WO1998044039A1 - Composition comprising mixture of synthetic resin and highly saturated carboxylated nitrile copolymer rubber - Google Patents

Abstract

A composition comprising a mixture of a synthetic resin and a highly saturated carboxylated nitrile copolymer rubber, characterized by comprising (A) 90 to 10 % by weight of at least one thermoplastic or thermosetting resin and (B) 10 to 90 % by weight of a highly saturated carboxylated nitrile copolymer rubber which has an acid equivalent of 2X10-3 ephr or higher, a value of [height of the peak assignable to carboxylic anhydride group]/([height of the peak assignable to carboxylic anhydride group] + [height of the peak assignable to carboxyl group) as determined by infrared absorption spectrometry of 0.50 or larger, a Mooney viscosity of 15 to 200, and an iodine value of 80 or lower. This rubber mixture composition has various improved properties because the synthetic resin and the rubber are in an improved mixed state.

Description

 Specification

 Mixed composition of synthetic resin and carboxylated nitrile group-containing highly saturated copolymer rubber

Technical field

 The present invention relates to a mixed composition of a synthetic resin and a rubber in which the mixing state is improved. More specifically, the present invention relates to a method of mixing a rubber with a synthetic resin having various improved physical properties by blending a thermoplastic resin or a thermosetting resin with a highly saturated copolymer rubber containing a carboxylated nitrile group. Composition.

Background art

 The nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating the unsaturated bond of the atarilonitrile butadiene copolymer rubber is known as a rubber having excellent heat resistance, weather resistance, oil resistance and the like. A thermoplastic elastomer composition combining the rubber with a synthetic resin such as a polyamide has been reported in order to take advantage of the properties (see, for example, Japanese Patent Application Laid-Open No. Hei 2-269391, 2-191656, JP-A-63-112656, etc.). Such a composition is said to exhibit excellent performance in balance among impact resistance, heat deterioration resistance, weather resistance and mechanical strength.

 However, the synthetic resin and the nitrile group-containing highly saturated copolymer rubber are often incompatible with each other, and the mixing state of these mixtures is not always good.

To improve the compatibility between the synthetic resin and the nitrile group-containing highly saturated copolymer rubber, it has been proposed to add maleic anhydride to the nitrile group-containing highly saturated copolymer rubber (for example, (Japanese Patent Application Laid-Open No. 643-60039). As a method for adding maleic anhydride, for example, a chemical reaction such as autoclave is used. A solution addition reaction in a container, a solid-phase heat addition reaction in a mixing machine such as a kneading extruder, or a radical addition reaction using a peroxide in a closed kneader. Used.

 However, the carboxylated nitrile group-containing highly saturated copolymer rubber obtained by these conventional methods has a high reaction rate with zinc oxide and the like, and thus tends to cause scorch and has low processability. In addition, various properties required for belts and hoses, such as abrasion resistance and low compression set, were not sufficiently satisfied.

 An object of the present invention is to improve the mixing state of a synthetic resin and a rubber in a mixed composition comprising a thermoplastic resin or a thermosetting resin and a nitrile group-containing highly saturated copolymer rubber. An object of the present invention is to improve various physical properties of a mixed composition.

 The present inventor has noticed that most of the carboxylic anhydride groups are decomposed into carboxyl groups in the carboxylated nitrile group-containing highly saturated copolymer rubber obtained by the conventional method. Therefore, the present inventors have repeatedly studied the state of addition of the carboxyl group and the addition reaction mechanism. As a result, the present inventor has found that a carboxylated nitrile group-containing highly saturated copolymer rubber in which the ratio of carboxylic acid anhydride groups to carboxyl groups is within a specific range can be used as a thermoplastic resin such as Niopene. The carboxylated nitrile group-containing highly saturated copolymer rubber is used for the ene-type addition reaction between hydrogenated acrylonitrile-butadiene copolymer rubber and maleic anhydride in a specific temperature range. We found what we can do by doing The present invention has been completed based on this finding.

Disclosure of the invention Thus, according to the present invention, (A) at least one thermoplastic resin or thermosetting resin 90 to 10% by weight and (B) an acid equivalent of at least 2 × 10-3 ephr, infrared absorption spectroscopy Of [peak height of carboxylic acid anhydride group] / ([peak height of carboxylic acid anhydride group] + [peak height of carboxyl group]) is more than 0.50, A synthetic resin comprising 10 to 90% by weight of a carboxylated nitrile group-containing highly saturated copolymer rubber having a viscosity of 15 to 200 and an iodine value of 80 or less, and a carboxylated nitrile group-containing high content. A mixed composition with a saturated copolymer rubber is provided. The carboxylated nitrile group-containing highly saturated copolymer rubber used in the present invention has an acid equivalent of 210-3 ephr or more and is measured by infrared absorption spectroscopy. [Peak height of acid anhydride group] Z ([acid anhydride Peak height of the substance group] + [peak height of the carboxyl group]) is 0.5 or more, the viscosity is 15 to 200, and the iodine value is 80 or less.

 The carboxylated nitrile group-containing highly saturated copolymer rubber used in the present invention is a copolymer having a nitrile group in the molecule, having few carbon-carbon unsaturated bonds, and exhibiting rubber elasticity. Thus, it further has a carboxyl group in the molecule.

 The amount of carbon-carbon unsaturated bonds is alternatively expressed by the iodine value. The highly saturated copolymer rubber containing a carboxylated nitrile group used in the present invention has an iodine value of 80 or less, preferably 60 or less. If the iodine value is too large, the oil resistance and heat resistance of the crosslinked product decrease.

The content of bound nitrile units in the rubber is not particularly limited, but is usually 10 to 60% by weight, preferably 15 to 40% by weight. In addition, The content of toll units is a value determined by the Geldar method. When the content of the bound nitrile unit is increased, the oil resistance and heat resistance of the crosslinked product are increased, and when the content of the bound nitrile unit is reduced, the rubber elasticity of the crosslinked product is increased. Therefore, it is appropriately selected according to the application.

Acid equivalent of the rubber, 2 X 10- ³ ephr or more, preferably 2 x 10 one ³ ~ 5x l 0- ² ephr, more preferably 5 x 10 - a 3~ 3 x 10 ² ephr. If the acid equivalent is too small, the compatibility with the thermoplastic resin or the like will not be improved.

 The acid equivalent is determined by dissolving the rubber in acetone, reprecipitating and refining with n-hexane, and re-dissolving the resulting reprecipitated purified rubber in acetone. This value was obtained by titration using thymolphthalein as an indicator using an ethanol solution of the above.

 The rubber used in the present invention has a value of [peak height of acid anhydride group] / ([peak height of acid anhydride group] + [peak height of carboxyl group]) of 0. It is 5 or more, preferably 0.75 or more, more preferably 0.85 or more, and particularly preferably 0.9 or more. If this value is too small, scorch is likely to occur during the crosslinking of the mixed composition, and the crosslinked product will not have sufficient abrasion resistance and the compression strain will tend to be large.

The rubber used in the present invention has a Mooney viscosity (ML = ₄ , 100 ° C.) of 15 to 200, preferably 30 to 150. If the viscosity is too high, the kneading processability will deteriorate, while if it is too low, the durability under high pressure will be insufficient, and the permanent compression set and crushing (compression relaxation) will be insufficient. The rubber used in the present invention has a methylethyl ketone insoluble content, Usually, it is at most 3% by weight, preferably at most 2% by weight, more preferably at most 1% by weight. The insoluble matter content of methyl ethyl ketone was determined by finely chopping the rubber, placing it in an 80 mesh wire mesh basket, immersing the basket in methyl ethyl ketone at room temperature for 48 hours, The remaining solid content is dried, the weight of the dried product is measured, and the weight of the dried product relative to the weight of the rubber initially placed in the basket is expressed as a percentage.

 The method for producing the carboxylated nitrile group-containing highly saturated copolymer rubber used in the present invention is not particularly limited, but a preferable method is a rubber temperature of 200 to 280 ° C. in a heat-sealing kneader. In the range of C, there can be mentioned a method of performing an ene-type addition reaction between a nitrile group-containing highly saturated copolymer rubber and an ethylenically unsaturated carboxylic acid or an anhydride thereof.

 The nitrile group-containing highly saturated copolymer rubber used for producing the carboxylated nitrile group-containing highly saturated copolymer rubber used in the present invention is an ethylenic unsaturated nitrile conjugated gen-based copolymer. It is a hydrogenated conjugated unit of rubber.

In the highly saturated copolymer rubber containing a ditolyl group, the content of the bound ditolyl unit (ie, the monomer unit derived from ethylenically unsaturated ditolyl) is usually 10 to 6%. 0% by weight, preferably 15 to 40% by weight, the iodine value is usually 80 or less, preferably 60 or less, and the Mooney viscosity (ML _{1 + 4} , 100 ° C.) Usually, it is 30 to 300, preferably 50 to 200, more preferably 60 to 150.

If the iodine value is too large, the heat resistance and strength of the crosslinked product will decrease. The lower limit of the iodine value is not particularly limited, but if the iodine value is excessively low, crosslinking of the mixed composition may be difficult. Can be. If the viscosity is too low, the durability of the crosslinked product under high pressure will be insufficient, and the compression set and crushing (compression relaxation> will not be improved. Also, if the Mooney viscosity is too large, Workability during kneading deteriorates.

 The ethylenically unsaturated nitrile-1 conjugated gen-based copolymer used for producing the nitrile group-containing highly saturated copolymer rubber usually contains ethylenically unsaturated nitrile and a conjugated gen. Obtained by polymerizing a monomer mixture.

 Specific examples of ethylenically unsaturated nitriles include ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile, black acrylonitrile, and methoxyacrylonitrile. Of these, acrylonitrile is preferably used. The amount of the ethylenically unsaturated nitrile is usually from 10 to 60% by weight in the monomer mixture.

 Specific examples of the conjugated diene include 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, and chloroprene. Of these, 1,3-butadiene is preferably used. The amount of synergist is usually from 40 to 90% by weight in the monomer mixture. When 1,3-butadiene and isoprene are used in combination as the conjugated gene (that is, in the case of isoprene butadiene-acrylonitrile copolymer rubber), the bond 1,3-butadiene in the bonded conjugated gen unit is usually used. The unit content is 30 to 70% by weight, and the bound isoprene unit content is 70 to 30% by weight.

The nitrile group-containing highly saturated copolymer rubber has, in its structure, ethylenically unsaturated nitrile and an ethylenically unsaturated monomer unit which can be co-polymerized with a conjugated diene. May be contained in the range of 0 to 50% by weight.

 Examples of ethylenically unsaturated monomers copolymerizable with unsaturated nitrile and conjugated diene include vinyl aromatic compounds such as styrene and α-methylstyrene;

Methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, methyl methacrylate, methyl methacrylate, butyl methacrylate, butyl methacrylate, propyl maleate, maleic acid Dimethyl, getyl maleate, dipropyl maleate, di-n-butyl maleate, diisobutyl maleate, di-maleic acid η-pentyl, di-maleic acid η-hexyl, di-maleic acid 2-ethylhexyl, dimethyl fumarate, getyl fumarate, dipropyl fumarate, di-i-fumarate-butyl, diisobutyl fumarate, di-i-fumarate η-pentyl, di-fumarate η-hexyl, di-fumarate 2-Ethylhexyl, dimethyl itaconate, getyl itaconate, dipropyl itaconate, di-itaconate η— Tyl, diisobutyl itaconate, di-η-pentyl itaconate, di-η-hexyl itaconate, di-2-ethyl hexyl itaconate, dimethyl citrate, getyl citrate, dipropyl citrate, Di-tert-butyl citrate, di-isobutyl citrate, di- citrate dia-pentyl, pentyl, di-di- citrate-hexyl hexyl, di-2-ethyl citrate-hexylhexyl, dimethyl mesaconate, mesacone Getyl acid, dipropyl mesaconate, di-η-butyl mesaconate, diisobutyl mesaconic acid, di-η-mesaconate pentyl, di-mesaconate _η-hexyl, di-2-methylhexyl mesaconate, glutaconic acid Dimethyl, dipropyl glutaconic acid dipropyl daltaconate, di-glutaconic acid η-butyl, gluta Phosphate Diisobutyl, di-glutaconate n-pentyl, di-glutaconate n-hexyl, di-glutaconate 2-ethylhexyl, dimethyl arylmalonate, getyl arylmalonate, dipropyl arylmalonate, di-n-butyl arylmalonate, Diisobutyl arylmalonate, di-n-butyl arylmalonate, di-n-hexyl arylmalonate, di-2-ethylethyl arylmalonate, dimethyl terraconate, dimethyl terraconate, dipropyl terraconate, dipropyl terraconate, di-n-butyl terraconate, Ethylenic unsaturated carboxylic acid alkyl esters such as diisobutyl terraconate, di-n-pentyl terraconate, di-n-hexyl terraconate, and di-2-ethyl terraconate;

 Ethylenically unsaturated carboxylic acid alkoxyalkyl esters such as methoxyacrylate, ethoxyquinacrylate, and methoxyethoxylate;

 -And /-cyanoethyl acrylate, α-, /-and-acrylopropyl acrylate, cyanobutyl acrylate, cyanobutyl acrylate, α-and / 5-cyanoethyl methacrylate, H, / S— and cyanopropyl methacrylate, cyanobutyl methacrylate, cyanooctyl methacrylate, etc .; ethylenically unsaturated alkyl cyano-substituted alkyl esters of carboxylic acids;

 Ethylenic unsaturated carboxylic acids such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyhexyl methacrylate, hydroxypropyl methacrylate Acid hydroxyl group-substituted alkyl esters;

Acrylamide, methacrylamide, Ν—methylolacrylamide. N, N-dimethylol acrylamide, N-ethoxyquin methyl acrylamide, N-methylol methacrylamide, N, dimethylol methacrylamide, N-ethylenic acrylate such as methyl methacrylamide Saturation amide;

 Non-conjugated diene such as vinyl norbornene, dicyclopentadiene, 1,4-hexadiene;

 Ethylenically unsaturated carboxylic acid fluoroalkyl esters;

And the like.

 Specific examples of the ethylenically unsaturated nitrile-conjugated gen-based copolymer rubber include acrylonitrile-butadiene copolymer rubber (NBR), acrylonitrile-butadiene-isoprene copolymer rubber (NBIR), and acrylonitrile Monoisoprene copolymer rubber (NIR), acrylonitrile butadiene butoxyacrylate copolymer rubber, acrylonitrile butadiene acrylate copolymer rubber, acrylonitrile butadiene acrylate copolymer Rubber and the like. Of these, NBR is preferably used.

 Such an ethylenically unsaturated nitrile-conjugated gen-based copolymer rubber is usually used in combination with an ethylenically unsaturated nitrile and a conjugated gen in the presence of a radical polymerization initiator, if necessary, using a molecular weight modifier as necessary. It is prepared by copolymerizing with other ethylenically unsaturated monomers according to the formula. As the radical polymerization initiator to be used,

 Persulfates such as potassium persulfate and ammonium persulfate;

4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis-1-methyl-N-1, 1-bis (hydroxymethyl) 1-2-hydroxyoxethyl propioamide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1, 1'-azo compounds such as azobis (1-cyclohexanecarbonitrile);

 Methylethylperoxide, cupramoxide, di-t-butylvaloxide, acetylperoxide, dicumylvaoxide, lauroylperoxide, benzoylperoxide, t-butylvaloxy1-2-ethylhexanoate, di-1 Peroxides such as isopropyl peroxydicarbonate and di-tert-butyloxy-isophthalate; and the like. Also, a redox initiator obtained by combining these polymerization initiators and a reducing agent can be used.

 The amount of the polymerization initiator is usually 0.005 to 3 parts by weight based on 100 parts by weight of the monomer mixture. The polymerization temperature varies depending on the type of the initiator, but is usually from 0 to 100 ° C.

Examples of the molecular weight modifier include 2,2 ', 4,6,6'-pentamethylheptane-1-thiol, 2,4,4-trimethylpentane-12-thiol, dodecane-12-thiol, 2,2,2 Alkyl thiol compounds such as 6,6—tetramethylheptane-1-methanthiol, 2,4,6-trimethylnonane-1-thiol, and the like; dimethylxanthogen disulfide, getylxanthogen disulfide, diisopropylxanthogen disulfide, and the like Xanthogen disulfides such as: thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide; halogenated hydrocarbons such as carbon tetrachloride and brominated ethylene. Pentaphenyle And hydrocarbons such as acetonitrile; acrolein, methacrolein, arylacryl, 2_ethylhexylthioglycolate, terpinolene, α-terbinene, alterbinene, dipentene, α-methylstyrene dimer (2-4-diphenyl) Lou 4 —Methyl-1 More than 50% by weight of pentene is preferred), 2,5-Dihydrofuran, 3, 6—Dihydro2 2-pin, phthalane, 1,2-butadiene, 1,4 _ Hexadene and the like. The amount of the molecular weight modifier is usually 0.005 to 3 parts by weight based on 100 parts by weight of the monomer mixture.

 The method of polymerization is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like can be appropriately selected as needed. Among them, emulsion polymerization is preferred. In the case of production by emulsion polymerization, for example, polymerization is carried out by a known emulsion polymerization technique, and when a predetermined conversion is reached, hydroxylamine, sodium carbamic acid, etc. are added to terminate the polymerization, and then the remaining The monomers are removed by heating, steam distillation, etc., and the obtained polymer latex is further coated with a coagulant used in ordinary emulsion polymerization, such as an inorganic coagulant, a polymer coagulant, or a thermosensitive coagulant. In addition, the copolymer can be coagulated and recovered.

 The method for hydrogenating the conjugated gen unit of the ethylenically unsaturated nitrile conjugated gen-based copolymer rubber is not particularly limited, and is carried out by using a usual hydrogenation method.

 Specifically, the reaction is carried out by blowing hydrogen in the presence of a hydrogenation catalyst in a state in which the ethylenically unsaturated nitrile conjugated gen-based copolymer rubber is dissolved in a solvent.

The solvent dissolves the ethylenically unsaturated nitrile conjugated gen-based copolymer rubber. It is solvable. Specific examples include aromatic compounds such as benzene, toluene, xylene, and chlorobenzene; ketones such as cyclohexanone, acetone, methylethyl ketone, and getyl ketone; tetrahydrofuran; ethyl acetate; dimethylformamide, and the like. . Examples of the hydrogenation catalyst include palladium / silica and a palladium complex (JP-A-3-252405). Further, Japanese Patent Application Laid-Open Nos. Sho 62-125258, Sho-62-42937, Sho-114-542, Sho-54-403 Rhodium or ruthenium compounds, such as those described in JP-A-144454, JP-A-145405 and the like, can also be used.

 The hydrogenation reaction temperature is usually 5 to 150 ° C., preferably 10 to: L 0 crc. At high temperatures, the hydrogenation catalyst is deactivated or side reactions are more likely to occur. Examples of the side reaction include a reaction in which a nitrile group is hydrogenated.

 The ethylenically unsaturated carboxylic acid or its anhydride used for producing the carboxylated nitrile group-containing highly saturated copolymer rubber is not particularly limited, but the ethylenically unsaturated dicarboxylic acid having 4 to 10 carbon atoms is used. Acids or their anhydrides, especially maleic anhydride, are preferred.

Examples of the ethylenically unsaturated carboxylic acids include ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; and maleic anhydride. Monoethyl maleate, monoethyl maleate; monopropyl maleate, mono-n-butyl maleate, and molybdate maleic acid, such as ethyl anhydride, citraconic anhydride, and citraconic anhydride; Monoisobutyl, mono-maleic acid n-pentyl, mono-maleic acid n-hexyl, mono-maleic acid-2-ethylhexyl, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monopropyl fumarate, mono-n-butyrate Mono-isobutyl fumarate, mono-n-fumarate, mono-n-pentyl, mono-n-hexyl fumarate, mono-2-ethylhexyl fumarate, monomethyl itaconate, monoethyl itaconate, monoethyl itaconate, monopropyl itaconate Mono-n-butyl, monoisobutyl itaconate, mono-n-itaconate n-pentyl, mono-n-itaconate n-hexyl, mono-2-ethyl itaconate, monoethyl citrate, monomethyl citrate, monoethyl citrate, and citracone Monopropyl acid, mono-n-butyl citraconic acid, citraconic acid Monoisobutyl, mono-n-citraconic acid n-pentyl, mono-n-hexyl citraconic acid, mono-2-ethyl citraconic acid, mono-methylhexyl citrate, monomethyl mesaconic acid, monoethyl mesaconic acid, monopropyl mesaconic acid, mono-mesaconate n-butyl, monoisobutyl mesaconic acid, mono-mesaconate n-pentyl, mono-mesaconate n-hexyl, mono-mesaconate-2-ethylenohexyl, monomethyl glutaconate, monoethyl glutaconate, monopropyl glutaconate, glutacon Mono-n-butyl acid, mono-isobutyl glutaconate, mono-n-glutaconic acid pentyl, mono-n-hexyl gluconate, mono-2-ethyl glutaconic acid, monomethyl arylmalonate, monomethyl arylmalonate, monoethyl arylmalonate , Arylmalonic acid monopro Mono-n-butyl arylmalonate, mono-isobutyl arylmalonate, mono-n-arylmalonic acid n-pentyl, mono-n-hexyl arylmalonate, mono-2-ethylhexyl arylmalonate, monomethyl terraconate, monomethyl terraconate, monoethyl terraconate, Monopropyl terraconate, terra Monoalkyl esters of unsaturated dicarboxylic acids such as mono-n-butyl monoconate, mono-isobutyl terraconate, mono-n-pentyl terraconate, mono-n-hexyl terraconate, mono-2-ethyl terraconate-ethylhexyl, etc. No.

 The carboxylated nitrile group-containing highly saturated copolymer rubber can be produced, for example, by subjecting the nitrile group-containing highly saturated copolymer rubber to an ethylenically unsaturated carboxylic acid or an anhydride thereof by an ene-type addition reaction. can get.

 The addition-type addition reaction is usually performed by kneading the nitrile group-containing highly saturated copolymer rubber and the ethylenically unsaturated carboxylic acid or its anhydride at a high temperature without using a radical generator. Occur.

 The use of a radical generator causes gel formation and an increase in the Mooney viscosity of the rubber, and radical addition of an ethylenically unsaturated carboxylic acid or its anhydride to a nitrile group-containing highly saturated copolymer rubber. Since a reaction occurs, it becomes impossible to carry out an ene-type addition reaction.

 The amount of the ethylenically unsaturated carboxylic acid or the anhydride thereof is not particularly limited, but usually, the amount of the ethylenically unsaturated carboxylic acid or the anhydride is 100 parts by weight of the nitrile group-containing highly saturated copolymer rubber. The anhydride is contained in an amount of 0.05 to 10 parts by weight, preferably 0.2 to 6 parts by weight.

In an addition-type addition reaction, for example, when an open-type kneader such as a roll-type kneader is used, molten ethylenically unsaturated carboxylic acid such as maleic anhydride or the anhydride thereof is scattered. However, sufficient addition reaction may not be performed. When a continuous kneader such as a single-screw extruder, a co-rotating twin-screw extruder, or a contra-rotating twin-screw extruder is used, the rubber staying at the outlet of the extruder is gelled and the die is formed. Head clogging occurs And the addition reaction cannot be performed efficiently. In addition, a large amount of unreacted ethylenically unsaturated carboxylic acid or its anhydride remains in the rubber. In the end-type addition reaction, it is preferable to use a heated closed kneader. The heating and mixing kneader can be arbitrarily selected from batch-type heating and mixing kneaders such as a pressure kneader, a Banbury mixer, a Brabender and the like, and among them, a pressure kneader is preferable.

 In the above production method, first, before the ethylenically unsaturated carboxylic acid or its anhydride is added to the nitrile group-containing highly-saturated copolymer rubber by the ene-type addition reaction, the ene-type unsaturated carboxylic acid or the substantially unsaturated carboxylic acid is added. At a rubber temperature at which the addition reaction does not occur, specifically, at 60 to 170 ° C, preferably at 100 to 150 ° C, the ethylenically unsaturated carboxylic acid or its anhydride Pre-kneading the nitrile group-containing highly saturated copolymer rubber and uniformly dispersing the ethylenically unsaturated carboxylic acid or anhydride in the nitrile group-containing highly saturated copolymer c If the temperature is too low, the rubber slips in the kneader, and it may not be possible to mix the ethylenically unsaturated carboxylic acid or its anhydride with the nitrile group-containing highly saturated copolymer rubber sufficiently. . If the pre-kneading rubber temperature is too high, a large amount of the ethylenically unsaturated carboxylic acid or its anhydride to be charged into the kneader may be scattered, and the ene-type addition reaction rate may decrease. is there.

Next, the temperature of the mixture of the rubber being kneaded and the ethylenically unsaturated carboxylic acid or its anhydride (hereinafter, sometimes referred to as rubber temperature) is usually set at 200 to carry out the ene-type addition reaction. 2280 ° C., preferably 220 ° -260 ° C. The method of maintaining the rubber temperature is not particularly limited, but usually, a method of flowing hot water or steam through a jacket of the kneader, or a method of generating heat by shearing is used. Achieved by using

When hot water or steam is allowed to flow through the jacket of the heated kneader, the jacket temperature is generally maintained at 70 to 250 ° C, preferably 130 to 200 ° C. When utilizing the heat generated by shearing, it is preferable to continue the kneading at a shear rate of 30 to: L 000 S—preferably 300 to 700 S— ^{1 using} a kneader. In particular, it is preferable to use the heat generated by shearing because the rubber temperature can be easily controlled. The kneading time in the heated closed kneader is not particularly limited, but is usually 120 seconds to 120 minutes, preferably 180 seconds to 60 minutes.

 If the rubber temperature during kneading is excessively low, the ene-type addition reaction may not proceed sufficiently. If it is excessively high, gelling or burning may occur, and as a result, the gel may be mixed into the product and may be preferred. On the other hand, if the shear rate is excessively high, it is difficult to control the rubber temperature due to the heat generated by the shearing, and the rubber temperature becomes too high to cause gels and burns, which is not preferable as an industrial production method. On the other hand, if the shear rate is excessively low, the rubber temperature becomes too low, so that a sufficient ene-type addition reaction cannot be expected. In the ene-type addition reaction, gelling of rubber and increase in Mooney viscosity can be prevented by adding an antioxidant during kneading. The type of anti-aging agent is not particularly limited, but an anti-aging agent for amines, amine ketones, phenols, benzimidazoles and other rubbers can be used.

Examples of amide-based antioxidants include polyvinyl 11-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4-bis (α, α-dimethylbenzyl) diphenylamine, ρ— (Ρ— Torr Ensulfonylamide) Diphenylamine, N, N-Gee 2-Naphthylene P-phenyleneamine, N, N-Diphenylene p-phenyleneamine, N-Felinel N— Isopropyl_p-phenylenediamine, N-phenyl-N- (1,3-dimethylbutyl) -p-phenylenediamine, N-phenylenediamine N- (3-methacryloyloxy-2-hydroxypropyl) p —Phenylene diamine and the like.

 Examples of amine ketone anti-aging agents include 2,2,4-trimethyl-1,2, -dihydroquinoline and 6-ethoxy-11,2-dihydro-1,2,2,4 And methylquinoline.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2-methylenebis (4-ethylphenyl). — Tert-butylphenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), 4,4-butylidenebis (3-methyl-16-tert-butylphenol), 4,4-thiobis (3 - methyl one 6- tert- Buchirufuwenoru), 2, 5-di-one tert one Buchiruhai mud quinone, 2, as an example of a _c Benzoi Midazo Ichiru based antioxidant 5- di tert- Amiruhai Dorokino emissions and the like are And 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and metal salts of 2-mercaptomethylbenzimidazole.

 The amount of the antioxidant used is usually 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of rubber.

According to the above-mentioned production method, usually, 80% or more of the charged amount of the ethylenically unsaturated carboxylic acid or its anhydride used in the ene-type addition reaction is reduced to two or more. And the unreacted ethylenically unsaturated carboxylic acid or anhydride remaining in the rubber can be reduced to 5% or less of the charged amount. Therefore, this method is extremely useful for industrially stable production.

 The thermoplastic resin used in the present invention includes a polymer exhibiting thermoplasticity and a thermoplastic polymer composition.

Specific examples of the thermoplastic resin include, for example, ABS resin, AES resin, MSB resin, AS resin, polystyrene, HIPS, styrene-mono-maleic anhydride copolymer, styrene-acrylonitrile-N-substituted maleide copolymer Copolymers, aromatic vinyl polymers such as styrene-methacrylic acid copolymers; polymethyl methacrylate, methyl methacrylate-to-styrene copolymer, methyl methacrylate-styrene-N-substituted maleimide copolymer, etc. Acrylic polymers such as 6-nylon, 46-nylon, 66-nylon, 11-nylon, 12-nylon, 61-nylon, 61-nylon, etc. Polymer: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. Polyolefin polymers such as polyethylene, polypropylene, polybutene-11; thermoplastic resins such as polycarbonate, polyphenylene ether, polyoxymethylene, polyphenylene sulfide, fluororesin; polyester elastomer , Polyamide elastomer, Polyamide polyester elastomer, Hydrogenated styrene-butadiene-styrene triblock copolymer elastomer, Styrene-butadiene-styrene triblock copolymer elastomer, Hydrogenated styrene-isoprene disulfide Thermoplastic elastomers such as copolymer elastomers and thermoplastic polyurethanes; Polymer compositions consisting of polystyrene and polyphenylene ether; Polymer compositions consisting of ABS resins and thermoplastic polyurethanes

A polymer composition consisting of ABS resin and polyamide; a polymer composition consisting of ABS resin and polycarbonate; a polymer composition consisting of polyamide and polyester; consisting of polypropylene and ethylene-propylene copolymer rubber. And a polymer composition.

 Among the thermoplastic resins, preferred are aromatic vinyl polymers, acryl polymers, polyamide polymers, polyester polymers, polycarbonate resins, polyether polymers, polyurethane polymers, polyvinylidene chlorides. It is at least one kind of thermoplastic resin selected from the group consisting of resin and fluororesin.

Particularly preferred are ABS resin, AES resin, MBS resin, AS resin, styrene-mono-maleic anhydride copolymer, 111-nylon, 121-nylon, 61-nylon, polyamide elastomer, Examples include polyester elastomer, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyoxymethylene, thermoplastic polyurethane, and polyvinylidene chloride. The thermosetting resin used in the present invention is a synthetic resin that is produced using a low-molecular-weight monomer as a raw material and that cures when heated. Specific examples of the thermosetting resin include bisphenol A type, brominated bisphenol A type, brominated novolak type, phenol novolak type, polyglycidyl amine type, alcohol type, ester type, and alicyclic type. Various epoxy resins; Xylene resin; Guanamin resin; Diaryl phthalate resin; Sterol resin; phenol resin; unsaturated polyester resin; furan resin: polyimide; poly (P-hydroxybenzoic acid)-; polyurethane; maleic acid resin; melamine resin; urea resin. Among the thermosetting resins, an epoxy resin, a phenol resin and an unsaturated polyester resin are preferred.

 The thermoplastic resin or the thermosetting resin and the carboxylated nitrile group-containing highly saturated copolymer rubber are usually used in an amount of 10 to 90% by weight, preferably 20 to 8% by weight of the thermoplastic resin or the thermosetting resin. 0% by weight, more preferably 30 to Ί0% by weight, 90 to 10% by weight, preferably 80 to 20% by weight, more preferably 90 to 10% by weight of a highly saturated copolymer rubber containing a carboxylated nitrile group It is used in a proportion of 70 to 30% by weight. If the amount of the thermoplastic resin or the thermosetting resin is too small, the mixed composition does not exhibit the properties as a resin and the workability is remarkably poor. On the other hand, if the amount is too large, the mixed composition does not exhibit the properties as rubber, and the performance as rubber is inferior.

The mixed composition of the synthetic resin and the rubber of the present invention has good compatibility between the resin and the rubber, and may further be combined with another heat-resistant rubber if necessary. Although the ratio of the heat-resistant rubber is not particularly limited, it is combined in the range of 100 to 500 parts by weight, preferably 50 to 300 parts by weight with respect to 100 parts by weight of the mixed composition of the present invention. be able to. Here, the heat-resistant rubber is a rubber generally known as a rubber having heat resistance in the rubber industry. This rubber is called a special rubber, while natural rubber and the like are called general-purpose rubbers, and is usually 10 to 200, preferably −20 to 150, and furthermore, It preferably has a viscosity of 30 to 100. Examples include nitrile group-containing unsaturated copolymer rubber or its hydrogenation. Rubber, ethylene-based saturated copolymer rubber, polyacrylate copolymer rubber, polyether rubber, fluorine rubber and the like. These heat-resistant rubbers can be used in combination of two or more different rubbers.

 Specific examples of the nitrile group-containing unsaturated copolymer rubber or its hydrogenated rubber may be the same as those described above.

 The ethylene-based saturated copolymer rubber is a substantially saturated copolymer rubber composed of ethylene, polyolefin, and non-co-functional agent. Typical examples are ethylene-propylene-non-conjugated gen terpolymer or multi-polymer rubber, ethylene-propylene_1-butene-non-conjugated-gen copolymer rubber, ethylene-1-1-butene-non-conjugated gen-multipolymer Low crystalline or amorphous elastomers having a degree of crystallinity of 20% or less, preferably 10% or less, mainly composed of ethylene such as rubber and one-year-old fins having 3 to 14 carbon atoms, or the like. These are mixtures. Among them, ethylene-propylene-non-conjugated gen terpolymer rubber is preferable. Here, as the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, 5-ethylidene-12-norbornene and the like are used. Of these, dicyclopentadiene and 5 — Copolymers having ethylidene-2-norbornene as the third component are preferred.

 The iodine value of these ethylene-α-olefin-based copolymer rubbers is preferably 20 or less.

In these ethylene-based saturated copolymer rubbers, the molar ratio of ethylene units / α-refin units is usually 50Ζ50 to 90Ζ10, preferably 6ΟΖΑθδΖΙ6, and (ethylene + α-refin) The molar ratio of units Ζ non-conjugated gen units (for ternary or multi-component copolymers) is usually 9 8 Z 2 to 9 0 Z 10, preferably 9 7 Z 3 to 9 4 Z 6.

 The polyacrylate copolymer rubber is composed of units derived from an alkyl acrylate having an alkyl group having 8 or less carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, and / or methoxy methyl acrylate. It is a copolymer rubber containing at least 80 mol% or more of units derived from an alkoxyalkyl acrylate having an alkoxyalkyl group having 8 or less carbon atoms such as a rubber.

 Monomers to be copolymerized include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyl pyridine; and fluoroalkyl vinyl ethers (for example, fluoroethyl vinyl ether and fluoropropyl). Vinyl ether, trifluoromethyl vinyl ether, trifluoroethyl vinyl ether, perfluoropropyl vinyl ether and perfluoromethyl vinyl ether), 0- or ρ — trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, Fluorine-containing vinyl monomers such as tetrafluoroethylene; unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, and maleic acid; Their anhydrides; (Meth) acrylates such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, epoxy (meth) acrylate, and polyurethane (meth) acrylate are listed. Can be

Further, a monomer which is usually used as a crosslinkable monomer of a polyacrylate polymer rubber can be copolymerized. Monomers that can be used include 2-chloroethyl vinyl ether, vinyl acetate, Active chlorine-containing unsaturated monomers such as aryl chloride acetate, vinyl benzyl chloride, 2-chloroethyl vinyl ether, chloromethyl vinylketone-, 5-chloromethyl-2-nornorpolene; 2-chloroethyl vinyl ether Such inert chlorine-containing unsaturated monomers; and epoxy group-containing unsaturated monomers such as daricidyl acrylate, glycidyl methacrylate, aryl glycidyl ether, and vinyl glycidyl ether. In addition, a carboxyl group-containing unsaturated monomer can also be used. Among these monomers, an active base-containing unsaturated monomer is preferred.

 Among the above polyacrylic acid ester-based polymer rubbers, in particular, 90 mol% or more, preferably 95 mol% or more of the ethyl acrylate unit, and 10 mol% or less of the monomer unit copolymerizable therewith. Preferably, a copolymer containing 5 mol% or less as a structural unit and containing substantially no carbon-carbon unsaturated bond is desirable. When such an ethyl acrylate copolymer is used, it is possible to obtain a rubber composition having high heat resistance and hardly causing hardening deterioration even when held for a long period of time. Monomers used for copolymerization with ethyl acrylate to obtain such an ethyl acrylate copolymer include, in addition to carbon-carbon double bonds involved in copolymerization with ethyl acrylate, Is a monomer having substantially no carbon-carbon double bond (excluding benzene ring).

Generally, unsaturated compounds having a carbon-carbon double bond in addition to the carbon-carbon double bond involved in copolymerization with acrylate (eg, butadiene, 2-butenyl acrylate, tetrahydrobenzyl acrylate) Rate, aryl acrylate, triallyl isocyanurate, divinylbenzene, etc.) Is also used as a crosslinking component of acrylic rubber. However, such an unsaturated compound having a carbon-carbon double bond can usually be used, but accelerates hardening-type deterioration, so that it is used in applications requiring high heat resistance. Not always available.

 The polyether-based rubber is a polymer or copolymer of at least one monomer selected from the group consisting of epichlorohydrin and alkyloxysilane having 2 to 10 carbon atoms, and a copolymer with these monomers. A maximum of 10 mol% of the possible unsaturated bond-containing epoxy compound (the copolymer composition of the monomer and the unsaturated bond-containing epoxy compound is 100 mol%).

 Specific examples of the alkyloxylan having 2 to 10 carbon atoms include oxysilane, methyloxylan, ethyloxylan, propyloxylan, butoxyloxylan, hexyloxylan, octyloxylan and the like. Of these, oxolane (ethylene oxide) and methyloxylan (propylene oxide) are preferred, and methyloxylan is particularly preferred.

Examples of the unsaturated bond-containing epoxy compound copolymerizable with these monomers include aryl glycidyl ether, vinyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, glycidyl itaconate, and the like. Of these, aryl glycidyl ether is preferred. Specific examples include polychlorohydrin rubber, epichlorohydrin-ethylene oxide copolymer rubber, epichlorohydrin-ethylene oxide monoaryl glycidyl ether copolymer rubber, epichlorohydrin-ethylene ethylene oxide propylene oxide copolymer rubber. United rubber, epik Rolhydrin-ethylene oxy-do-propylene oxy-dolyl glycidyl ether copolymer rubber, propylene oxai-doaryl glycidyl ether copolymer rubber, and the like.

Examples of fluororubbers include vinylidene fluoride, hexafluoropropene, pentafluorofluorene, trifluoroethylene trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinylfluoride, perfluoro (methyl vinyl ether), In addition to copolymer rubbers composed of a combination of fluorine-containing monomers such as perfluoro (propylvinylidene), etc., these fluorine-containing monomers and monomers copolymerizable therewith (for example, acrylic acid esters, etc.) Copolymer rubbers with vinyl compounds, olefin compounds such as propylene, gen compounds, halogen-containing vinyl compounds, etc. _c Examples of such fluororubbers include vinylidene fluoride-trifluorene chloroethylene. Rene copolymer, vinylidene fluoride hexafluoropropylene copolymer rubber, vinylidene fluoride hexafluoropropylene monotetrafluoroethylene terpolymer rubber, tetrafluoroethylene titanium propylene copolymer rubber And terpolymer tetrafluoroethylene-vinylidene fluoride-propylene terpolymer rubber.

Specific examples of the fluororubber include a type that crosslinks with a combination of an organic peroxide and a crosslinker but does not crosslink with a polyol or amine crosslinker, such as JSR Afras 150P (Japan Synthetic rubber); Eve that hardly crosslinks with organic peroxides but crosslinks with polyols or amines, such as Viton A, B and E60C (manufactured by Dupont); technofuron (Monte Edison) Manufactured), and the like. Further, as a heat-resistant rubber, a high-strength elastomer composition obtained by blending an ethylenically unsaturated carboxylic acid metal salt with a nitrile group-containing highly saturated copolymer rubber (for example, see Japanese Patent Application Laid-Open No. 644 publication) can be used to obtain a heat-resistant rubber mixture having higher strength.

 As such a metal salt of an ethylenically unsaturated carboxylic acid, one having an ion-bonded structure of an ethylenically unsaturated carboxylic acid having 5 or less carbon atoms having 1 or more carboxyl groups and a metal is used. .

 Examples of the ethylenically unsaturated carboxylic acids include monocarboxylic acids such as acrylic acid and methacrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; monomethyl maleate and monoethyl itaconate; Monoester compounds having an alkyl group having 1 to 8 carbon atoms of such unsaturated carboxylic acids, and the like.

 The metal is not particularly limited as long as it forms a salt with the above-mentioned ethylenically unsaturated carboxylic acid, but is usually zinc, magnesium, calcium, potassium, titanium, chromium, iron, cobalt, nickel, aluminum, silver. , Lead, etc. can be used. Among these, zinc, magnesium, calcium and aluminum are suitable from the viewpoint of strength properties, and zinc is particularly preferable.

 The molar ratio between the ethylenically unsaturated carboxylic acid and the metal is preferably in the range of 1Z0.5 to 1Z3.

These metal salts of ethylenically unsaturated carboxylic acids are usually blended into the elastomer in the form of a metal salt when an elastomer composition is produced by mixing and kneading with other components. However, an operation such as kneading the ethylenically unsaturated force rubonic acid and the oxide, hydroxide or carbonate of the metal is performed. The metal salt may be generated in situ by reacting in the reaction.

 The amount of the metal salt of the ethylenically unsaturated carboxylic acid is not particularly limited, but is usually 3 to 120 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 1 to 100 parts by weight of the elastomer. It is in the range of 0 to 60 parts by weight. An excessively small amount or an excessively large amount is not preferred because the strength properties of the elastomer product are inferior.

 Various components are added to the mixed composition of the present invention depending on the use. Generally, a crosslinking agent, other rubber components, resin components, and the like can be added. Other common compounding agents used in the rubber field, such as reinforcing agents (carbon black, silica, talc, etc.), fillers (calcium carbonate, clay, etc.), processing aids, process oils, other An antioxidant, an ozone deterioration inhibitor, a silane coupling agent, a coloring agent, and the like can be added.

 In particular, by combining a sulfur-based crosslinking agent or an organic peroxide-based crosslinking agent as the crosslinking agent, a good crosslinking composition can be obtained.

 Examples of sulfur-based crosslinkers include sulfur, such as powdered sulfur, sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, and the like. Do,

N, N'-Sulfur compounds such as dithio-bis (hexahydro-1H-azevinone-12), phosphorus-containing polysulfides, high-molecular polysulfides, etc .; and -tetramethylthiuram disulfide, dimethyldisulfide Crosslinking accelerators containing sulfuric acid such as selenium thiocarbamate and 2- (4′-morpholinodithio) benzothiazole can be mentioned.

Furthermore, in addition to these sulfur-based crosslinking agents, zinc oxide, zinc peroxide, active Crosslinking accelerators such as reactive zinc, stearate, etc .; guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, xanthate, etc. Other crosslinking accelerators can be used.

 The amount of the sulfur-based crosslinking accelerator used is not particularly limited, but is usually a mixed composition.

The amount is 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight.

 Examples of the organic peroxide crosslinking agent include, for example, t-butyl hydroperoxide, cumene hydroperoxide, g-t-butyl peroxide, t-butylcumylperoxide, 2,5-dimethyl-t-butylperoxyquinhexane, 5-dimethyl-t-butylperoxyhexine, 1,3-bis (t-butylperoxyisopropyl) benzene, p-chlorobenzoylperoxide, t-butylperoxybenzoate, t-butyl Examples include peroxysopropyl carbonate and t-butyl benzoate. The amount of the organic peroxide-based crosslinking agent to be used is generally from 0.01 to 30 parts by weight, preferably from 0.1 to 10 parts by weight, per 100 parts by weight of the mixed composition.

Other usable crosslinking agents include polyfunctional compounds such as trimethylolpropane trimethacrylate, divinylbenzene, ethylenedimethacrylate and triaryl isocyanurate. In addition, metal-sulfur-based, triazine / dithio-ammonium salt-based, polycarboxylic acid-onium salt-based, and polyamine-based (hexamethylene diamine-triethylene tetramin, hexamethylene diamine) , Ethylenediamine carbamate, triethyleneamine, etc.), benzoic acid A cross-linking agent such as a monium salt can be used in combination, if necessary.

 The method for producing the mixed composition of the present invention is not particularly limited. However, when the thermoplastic resin and the carboxylated nitrile-containing highly saturated copolymer rubber are mixed, a conventional mastication apparatus such as a rubber mill or a brassier is used. It can be carried out using a ender mixer, a Banbury mixer, a pressurized screwdriver, a twin screw extruder, or the like. These devices, whether of the closed type or the open type, are preferably of the type that can be replaced by an inert gas. The kneading temperature must be a temperature at which all the components to be mixed are melted, and is usually in the range of 150 to 350 ° C, preferably in the range of 170 to 300 ° C. On the other hand, when the thermosetting resin and the carboxylated nitrile-containing highly saturated copolymer rubber are mixed, usually, a low-molecular-weight monomer, a curing agent, etc. are mixed with the carboxylated nitrile-containing highly saturated copolymer rubber. A method is employed in which a homogeneous mixture is first prepared and then a hardening reaction is performed to produce the mixture.

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. Parts and% in Reference Examples, Examples and Comparative Examples are based on weight unless otherwise specified.

The test methods for the physical properties described in each example are as follows ₍ (1) Impact test

 According to JISK 711, the test was carried out at room temperature by the Izod impact strength test method (with notch) (unit: kgfZcm).

 (2) Tensile test

For a mixed composition of thermoplastic resin and hydrogenated NBR, the diameter is 2 Om The resin and rubber are melt-kneaded at 240 ° C to 350 ° C using a twin-screw extruder of m to form a mixed composition, dried at 80 ° C for 12 hours, and then formed as a vertical molding machine. Using an injection molding machine (Yamashiro Seiki Seisakusho, SAV-30Z30), a test piece for measuring physical properties was prepared at 240 ° C (mold temperature 50 ° C), and a tensile test [tensile strength (kgf Zcm ² ), 100% tensile stress (kgf / cm ² ), elongation (%)]. The hardness was measured using a JIS spring type A hardness tester.

 (3) Heat resistant adhesive test

 For epoxy resin and phenolic resin, prepare an adhesive solution with the composition shown in Table 7 and dry the adhesive layer on polyimide film (50 / m thickness, manufactured by Kapton Dupont) to a thickness of 25 z / m, and dried at 120 ° C. for 10 minutes to prepare a test tape.The heat-resistant adhesive test for electronic components was performed according to the method described in JP-A-4-1370183. Was conducted.

 Attach the test tape to a 42-pin, 42 alloy lead frame with a width of 1.5 mm mx 10 mm in length, tap for 0.3 seconds at a temperature of 200 ° C and a pressure of 4 kgf / cm2. The adhesive strength at room temperature immediately after taping and the adhesive strength after heating at 250 ° C for 1 hour (the adhesive strength after thermal history) were measured.

(4) Measurement of acid equivalent and carboxylic acid addition rate

The rubber is dissolved in acetone, purified by reprecipitation with n-hexane, and the resulting reprecipitated purified rubber is redissolved in acetone, and this rubber solution is dissolved in potassium hydroxide in ethanol. The acid equivalent was determined by titration with thymolphthalein as an indicator. The carboxylic acid addition rate is obtained by converting an acid equivalent to a carboxylic acid addition rate, and adding the carboxylic acid to the amount of maleic anhydride charged. It was determined by calculating the percentage of addition.

 (5) Measurement of carboxylic acid residual rate

 The rubber was dissolved in acetone, and this solution was titrated with thymol phthalein as an indicator using an ethanol solution of potassium hydroxide, and the obtained carboxylic acid addition amount was subtracted from the obtained value. It was determined by calculating the percentage based on the amount of maleic anhydride charged.

 (6) Infrared absorption analysis

The measurement was carried out using an infrared absorption spectrometer (ST Japan Japan Co., Ltd., infrared scanning infrared microscope system). A peak appears at around 1785 cm ^{1 for} carboxylic anhydride groups and around 1710 to 1740 cm ^{1 for} carboxyl groups.

 (7) Measurement of MEK insoluble matter content

 Finely chop the rubber, place it in an 80 mesh wire mesh basket, immerse the basket in methyl ethyl ketone at room temperature for 48 hours, dry the solids remaining in the basket, and weigh the dried material. The percentage of the weight of the dry matter relative to the weight of the rubber initially placed in the basket was determined.

Reference Example 1 (Production of maleic anhydride-added hydrogenated acrylonitrile butadiene copolymer rubber)

100 parts of nitrile group-containing highly saturated polymer rubber (hydrogenated acrylonitrile butadiene copolymer rubber, iodine value 28, bound nitrile unit content 36%, Mooney viscosity 58) Using a pressure kneader (Moriyama Seisakusho, mixing amount: 75 liters, MS type), mastication was performed. At this time, a pressure kneader scratch, jacket its mixing tank, the side plates, the Ja Kek Bok of pressurizing lid and blade shaft by flowing steam at a pressure of the vapor pressure of 3 kgf / cm ² While operating at 130 ° C, the blade was operated under the conditions of a blade rotation speed of 30/25 rpm and a shearing speed of 500 S- ¹ . The filling rate in the pressure kneader was about 89.5% by volume based on the total volume of the kneader.

 After the rubber temperature increased to 130 ° C, 1.8 parts of maleic anhydride and 0.5 part of 2,6-di-tert-butyl-4-methylphenol (BHT) melted by heating at 65 ° C were planned. The mixture was charged into a pressurized kneader using a jar pump, and was continuously kneaded (pre-kneaded). The rubber temperature was adjusted to 250 ° C using the shear heat generated by kneading, and kneading was continued at this temperature for 20 minutes to cause an en-type addition reaction. The rubber temperature was controlled by flowing water at 35 ° C through the jacket of the pressure kneader.

 Finally, the mixing tank of the pressurized kneader was turned down, kneaded for about 30 seconds, and the rubber mixture was dropped and removed from the pressurized kneader to obtain a carboxylated nitrile group-containing highly saturated copolymer rubber. . No dirt was found on the blade of the pressure kneader. It takes 33 minutes from the start of mastication by charging the nitrile group-containing highly saturated polymer rubber into the pressure kneader and finally dropping the rubber mixture from the pressure kneader. Cost me. The carboxylated nitrile group-containing highly saturated copolymer rubber obtained had a carboxylic acid addition rate of 89% and an acid equivalent of 16.3 X 10-3 ephr. The carboxylic anhydride group was measured by infrared absorption analysis. Peak height] / ([Carbonic anhydride group peak height] + [carboxyl group peak height]) 0.96, MEK insoluble content 0.2%, carboxylic acid residual ratio 3%, maleic anhydride Acid-added hydrogenated acrylonitrile butadiene copolymer rubber (maleic acid-modified ZP-1).

In the same manner as above, the amount of maleic anhydride used was changed to 3.5 parts, and A maleic anhydride addition reaction was carried out in the same manner as described above, except that the kneading time at a system temperature of 250 ° C was changed to 45 minutes. The resulting highly saturated copolymer rubber containing a carboxylated ditolyl group has a carboxylic acid addition rate of 80%, an acid equivalent of 2.8 x 10-3 ephr, and is measured by infrared absorption spectroscopy. Of peak] / ([peak height of carboxylic acid anhydride group] + [peak height of carboxyl group]) 0.89, 0.5% of MEK-insoluble matter, 5% of carboxylic acid residual ratio Acid-added hydrogenated acrylonitrile-butadiene copolymer rubber (maleic acid-modified ZP-2). Reference Example 2 (Production of maleic anhydride-added acrylonitrile copolymer rubber by autoclave)

 Methyl ethyl ketone solution of nitrile group-containing highly saturated polymer rubber (hydroacrylonitrile-butadiene copolymer, iodine value 28, bound acrylonitrile unit content 36%, mu-212 viscosity 58) in autocrepe (Concentration: 11%), 30 parts of maleic anhydride was added to 100 parts of the rubber, and then a methyl ethyl ketone solution in which 7 parts of benzoylvaloxide was dissolved under an inert gas atmosphere was continuously applied. The reaction was allowed to proceed at 95 ° C for 4 hours with the addition. The reaction product was reprecipitated and purified with a mixed solvent of n-hexanenoethyl ether. The obtained reaction product had a carboxylic acid addition ratio of 6%, an acid equivalent of 18.3 x 10-3 ephr, and a peak height of the carboxylic acid anhydride group measured by infrared absorption spectroscopy. Z ([carboxylic acid anhydride Group peak height] + [carboxyl group peak height]) value 0.45, MEK insoluble content 7.1%, maleic anhydride-added hydrogenated acrylonitrile lubricant It is a polymer rubber (maleic acid-modified ZP-3).

Example;! To 27 and Comparative Examples 1 to 36 Tables 1 to 6 show thermoplastic resin and maleic anhydride-added hydrogenated acrylonitrile relubutadiene copolymer rubber (Examples of the present invention using maleic acid-modified ZP-1 or ZP-2), and Table 7 shows epoxy resin and phenol resin. The results of the heat-resistant adhesive test for electronic parts are shown below.

 The synthetic resins used are as follows.

 Polyamide resin: Nylon 6 (Ube Nylon 1013 B manufactured by Ube Industries)

 Polyamide elastomer: (Bax 6312MNOO Toray) Polyester resin: Polybutylene terephthalate, PBT (Juranex 600 F P Polyplastic)

 Polyester elastomer: (Pelprene 9001 Toyobo Co., Ltd.) Polycarbonate resin (PC): Iupilon S-2000 (Mitsubishi Gas Chemical Co., Ltd.)

 Polyethersulfone resin (pES): Bistrex 3601 G L20 (Mitsui Toatsu Chemicals)

 Polyphenylene sulfide resin (PPS): Novaps 704 G40 (Mitsubishi Engineering Plastics)

 Epoxy resin: Cresol novolak type epoxy resin (ECN1280 Ciba-Geigy Chemical Co., Ltd.)

 Phenol resin: Resin type phenolic resin (SHONOL CKS 343 manufactured by Showa Kogyo Co., Ltd.)

The commercially available rubber used is as follows.

Hydrogenated acrylonitrile-butadiene copolymer rubber: Zp2020 (produced by Zeon Corporation) Acrylonitrile butadiene copolymer rubber: NBR DN 1042 (manufactured by Zeon Corporation) Carboxylated acrylonitrile-butadiene copolymer rubber: NBR DN 1072 J (manufactured by Zeon Corporation) Ethylene-propylene-one Conjugated gen copolymer rubber: EPDM Kertan 4778 F (made by Idemitsu Petrochemical Co.) Polyacrylic acid ester-based copolymer rubber: acrylic rubber AR31 (made by Zeon Co., Ltd.) Table 1 Example Comparative Example Comparative example

 1 2 1 2 3 3 4 4 5 6 Nylon 6 60 60 60 60 60

 Polyamide elastomer 60 60 60 60 60 Maleic acid-modified ZP—1 40 40

 Maleic acid modified ZP—2 40 40

 Z p 2020 40 40

 Maleic acid-modified ZP— 3 40 40

 DN 1072 J 40 40 Twin screw extruder kneading 240 ° C

 Tensile test

Tensile strength (kgf / cra ² ) 521 575 357 374 220 376 396 278 298 289 Elongation (%) 400 410 310 350 120 420 380 240 280 180

100% stress (kgf / cra ² ) 198 209 245 212 210 234 247 247 256 216 Hardness (Shore D) 61 62 68 67 65 53 52 58 56 56

Izod impact strength (kgf / cm) 75 68 13 21 22 67 64 43 32 23 Table 2

Table 3

 Example Comparative Example Example Comparative Example Example Comparative Example

9 13 14 10 15 16 11 17 18

PC resin 90 90 90

 P E S resin 90 90 90

 PPS resin 90 90 90 Maleic acid-modified ZP—1 10 10 10

 Z p 2020 10 10 10 Maleic acid-modified Z P— 3 10 10 10

PC resin, twin screw extruder kneading 240 ° C

 PES resin, twin screw extruder kneading 330 ° C

 P P S grease, twin screw extruder kneading 290 ° C

 Tensile test

 Elongation (%) 180 90 110 120 50 60 90 40 40

Izod impact strength (kgf / cm) 120 78 85 75 28 43 98 56 87 Table 4 Example Comparative example

12 13 14 15 19 20 21 22

+ Α 1 α ζ β re 60 60 60 60 60 60 60 60 Male ?? Koi Shin 伸 Ρ — 1 10 10 10 10

Maleic acid modified Ζ Ρ — 3 10 10 10 10

D N 1 0 4 2 30 30 30 30

η π U 7/9 Otsu J Τ 30 30

F P Π M 30 30

A R

 —Naoyoshi OQ machine T ^^ 9 A 4 C U] ° C Tensile test

Tensile strength (kgf / cm ² ) 412 487 396 423 128 374 165 387 Elongation (%) 280 390 330 320 80 350 60 350

100% stress (kgf / cm ² ) 274 286 258 289 212 269 Hardness (Shore D) 58 57 62 64 56 67 52 58

Izod Impact strength (kgf / cm) 47 58 39 51 8 21 9 28

Table 5

Table 6

 Example Comparative example

 20 21 22 23 24 25 27 28 29 30 31 32

PC resin 80 80 80 80

 PES resin 80 80 80 80

PPS resin 80 80 80 80 Maleic acid-modified ZP-1 10 10 10 10 10 10

 Maleic acid-modified ZP— 3 10 10 10 10 10 10

EPDM 10 10 10 10 10 10

AR 10 10 10 10 10 10

PC resin, twin screw extruder kneading 240 ° C

 PES resin, twin screw extruder kneading 330 ° C

 PPS resin, twin screw extruder kneading 290 ° C

 Tensile test

 Elongation (%) 160 110 120 180 120 130 60 80 70 60 40 40

Izod Impact strength (kgf / cm) 85 68 85 96 74 98 38 56 43 35 48 57 Table 7

From the results of Tables 1 to 7, it can be seen that the mixed composition of the present invention provides a significant improvement in the impact resistance of the thermoplastic resin as compared with the prior art. Further, an adhesive using a thermosetting resin is improved in adhesive strength and heat resistance, and is therefore suitable as a heat-resistant adhesive for electronic components.

The fact that various physical properties are improved as shown in Tables 1 to 7 by the present invention using the carboxylated nitrile group-containing highly saturated copolymer rubber can be measured by infrared absorption spectroscopy. Group peak height] no ([carboxylic acid anhydride group peak height] + [carboxyl group peak height]) It is considered that, because the value of is larger than that of the conventional carboxylated NBR, the compatibility with the thermoplastic resin and the like is improved, and the mutual dispersibility is improved.

Examples 28 to 31 and Comparative Example 37

 Maleic acid-modified ZP-1 (the value of [peak height of carboxylic acid anhydride group] / ([peak height of carboxylic acid anhydride group] + [peak height of carboxyl group]) determined by infrared absorption spectroscopy) is 0 96) and nylon 6 in an air heating aging test (150 ° C, 72 hours) according to JISK 6301, a gasoline permeation resistance test according to the following procedure, and evaluation of thin wall extrudability. A test and a freon resistance test were performed.

 As a comparative example, maleic anhydride-added hydrogenated acrylonitrile butadiene copolymer rubber (maleic acid-modified ZP_3, [peak height of carboxylic anhydride group] / ( A mixture composition using [the peak height of the carboxylic acid anhydride group] + [the peak height of the carboxyl group]) was 0.45). Table 8 shows the results.

The mixed composition is obtained by mixing a rubber component, an antioxidant, and a processing aid with a pressurized kneader (Moriyama Seisakusho Co., Ltd., MS pressurized Niegu DS 3-7.5 type)-pellet granulator (Moriyama) After pelletizing the pellets in advance using a MS feeder-ruder FR-35 (manufactured by Seisakusho Co., Ltd.), a twin-screw extruder (BT-40, manufactured by Plastics Engineering Laboratory Co., Ltd.) as a heat-sealing kneader. Diameter 38 mm. Screw length 1600 mm, L / D = 42. Screw shearing speed 20001ZS, extrusion rate 20 Kg / h). By mixing with resin Prepared.

 (8) Thin wall extrudability evaluation test-The gap between the T dies of the above single screw extruder was narrowed to 0.2 mm, extruded at a temperature of 230 to 240 ° C, at a rotation speed of 5 rpm, and a surface with a length of 1.5 m Was slowly taken up on a belt conveyor that had been treated with a teflon to obtain a sheet molded product having a thickness of about 0.1 mm.

 The extrudability was evaluated on the basis of the appearance of the extruded skin on a 4-point scale (excellent, good, acceptable, unacceptable X). Bushings are those that are less than 1 mm on the extruded surface, and the rating of the buddings is shown in terms of the number of those sheets per lm. The dispersibility was represented by the average diameter (/) of dispersed rubber particles observed from a transmission electron microscope photograph.

 (9) Gasoline penetration test

A 5 cm diameter disk-shaped sample sheet was punched from a 0.5 mm thick sheet obtained by press molding at 240 ° C for 4 minutes. A 30 cc fuel D was placed in an aluminum cup with a capacity of 50 cc, a sample sheet was placed over the cup, a disc-shaped metal fitting was attached to the rim, and it was fixed with screws. After that, the aluminum cup is turned upside down, and the gasoline permeation amount per 24 hours is calculated based on the weight change from 24 hours to 168 hours, and the gasoline permeation amount is calculated based on that value. coefficient was _c the permeability coefficient is preferably as small.

 (10) Freon resistance test

A sample punched into a disk having a thickness of 0.2 mm and a diameter of 78 mm was fixed to a pressure vessel for Freon transmission test filled with 50% of Freon R-134a in volume. One side of the sample seals the freon and the other side is open to the atmosphere I'm touching. The pressure vessel equipped with the sample for the freon transmission test was placed downward in a 90 ° C gear oven so that the sample was in contact with the freon. After 24 hours, the container was taken out, and after the temperature of the container had sufficiently returned to room temperature, the weight of the container was measured. The weight loss of the container corresponds to the amount of freon permeated into the atmosphere. The same measurement was repeated five times for the same sample, and the average value obtained from the second to fifth measurements was taken as the Freon transmission coefficient (mg · mm / cm ² · 24 h). The smaller the permeability coefficient, the better the permeation resistance.

Table 8 Example-Comparative example

28 29 30 31 37 u mouth

 'ロ "60 60 60 60 60 60 60 OU

 7 P Q Π u 9 perimeter 30 20 10

 Rei ¾o ¾ ^ 7 o 40 Suko Rino S g¾ ^ 0.5 0.5 0.5 0.5 υ.5 1?-F'— \ ^ Λ Λ

 "O 1 1 1 1 1

51 5fe 频

 5 worms <ί 567 564 543 544 357 Others Ψ 420 410 380 430 310 丄 U U J 236 213 208 220 245

 65 63 60 61 68 "Contribution ¾f

S VJU 1

La 1 1¾

 I 1 ^ ^ HE ftte

 V ¾K 532 518 492 525 332

1 Nakahi 330 280 300 310 210 丄 U Ζθ Shino J 245 227 219 230 238

 65 65 63 65 69

II1TJ "/ S

 0.2 0.4 0.3 0.2 4.8 Thin wall extrusion test

 Extruded skin © ◎ © ◎ X Number of pieces None None None None 108 Dispersibility 0.5 2 0.5 2 0.5 2 0.2 2 5 10 Freon resistance test

Transmission coefficient 0.04 0.08 0.12 0.08 0.24 From the results in Table 8, the value of [peak height of carboxylic anhydride group] / ([peak height of carboxylic anhydride group] + [peak height of carboxyl group]) measured by infrared absorption analysis is 0. The mixture composition of Examples 28 to 31 comprising maleic anhydride-modified nitrile group-containing highly saturated copolymer rubber (maleic acid-modified ZP-1) having a high value of 0.96 and nylon 6 is as follows: It can be seen that, in addition to the strength characteristics and heat resistance being improved, the gasoline permeation resistance and freon gas permeation resistance are significantly improved. Furthermore, the extrudability of a thin sheet with a thickness of about 0.1 mm is good, indicating that the workability has been significantly improved.

 On the other hand, the mixed composition of Comparative Example 37 using maleic anhydride-added hydrogenated acrylonitrile-butadiene copolymer rubber (maleic acid-modified ZP-3) prepared by the conventional technique has strength characteristics. Etc., and the effects of improving gasoline permeation resistance, Freon gas permeation resistance, and thin wall extrusion property are also insufficient. The maleic anhydride-added hydrogenated acrylonitrile-butadiene copolymer rubber prepared by the conventional technique has a [peak height of carboxylic acid anhydride group] Z ([peak of carboxylic acid anhydride group] measured by infrared absorption spectroscopy). In view of the low [height] + [peak height of carboxyl group]), it is assumed that most of the carboxylic anhydride groups in the molecule have been decomposed into carboxyl groups. For this reason, the copolymer rubber of Comparative Example 37 was inferior in compatibility with Nylon 6 and was insufficient in mutual dispersibility. As a result, no improvement was observed in various physical properties. It is considered something.

Industrial applicability

Since the composition of the present invention is excellent in mechanical strength and has good oil resistance, heat resistance, weather resistance, etc., it can be used for 0-ring, gasket, oil seal, Freo, etc. Various seal materials such as automotive seals; V-belts for automobiles, poly-ribbed belts, belts such as toothed conduction belts, etc .; Power steering hoses for automobiles, high-pressure for various machines (for example, construction machinery) Hoses such as oil-resistant hoses, fuel hoses for automobiles, etc .; Rolls; Rubber products used in oil and gas wells [Packers, blowers, tubers, etc.]. Various diaphragms; clutch plates and brake shoes for automobiles (these are molded by blending thermosetting resins such as phenolic resin or epoxy resin with other compounding agents), etc. In addition to applications, it can be widely used for various applications such as anti-vibration rubber, electrical products, automotive parts, industrial supplies, footwear, etc. In particular, rack and pinion boots, bellows, vacuum connectors, tubes, side malls, headless, registraters, amalests, shift toreno boots, user strips, side malls, air boilers, Suspension boots, belt covers, wheel covers, knobs, bumpers, site shields, bumper moldings, etc., as well as hydraulic hoses, air tubes, rubber hoses, rubber covers, various gaskets, etc. It is useful as industrial parts such as metal, containers, 0-rings, packing materials, etc.

Claims

The scope of the claims

1. (A) 90 to 10% by weight of at least one thermoplastic or thermosetting resin and (B) an acid equivalent of at least 2 x 10 " ³ ephr, which is measured by infrared absorption spectroscopy. Peak height] / ([Carboxylic anhydride group peak height] + [Carboxyl group peak height]) value of 0.50 or more, Mooney viscosity of 15 to 200, and iodine value of 80 or less carboxylation A mixed composition of a synthetic resin and a carboxylated nitrile group-containing highly saturated copolymer rubber, characterized by comprising 10 to 90% by weight of a nitrile group-containing highly saturated copolymer rubber.

 2. A carboxylated nitrile group-containing highly saturated copolymer rubber is heated in a heat-sealing kneader at a rubber temperature of 200 to 280 ° C and a nitrile group-containing highly saturated copolymer rubber and an ethylenically unsaturated carboxylic acid or the same. 2. The mixed composition according to claim 1, which is obtained by performing an ene-type addition reaction with an anhydride.

3. The nitrile group-containing highly saturated copolymer rubber is obtained by hydrogenating the conjugated gen unit of the ethylenically unsaturated nitrile conjugated gen-based copolymer rubber, and the amount of bound ditrile is 10%. 3. The mixed composition according to claim 2, wherein the composition has an iodine value of 80 or less, a viscosity of ML (ML _{1 + 4} , 100 ° C), usually 30 to 300.

 4. Claims wherein the ethylenically unsaturated carboxylic acid or anhydride thereof is an ethylenically unsaturated dicarboxylic acid having 4 to 10 carbon atoms or an anhydride thereof.

4. The mixed composition according to 2 or 3.

5. A carboxylated nitrile group-containing highly saturated copolymer rubber having an acid equivalent of at least 2 x 10 " ³ ephr is measured by infrared absorption spectroscopy. [Peak height of carboxylic anhydride group] / ([carboxylic acid Anhydrous peak height] + [force The mixed composition according to any one of claims 1 to 4, wherein the value of the peak height of the lipoxyl group]) is 0.75 or more.

 6. Thermoplastic resin or thermosetting resin and carboxylated nitrile group-containing highly saturated copolymer rubber are thermoplastic resin or thermosetting resin 20 to 80% by weight and carboxylated nitrile group-containing The mixed composition according to any one of claims 1 to 5, which is used in a proportion of 80 to 20% by weight of the highly saturated copolymer rubber.