
The amount is 10 to 180 parts by weight based on 100 parts by weight of the solid content of the nitrile group-containing highly saturated copolymer rubber aqueous emulsion.

Within a range not impairing the gist of the present invention, a part of the nitrile group-containing highly saturated copolymer rubber aqueous emulsion is replaced with styrene-butadiene copolymer rubber latex, its carboxy-modified latex, and acrylonitrile-butadiene copolymer. Polymer rubber latex, carboxy-modified latex thereof, natural rubber latex and the like can be substituted.

Treatment of Organic Synthetic Fibers with Adhesive Composition The adhesive composition of the present invention can be suitably used for treating organic synthetic fibers. The organic synthetic fiber that can be used is not particularly limited, and specific examples thereof include polyvinyl alcohol fiber, polyester fiber, polyamide fiber, aramid fiber (aromatic polyamide fiber) and the like. Examples of the form of these fibers include staples, filaments, cords, ropes, and other woven fabrics, but other forms are also possible.

The method of treating the fibers with the adhesive composition of the present invention is not particularly limited, and the same method as in the case of using a known resorcin-formaldehyde resin-polymer latex adhesive composition can be adopted. However, an example of the method is as follows. The fibers are soaked with the adhesive composition and, if necessary, usually from 100 to 1
After drying at 50 ° C. for about 0.5 to 10 minutes, heat treatment is performed. The heating conditions are not particularly limited, and are a time and temperature sufficient for reaction-fixing the adhesive composition adhered by immersion, and usually about 140 to about 25.
It is carried out at 0 ° C. for several minutes.

Highly saturated organic synthetic fibers with adhesive composition
Adhesion with Nitrile Rubber The adhesive composition of the present invention can be effectively used for vulcanization adhesion of organic synthetic fiber and highly saturated nitrile rubber, and thus has excellent adhesive strength, organic synthetic fiber and highly saturated nitrile. A composite with rubber can be obtained. Highly saturated nitrile rubber (hereinafter, sometimes referred to as adherend rubber) is α, β-
Any copolymer rubber or a derivative thereof of an ethylenically unsaturated nitrile and a conjugated diene and / or an ethylenically unsaturated monomer may be used. The content of the monomer unit containing a nitrile group in the adherend rubber is usually in the range of 10 to 60% by weight from the viewpoint of the oil resistance of the rubber product compounded with the fiber, and the iodine value is the heat resistance. From the point, it is 120 or less, preferably 100 or less, more preferably 80 or less. In the synthesis of the adherend rubber, the same monomers as those used in the synthesis of the nitrile group-containing unsaturated copolymer rubber aqueous emulsion can be used.

The adherend rubber can be directly obtained as a highly saturated nitrile rubber by copolymerizing the above-mentioned monomers, or can be obtained by hydrogenating a nitrile group-containing unsaturated copolymer rubber. The polymerization method and hydrogenation method therefor are not particularly limited. Specific examples of the adherend rubber include highly saturated butadiene-acrylonitrile copolymer rubber, highly saturated isoprene-butadiene-acrylonitrile copolymer rubber, highly saturated isoprene-acrylonitrile copolymer rubber; highly saturated butadiene-methyl acrylate- Acrylonitrile copolymer rubber, highly saturated butadiene-acrylic acid-
Acrylonitrile copolymer rubber, highly saturated butadiene-ethylene-acrylonitrile copolymer rubber, butyl acrylate-ethoxyethyl acrylate-vinyl nobornene-
Examples thereof include acrylonitrile copolymer rubber. In particular, when the nitrile group-containing highly saturated copolymer rubber used when preparing the aqueous emulsion of the present invention is used as the adherend rubber, the adhesive strength due to vulcanization adhesion is further increased.

The method of vulcanizing and adhering the highly saturated nitrile rubber and the organic synthetic fiber treated with the adhesive composition of the present invention is not particularly limited, and is conventionally adopted for the vulcanizing and adhering of rubber and fiber. The same method can be adopted. Specifically, it is achieved by embedding organic synthetic fibers in a rubber compound prepared by adding a compounding agent such as a vulcanizing agent and a filler to rubber and then vulcanizing it. The vulcanization conditions are usually 0.5 to 10 MP.
It is at 120 to 180 ° C. for 1 to 120 minutes under the pressure of a.

When the rubber is adhered by using the aqueous emulsion of the present invention as an adhesive, it is necessary to add a sulfur vulcanizing agent to the adherend rubber. As the sulfur-based vulcanizing agent used, powdered sulfur, sulfur flower, precipitated sulfur, colloidal sulfur,
Surface-treated sulfur, sulfur such as insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, N, N'-dithio-bis (hexahydro-2H-azepinone-2), phosphorus-containing polysulfide, polymer polysulfide And sulfur compounds such as tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, and 2- (4'-morpholinodithio) benzothiazole.

Furthermore, in addition to these sulfur-based vulcanizing agents,
Vulcanization accelerators such as zinc white and stearic acid; guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based,
Other vulcanization accelerators such as the xanthate type can be used. The amount of the sulfur-based vulcanization accelerator used is not particularly limited, but is usually 0.10 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the nitrile group-containing highly saturated copolymer rubber.
5 parts by weight.

If the adherend rubber composition does not contain a sulfur-based vulcanizing agent as a vulcanizing agent, good high-speed vulcanization cannot be achieved in high-temperature short-time vulcanization, and the adhesive strength should be increased. I can't. However, for example, a vulcanizing agent other than the sulfur-based vulcanizing agent such as an organic peroxide-based vulcanizing agent can be appropriately used in combination with the sulfur-based vulcanizing agent.

If necessary, the vulcanizable rubber composition forming the adherend may include other conventional compounding agents used in the rubber field, such as reinforcing agents (various carbon black, silica, talc). Etc.), filler (calcium carbonate,
Clay), processing aids, process oils (plasticizers), antioxidants, antiozonants and the like.

[0064]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The parts and% in Examples, Comparative Examples and Reference Examples are based on weight unless otherwise specified. In the examples, the characteristics of the polymer were measured as follows. (1) Amount of bound nitrile According to Japanese Industrial Standard JIS K6384, the nitrogen content in the copolymer was measured by the Kjeldahl method, and the amount of bound nitrile was calculated (unit:%). (2) Mooney viscosity According to Japanese Industrial Standard JIS K6383, about 40 g of the copolymer was used and measured at 100 ° C.

(3) Number average molecular weight Mn Component amount of 35,000 or less By gel permeation (solvent: tetrahydrofuran), the number average molecular weight (Mn) converted to standard polystyrene of the unsaturated nitrile-conjugated diene copolymer before hydrogenation. ) And the weight average molecular weight (Mw) were measured, and the weight% of the component was obtained using the measured area of the entire molecular weight distribution and the area of the component having a number average molecular weight Mn of 35,000 or less.

(4) Composition Distribution Width of Unsaturated Nitrile of Copolymer Before Hydrogenation (ΔAN) The composition distribution width of unsaturated nitrile was determined by high performance liquid chromatography, and its outline is summarized in Rubber Chemistry and・ Technology (Rubber Chemistryand Tech
nology) 63 , (2), P181-191 (199)
0). That is, the unsaturated nitrile-conjugated diene copolymer was measured by high performance liquid chromatography under the following measurement conditions, and the half width of the chromatogram was Δ.
It is AN. When determining ΔAN, a calibration curve of elution amount-unsaturated nitrile amount is prepared using a sample with a known unsaturated nitrile amount.

1. Column gel: (2-chloroacrylonitrile / ethylene dimethacrylate) crosslinked polymer gel Particle size: 2 to 6 μm Column: Stainless steel column Column diameter x length: 0.46 cm x 25 cm 2. Eluent chloroform / n-hexane (weight ratio) 30/70 → 1
00/0 (gradient elution in 30 minutes). However, 20 with initial setting chloroform / n-hexane = 30/70
Run for minutes. 3. Flow rate 0.5 ml / min 4. Sample concentration 1% by weight chloroform solution 5. Injection volume 10 to 20 μl 6. Detector Light Scattering Mass Detector (Mass Detecto
r: Model 750 / I4 ACS Co.) 7. Equipment Trirotor VI type (made by JASCO Corporation)

(4) Concentration of 1,1-di (2,2-dimethylpropyl) -1-ethylthio group in the copolymer before hydrogenation The copolymer is dissolved in benzene and then solidified in methyl alcohol. The procedure was repeated 3 times for purification, and NMR measurement was performed on the purified copolymer. ¹ H-NMR measurement (4
00 MHz), a peak due to the proton of the terminal methyl group in the ethylthio group was detected at around 1.05 ppm, and further due to ¹³ C-NMR measurement (100 MHz), due to the carbon of the methylene group in the ethylthio group. Peak is detected around 54.6 ppm.

The concentration of the ethylthio group in the copolymer before hydrogenation was quantified by the integrated value of the peak due to the terminal methyl group in ¹ H-NMR measurement and the butadiene detected in the vicinity of 4.8 to 5.8 ppm. Was calculated by using the ratio with the integral value of the peak due to the proton bound to the unsaturated bond (unit: mol%).

Examples 1 to 5 In a reactor having an internal volume of 10 liters, 2 parts of potassium oleate as an emulsifier and 0.1 part of potassium phosphate as a stabilizer.
And 150 parts of water were charged, and butadiene and acrylonitrile in the amounts shown in Table 1 and 2,2 ', 4,6,6'-pentamethylheptane-4-thiol (hereinafter referred to as PMHT) as a molecular weight modifier. ) Was added, and emulsion polymerization was initiated at 10 ° C. in the presence of 0.015 part of ferrous sulfate as an activator and 0.05 part of paramenthane hydroperoxide as a polymerization initiator. Acrylonitrile (production of copolymers I to IV), butadiene (production of copolymer V) and PMHT (production of copolymers I to V) were carried out under the conditions shown in Table 1 when a predetermined polymerization addition rate was reached. Each was added in portions. When the predetermined polymerization addition rate is reached,
Polymerization was terminated by adding 0.2 part of hydroxylamine sulfate per 100 parts of the monomer. Subsequently, after heating and recovering the residual monomer by steam distillation under reduced pressure at about 70 ° C., 2 parts of alkylated phenol as an antioxidant was added to obtain a copolymer latex. The properties of these copolymers (before hydrogenation) are shown in Table 1.

Next, after adjusting the solid content concentration of each of the above copolymer latexes to 12%, 400 ml thereof was put into an autoclave with an internal volume of 1 liter equipped with a stirrer, and nitrogen gas was flowed for 10 minutes to put the latex in the latex. After removing the dissolved oxygen in Example 1, palladium acetate as a hydrogenation catalyst was dissolved in 240 ml of acetone and added. The atmosphere in the system was replaced with hydrogen gas twice, and the system was pressurized with hydrogen gas until the pressure in the system reached 30 atm. Then, the content was heated to 50 ° C. and reacted for 6 hours with stirring. After cooling the contents to room temperature, excess hydrogen was purged, and the obtained latex was removed of the organic solvent using an evaporator,
The mixture was concentrated to a solid content concentration of 40% to obtain an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber shown in Table 1. Table 1 shows the pH, average particle size and iodine value of these aqueous emulsions. Next, a formulation of these aqueous emulsions was prepared according to the formulation of Table 2, spread on a glass plate, and dried at 20 ° C. and a humidity of 65% for 3 days,
Then, it was vulcanized at 100 ° C. for 30 minutes, and the obtained film was punched with JIS No. 3 dumbbell to prepare a test piece,
The vulcanized physical properties [300% tensile stress (kg / cm ² ) and breaking elongation (kg / cm ² )] were measured according to JISK6301. The results are shown in Table 3.

Comparative Examples 1 to 3 The molecular weight modifier was changed to commercially available t-dodecyl mercaptan (manufactured by Phillips Petroleum Co., Ltd.), and acrylonitrile, butadiene and PMHT were not added separately, and otherwise the same as in Example 2. Under the conditions, butadiene and acrylonitrile were copolymerized to obtain copolymers VI to VIII. Then, it was hydrogenated to obtain an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber. The polymerization results are shown in Table 1. next,
The results of evaluating the physical properties of the vulcanizate of the highly saturated copolymer rubber in the same manner as in Example 1 are shown in Table 3.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

The H-NMR measurement chart of the copolymer I obtained in Example 1 before hydrogenation is shown in FIG.
The ¹³ C-NMR measurement chart is shown in FIG. In addition, H of the highly saturated copolymer rubber obtained by hydrogenating the copolymer I
-The NMR measurement chart is shown in FIG. In addition, N of the acrylonitrile-butadiene copolymer obtained in other examples
The presence of 1,1-di (2,2-dimethylpropyl) -1-ethylthio group was confirmed by MR measurement.

From Table 3, the films (Examples 1 to 5) obtained from the aqueous emulsion of the present invention are all 300
The% tensile stress is high and the breaking strength is also high, indicating that the vulcanized physical properties are improved. On the other hand, those obtained by emulsion polymerization using t-dodecyl mercaptan (commercially available product), which is conventionally known as a general-purpose molecular weight modifier in radical polymerization, are 3
Both 00% tensile stress and breaking strength are low. Also,
NMR measurement was performed on the copolymer obtained by using commercially available t-dodecyl mercaptan.
The presence of 2-dimethylpropyl) -1-ethylthio group was not confirmed.

Examples 6 to 10 and Comparative Examples 4 to 6 Preparation of Adhesive Rubber Blends According to the blending recipe shown in Table 4, a highly saturated nitrile rubber and a blending agent were kneaded on a roll to give a thickness of about 2.5 mm. A sheet of the rubber compound of was prepared.

[0079]

[Table 4]

Next, Examples 1 to 5 and Comparative Examples 1 to 3
According to the formulation of Table 5, using the aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber described in Table 1 used in
Each adhesive composition was prepared.

[0081]

[Table 5]

A treated cord was prepared by dipping each fiber in a test single cord dip machine with each adhesive composition. The types of fibers used and the treatment method are as follows. Nylon cord (6-nylon, structure 1260D / 2) and rayon cord (3-
Super, structure 1650D / 2) are RFLs, respectively.
Adhesion pretreatment was performed with the mixture to produce a cord for a tension body. The polyester cord (polyethylene terephthalate, structure 1500 D / 3) was dipped in a mixed solution containing 600 parts of the RFL solution and 400 parts of the 2,6-bis (2,4-dihydroxyphenylmethyl-4-chlorophenol composition). Then, it was heat-treated at 245 ° C. for 1 minute and then immersed in an RFL solution, and then heat-treated at 230 ° C. for 1 minute to prepare a cord for a tensile body. Aramid fiber (Kevlar manufactured by DuPont, structure 1500D / 2127T / m) Immerse in the following pretreatment liquid and heat treatment at 220 ° C for 2 minutes, then RF
It was dipped in the liquid L and heat-treated at 230 ° C. for 1 minute to obtain a cord for tensile body.

[0083]   Pretreatment liquid composition     2.22 parts by weight of diglycidyl ether of glycerin     10% NaOH aqueous solution 0.28〃     5% “AEROSOL” OT 0.56 〃     (75% solids) *     Water 96.94 〃                             Total 100.00〃   * Nippon Aerosil products

Glass fiber cord (ECG150 3/1
(020S structure) is immersed in a 5% aqueous dispersion of α-aminopropyltriethoxysilane, heat-treated at 150 ° C. for 3 minutes, then immersed in RFL solution, and further heat-treated at 200 ° C. for 1 minute to form a tensile body. Got the code for. The treated cord thus obtained was embedded in the adherend rubber compound to a length of 8
mm, and press pressure 5 MPa. It was vulcanized at 150 ° C. for 30 minutes to obtain a composite of fiber and rubber.

For the resulting composite, ASTM D21
A cord pull-out test was performed according to 38-72 and the like to measure the initial adhesive force. 1 obtained in the same manner
A cord pull-out test was performed after heat-resistant treatment in an air oven at 20 ° C. for 168 hours to measure heat-resistant adhesive strength.
The results are shown in Table 6.

[0086]

[Table 6]

From Table 6, it can be seen that the composite of highly saturated nitrile rubber and fiber using the adhesive composition of the present invention has improved adhesive strength as compared with the conventional composite using the same composition.

[0088]

Thus, according to the present invention, an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber and an adhesive composition containing the emulsion, which gives a vulcanized adhesive having good adhesive strength and mechanical strength. Will be provided. In particular, when the aqueous emulsion or adhesive composition of the present invention is used for adhesion, if a rubber containing a sulfur-based vulcanizing agent is used as the rubber to be adhered, the adhesive strength and mechanical strength of the vulcanized adhesive material are further improved. It will be excellent. The vulcanized adhesive formed from the aqueous emulsion or adhesive composition of the present invention retains the good weather resistance, oil resistance and heat resistance generally possessed by the nitrile group-containing highly saturated copolymer rubber.

The composite of the highly saturated nitrile rubber and the organic synthetic fiber obtained by using the adhesive composition of the present invention has an excellent initial adhesion as compared with the case of using the conventional similar adhesive composition. Since it has strength, adhesive strength after heat aging (heat resistant adhesion) and water resistant adhesion, it is especially useful for toothed conductive belts using organic synthetic fibers as a tensile body, various belts for automobiles and other V belts, and automobiles. It is useful for manufacturing pressure resistant hoses such as power steering hoses and hydraulic hoses for various machines such as construction machinery, freon hoses, and various hoses such as automobile fuel hoses.

Further, the aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber of the present invention has extremely strong unvulcanized film strength and vulcanized film strength, and has excellent oil resistance, heat resistance and weather resistance. It can be used for fiber treatment of non-woven fabric binders, paper treatment of impregnated papers, special dipping products requiring oil resistance, and binders of foam rubber, thread rubber, cork and the like.

Preferred specific embodiments of the aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber and the adhesive composition of the present invention described in claims 1 and 2 are as follows.

(Claim 1) A nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating a conjugated diene moiety of an unsaturated nitrile-conjugated diene copolymer, comprising at least three tertiary carbon atoms and the same. Having 12 to 1 carbon atoms having a sulfur atom directly bonded to at least one tertiary carbon atom therein
It has 6 alkylthio groups in the molecule and has a Mooney viscosity of 1
An aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber having an iodine value of 5 to 200 and an iodine value of 80 or less.

(1) The nitrile group-containing highly saturated copolymer rubber has the alkylthio group as the monomer unit 10 constituting the molecule.
0.03 mol or more per 0 mol, more preferably 0.07 mol
The aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to claim 1, which is present in the molecule in a molar ratio of at least 1. (2) The alkylthio group is a 1,1-di (2,2-dimethylpropyl) -1-ethylthio group and 1- (2,2-
The aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to claim 1, which is at least one selected from dimethylpropyl) -1- (2,2,4,4-tetramethylpentyl) -1-ethylthio group.

(3) The aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to claim 1, wherein the alkylthio group is a 1,1-di (2,2-dimethylpropyl) -1-ethylthio group. (4) The aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber according to claim 1, wherein the amount of bound unsaturated nitrile in the unsaturated nitrile-conjugated diene copolymer is 10 to 60% by weight. (5) The nitrile group according to claim 1, wherein the nitrile group-containing highly saturated copolymer is a hydride of a copolymer of 10 to 60% by weight of acrylonitrile and 90 to 40% by weight of butadiene and has a Mooney viscosity of 20 to 90. Aqueous emulsion of highly saturated copolymer rubber containing.

(6) The nitrile group-containing highly saturated copolymer according to claim 1, wherein the unsaturated nitrile-conjugated diene copolymer contains 3 to 20% by weight of a low molecular weight component having a number average molecular weight (Mn) of 35,000 or less. Aqueous emulsion of polymer rubber. (7) Ratio (Mw /) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the unsaturated nitrile-conjugated diene copolymer.
The aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to claim 1, wherein Mn) is 2.3 to 5.5.

(8) The composition of the unsaturated nitrile in the unsaturated nitrile-conjugated diene copolymer (ΔAN) has a composition distribution width (ΔAN) of 35 or less, more preferably 3 to 20. Aqueous emulsion of copolymer rubber. (9) The aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber according to claim 1, wherein the nitrile group-containing highly saturated copolymer rubber does not substantially contain a halogen atom.

(10) The unsaturated nitrile-conjugated diene copolymer comprises, in addition to the unsaturated nitrile and the conjugated diene, 1 to 80% by weight of unsaturated carboxylic acid ester or unsaturated carboxylic acid based on all monomers. The aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to claim 1, which is obtained by copolymerizing an ester and a fluorine-containing vinyl monomer. (11) A nitrile group-containing highly saturated copolymer rubber solution and an emulsifier aqueous solution are used by a phase inversion method or unsaturated nitrile-
The aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to claim 1, which is produced by directly hydrogenating a conjugated diene copolymer latex.

(Claim 2) An adhesive composition comprising the aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to Claim 1 and a resorcin-formaldehyde resin. (12) The adhesive composition according to claim 2, wherein the resorcin-formaldehyde resin is contained in an amount of 10 to 180 parts by weight based on 100 parts by weight of the solid content of the nitrile group-containing highly saturated copolymer rubber aqueous emulsion.

(13) The adhesive composition according to claim 2, which is used for adhering a rubber composition containing a sulfur-based vulcanizing agent and fibers. (14) The adhesive composition as described in (13) above, wherein the rubber composition is the same rubber composition as the nitrile group-containing highly saturated copolymer rubber in the aqueous emulsion.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR measurement chart of unsaturated nitrile-conjugated diene copolymer I obtained in Example 1.

FIG. 2 is a ¹³ H-NMR measurement chart of the unsaturated nitrile-conjugated diene copolymer I obtained in Example 1.

FIG. 3 H of a nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating the above unsaturated nitrile-conjugated diene copolymer I.
-NMR measurement chart.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09J 161/04 C09J 161/04 (72) Inventor Motofumi Oyama 1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan ZEON CORPORATION Company General Development Center (56) Reference JP-A-2-160882 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 9/04 C09J 109/04

Claims (2)

(57) [Claims] 1. A nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating a conjugated diene portion of an unsaturated nitrile-conjugated diene copolymer, comprising at least three tertiary carbon atoms and at least three of them. It has an alkylthio group having 12 to 16 carbon atoms having a sulfur atom directly bonded to one tertiary carbon atom in the molecule, and has a Mooney viscosity of 15 to 200.
And an aqueous emulsion of a nitrile group-containing highly saturated copolymer rubber having an iodine value of 80 or less. 2. An adhesive composition comprising the aqueous emulsion of the nitrile group-containing highly saturated copolymer rubber according to claim 1 and a resorcin-formaldehyde resin.