JPH0443937B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a hydrogenated block copolymer composition having excellent heat resistance and oil resistance, and more specifically to a hydrogenated block copolymer composition containing a carboxylic acid group or a derivative group thereof. A modified hydrogenated block copolymer composition prepared by blending a modified hydrogenated block copolymer in which units are bonded, a polyolefin resin, an olefin copolymer rubber, and, if necessary, a rubber softener, is heated and melted. The following relates to a dynamically vulcanized modified hydrogenated block copolymer composition with excellent heat resistance and oil resistance, which is obtained by kneading with a specific thermosetting resin. [Prior Art] In recent years, thermoplastic elastomers, which do not require a vulcanization process and have moldability similar to thermoplastic resins, have been widely used in fields such as automobile parts, home appliance parts, miscellaneous goods, and footwear. I'm getting old. Among these, vinyl aromatic compound-conjugated diene compound block copolymers such as styrene-butadiene block copolymer and styrene-isoprene block copolymer have elasticity and feel similar to conventional vulcanized rubber. The vulcanized rubber has been evaluated as being suitable as a material for molded products. However, as a thermoplastic elastomer, the above-mentioned vinyl aromatic compound-conjugated diene compound block copolymer has inferior heat resistance, weather resistance, and oil resistance compared to vulcanized rubber, so its range of use is limited. . Vinyl aromatic compounds that improve these drawbacks
Thermoplastic elastomers made of hydrogenated products of conjugated diene compound block copolymers (hereinafter referred to as hydrogenated block copolymers) have improved weather resistance and heat resistance, but oil resistance remains the same as before.
Heat resistance was also still insufficient. Several proposals have been made to improve the drawbacks of these hydrogenated block copolymers. For example, in JP-A-59-6236 and JP-A-59-131613, an elastomer composition in which a hydrogenated block copolymer is blended with a hydrocarbon oil, a polyolefin resin, and an inorganic filler is prepared using organic peroxide. It has been proposed to dynamically vulcanize the elastomer composition in the presence of a crosslinking monomer to improve the rubber elasticity at high temperatures of the resulting elastomer composition. [Problem to be solved by the invention] However, the hydrogenated block copolymer composition dynamically vulcanized with an organic peroxide disclosed in the above-mentioned JP-A-59-6236 and JP-A-59-131613 Although the rubber elasticity at high temperatures is improved, radicals based on organic peroxides cause scission of polymer chains, resulting in a decrease in mechanical strength. [Means for Solving the Problems] In view of the current situation, the present inventors have conducted intensive studies to solve various problems with the aromatic vinyl compound-conjugated diene compound block copolymer, and have found that
A modified hydrogenated block copolymer obtained by introducing a specific reactive group into a hydrogenated block copolymer, a polyolefin resin, and an olefin copolymer rubber are dynamically melted and kneaded using a specific thermosetting resin. By vulcanizing, it has excellent mechanical strength and heat resistance.
The present invention was completed based on the discovery that a thermoplastic elastomer with excellent oil resistance can be obtained. That is, the present invention (a) hydrogenates a block copolymer consisting of at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. 100 parts by weight of a modified hydrogenated block copolymer in which a molecular unit containing a carboxylic acid group or its derivative group is bonded to the hydrogenated block copolymer obtained by (b) 20 to 500 parts by weight of a polyolefin resin; c) Olefin copolymer rubber 0.5 to 30 parts by weight of a reactive alkylphenol/formaldehyde resin is blended with 100 parts by weight of a modified hydrogenated block copolymer composition consisting of 5 to 150 parts by weight, and kneaded under heating and melting. The present invention provides a modified hydrogenated block copolymer composition obtained by dynamic vulcanization. The present invention will be explained in detail below. The modified hydrogenated block copolymer used as component (a) in the present invention comprises at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound. This is a modified hydrogenated block copolymer in which a block copolymer consisting of B is hydrogenated and a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to the hydrogenated block copolymer. That is, for example, A-B, A-B-A, B-A-B-A,
(A-B) _-4 Si, (B-A-B) _-4 Si, A-B-A-
Hydrogenating a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as B-A,
It is produced by subjecting the hydrogenated block copolymer to an addition reaction with an unsaturated carboxylic acid or a derivative thereof. This hydrogenated block copolymer contains a vinyl aromatic compound in an amount of 5 to 60% by weight, preferably 10 to 55% by weight. A is a structure of a vinyl aromatic compound polymer block or a copolymer block of a vinyl aromatic compound containing more than 50% by weight and preferably 70% by weight or more and a hydrogenated conjugated diene compound. Further, the polymer block B mainly composed of a hydrogenated conjugated diene compound is a hydrogenated conjugated diene compound polymer block, or a hydrogenated conjugated diene compound containing 50% by weight. Over preferably 70
It has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing at least % by weight. In addition, polymer block A mainly composed of these vinyl aromatic compounds,
Polymer block B mainly composed of hydrogenated conjugated diene compounds has a random distribution of hydrogenated conjugated diene compounds or vinyl aromatic compounds in the molecular chains of each polymer block.
It may be tapered (the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof, and the polymer block mainly composed of the vinyl aromatic compound and the hydrogen When there are two or more polymer blocks each consisting mainly of the added conjugated diene compound, each of the polymer blocks may have the same structure or may have different structures. Examples of vinyl aromatic compounds constituting the hydrogenated block copolymer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene,
One or more types can be selected from p-tert-butylstyrene, 1,1'-diphenylethylene, etc., and styrene is preferred among them. Further, as the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound, for example, one selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. One or more species are selected, with butadiene, isoprene, and combinations thereof being preferred. The microstructure of a polymer block mainly composed of a conjugated diene compound before hydrogenation can be arbitrarily selected, but for example, in a polybutadiene block, the amount of 1,2-vinyl bonds is 10 to 10. 65%, preferably 20-55%. Further, the number average molecular weight of the hydrogenated block copolymer used in the present invention having the above structure is 5000 to 5000.
1,000,000, preferably 10,000 to 500,000, and a more preferable range of 30,000 to 300,000 from the viewpoint of maintaining a balance between the physical properties and processability of the composition of the present invention, and the molecular weight distribution [weight average molecular weight (w) and number average molecular weight (n)] is 10 or less. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof. The method for producing these block copolymers is as follows:
As long as it has the above-described structure, it may be obtained by any manufacturing method. For example, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798, and then, for example,
Hydrogenation in an inert solvent by the method described in Japanese Patent Publication No. 8704 and Japanese Patent Publication No. 43-6636, particularly preferably by the method described in Japanese Patent Publication No. 63-4841 and Japanese Patent Publication No. 63-5401. The hydrogenated block copolymer used in the present invention can be synthesized by hydrogenation in the presence of a catalyst. At this time, at least 80% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is transformed into an olefin. The compound can be converted into a polymer block. In addition, hydrogen of an aromatic double bond based on a vinyl aromatic compound copolymerized into a polymer block A mainly composed of a vinyl aromatic compound and, if necessary, a polymer block B mainly composed of a conjugated diene compound. Although there is no particular restriction on the addition rate, it is preferable that the hydrogenation rate is 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like. Next, by adding an unsaturated carboxylic acid or a derivative thereof to the above-mentioned hydrogenated block copolymer in a solution state or melt state, with or without the use of a radical initiator, the modified hydrogenated copolymer used in the present invention can be obtained. A block copolymer is obtained. The hydrogenated block copolymer that can be used for such addition modification can be any of those specified above, and the unsaturated carboxylic acid or its derivative added to the hydrogenated block copolymer Examples include maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-
1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc. Examples include derivatives of acids such as crotonic acid and esters of these monocarboxylic acids, such as methyl methacrylate, glycidyl methacrylate, and amides. Among these, maleic anhydride is particularly preferred. The method for producing these modified hydrogenated block copolymers is not particularly limited in the present invention, but the modified hydrogenated block copolymers obtained may contain undesirable components such as gel or have a significantly high melt viscosity. A manufacturing method that increases the number of particles and deteriorates workability is not preferable. A preferred method is, for example, a method in which an unmodified hydrogenated block copolymer is reacted with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical initiator in an extruder. The amount of unsaturated carboxylic acid or its derivative added to the hydrogenated block copolymer is preferably 20 parts by weight or less per 100 parts by weight of the hydrogenated block copolymer, and 10 parts by weight or less.
Parts by weight or less are more preferred. Even if the amount added exceeds 20 parts by weight, there is hardly any increase in the improvement effect compared to when the amount is less than 20 parts by weight. The unsaturated carboxylic acids or derivatives thereof used in the present invention can be used not only alone but also as a mixture of two or more. Next, the polyolefin resin as component (b) of the present invention is used as an effective component for improving processability during molding as well as for improving oil resistance and heat resistance. The polyolefin resin used has a melting point of 120℃
The above crystalline polyolefin resins include, for example, polyethylene (low density, medium density, or high density), polypropylene, and copolymers of propylene and other α-olefins, such as ethylene-propylene copolymers. Examples include polypropylene resins such as -hexene-propylene copolymer and 4-methyl-1-pentene-propylene copolymer, and poly(4-methyl-1-pentene). Among them, polypropylene resin is preferred, and MFR (ASTM-D-1238-L conditions, 230
C) is preferably in the range of 0.1 to 50 g/10 minutes, particularly 0.5 to 30 g/10 minutes. The blending amount of these components (b) can be within the range of 20 to 500 parts by weight, preferably 30 to 250 parts by weight, based on 100 parts by weight of the modified hydrogenated block copolymer of component (a). . If more than 500 parts by weight is added,
The hardness of the resulting composition becomes so high that it not only loses its rubbery feel, but also loses flexibility and significantly deteriorates its rubber elasticity. In addition, if the amount is less than 20 parts by weight, the resulting composition not only has poor moldability but also poor oil resistance, which is not preferable. The olefin copolymer rubber used as component (c) of the present invention is a rubber that is more useful in improving compression set at high temperatures than the modified hydrogenated block copolymer alone of component (a). It is an elastic body of an amorphous random copolymer mainly composed of olefin, such as ethylene/propylene copolymer rubber (EPM) and ethylene/propylene/non-conjugated diene copolymer rubber (EPDM). Such rubbers used in the present invention include:
The above two types of rubber are preferred, and among them, a terpolymer (EPDM) rubber containing a non-conjugated diene component is particularly preferred. Examples of the non-conjugated diene in this case include dicyclopentadiene, cyclooctadiene, methylnorbornene, ethylidenenorbornene, 1,4-hexadiene, etc.
Among them, ethylidene norbornene is preferred. Among this terpolymer (EPDM) rubber,
In the present invention, ethylene/propylene/ethylidene norbornene copolymer rubber is preferred. The Mooney viscosity of the rubber used here, ML ₁₊₄ (100℃) is 10
-120, preferably 40-100. If a material having a Mooney viscosity of less than 10 is used, preferred crosslinking cannot be obtained and no improvement in compression set can be expected at high temperatures, which is undesirable. Moreover, if it exceeds 120, molding processability deteriorates and the appearance of the molded product further deteriorates, which is not preferable.
The iodine value of this rubber is preferably 5 to 30, and the propylene content in the copolymer is 20 to 30.
50% by weight is preferred. The amount of component (c) mentioned above can be suitably selected in the range of 5 to 150 parts by weight, with 50 to 150 parts by weight based on 100 parts by weight of the modified hydrogenated block copolymer of component (a).
~120 parts by weight is preferred. If the amount exceeds 150 parts by weight, the mechanical strength and elongation of the resulting composition will decrease, and the moldability and appearance of the molded product will deteriorate, which is undesirable. Furthermore, when the amount is less than 5 parts by weight, the effect of adding component (c) on rubber elasticity (compression set) at high temperatures is not significant and is equivalent to the case without addition. Next, the reactive alkylphenol/formaldehyde resin used as component (d) of the present invention is generally known as a resol type phenol resin, and is a known reactive alkylphenol that can be used as a resin vulcanizing agent for rubber. / formaldehyde resin. As a preferable example of the resin, for example, general formula (A) (Here, n is an integer of 2 to 5, X is a hydroxyl group or a halogen group, and R is a hydrocarbon group having 1 to 20 carbon atoms.) Examples include reactive alkylphenol/formaldehyde resins represented by the general formula ( It may have a structure in which A) is partially modified. This resin is generally obtained by a condensation reaction between a substituted phenol and formaldehyde in an alkaline medium, or is a phenolic curing resin obtained by a condensation reaction of difunctional phenolic dialcohols. . It may be manufactured by any method, for example, US Pat. No. 3,287,440;
Same No. 3709840, Same No. 2972600 and Same No.
The method for producing a phenol curing resin disclosed in No. 3093613 and the method using a vulcanization system using the same can be used. In addition, specifically as this resin, commercially available Tackirol 201, Tackirol 250-1 (Sumitomo Chemical
Co., Ltd.) Schenectady SP-1045, Schenectady
Examples include SP-1055 (manufactured by Schenectady Chemicals Co.). This resol type phenolic resin can be used alone, or a vulcanization accelerator can be used in combination to adjust the vulcanization rate. Examples of the vulcanization accelerator include metal halides (stannic chloride,
(ferric chloride, aluminum trifluoride), organic halides (chlorinated polyethylene, chlorosulfonated polyethylene, chlorinated paraffin, brominated butyl rubber, chloroprene), etc. can be used. The modified hydrogenated block copolymer composition of the present invention dynamically vulcanized using this component (d) is a hydrogenated block copolymer composition dynamically vulcanized using a known organic peroxide. provides a composition that exhibits superior performance in mechanical strength and compression set at high temperatures (100°C). Here, the dynamically vulcanized modified hydrogenated block copolymer composition is defined as refluxing 1 g of the composition obtained in the present invention in a Soxhlet extractor using boiling xylene for 10 hours, and extracting the residue into 80 mesh. Dry weight of insoluble matter remaining on the mesh after filtering through a wire mesh (g)/Weight of component (a) contained in 1 g of the composition
(c) The gel content (%) expressed as the ratio of the sum of the weights (g) of the components multiplied by 100 is at least 30%, preferably 50% or more (however, this does not include insoluble components such as inorganic fillers). It is characterized in that the vulcanization is performed during melt-kneading of the modified hydrogenated block copolymer composition. In order to obtain such a dynamically vulcanized modified hydrogenated block copolymer composition, the blending amount of component (d) is
0.5 to 30 parts by weight for a total of 100 parts by weight of (a) to (c),
Preferably, it can be selected from 1 to 20 parts by weight, and the gel content can be adjusted.
Further, when a vulcanization accelerator is used, 0.2 to 15 parts by weight of the vulcanization accelerator can be optionally added to 100 parts by weight of components (a) to (c) in total. In the present invention, the method for producing the dynamically vulcanized modified hydrogenated block copolymer composition can be any method used in the production of ordinary resin compositions or rubber compositions, such as single-screw extruder, twin-screw extruder, etc. The composition can be compounded using a melt kneading machine such as a machine, a Banbury mixer, a heating roll, a Brabender, or various kneaders. At this time, preheat ingredients (a) to (c) to 150 to 300℃.
If the scorch time of the (d) component used is long, the (a) component is heated and melt-kneaded at a temperature of It is also possible to adopt a method in which components (d) are melt-kneaded in advance, a vulcanization accelerator is added, and the mixture is dynamically vulcanized while being melt-kneaded. At this time as well, the temperature setting of the processing equipment can be suitably selected from 150 to 300°C. Therefore, there are no particular limitations on the production method as long as it has the characteristics of the dynamically vulcanized modified hydrogenated block copolymer composition described above. Further, a rubber softener may be added to the composition of the present invention as required. The rubber softener referred to here is a softener that is generally used to improve the flexibility, rigidity, fluidity, etc. of rubber and plastics, and includes petroleum-based softeners, aliphatic softeners, and synthetic organic compounds. For example, paraffinic process oil, naphthenic process oil, aromatic process oil, vaseline, paraffin, polyethylene wax, linseed oil, soybean oil, ester plasticizers such as dioctyl phthalate, dioctyl adipate, etc. can be mentioned. Among these, process oils are preferred, and paraffinic process oils are particularly preferred. These rubber softeners may be blended into the composition of the present invention, or may be blended in advance with at least one of the components (a), (b), and (c).
After mixing components (a), (b), (c) and (d) with a rubber softener, dynamic vulcanization as referred to in the present invention may be performed. The above-mentioned rubber softener is added as necessary to impart flexibility and fluidity to the composition of the present invention. There is no particular restriction on the amount of the compound added, but it is preferably 500 parts by weight or less per 100 parts by weight of the modified hydrogenated block copolymer (a). If the amount exceeds 500 parts by weight, the softener may bleed out or the mechanical strength may decrease, which may lead to unfavorable results. It is also possible to add an unmodified hydrogenated block copolymer to the composition of the present invention. The unmodified hydrogenated block copolymer may be the unmodified modified hydrogenated block copolymer used in the present invention, or may be another hydrogenated block copolymer. Two or more types may be used. These unmodified hydrogenated block copolymers may be blended into the composition of the present invention, and may also be used as component (a), component (b) and component (c).
It may be pre-blended with at least one of the following ingredients: (a) ingredient, (b) ingredient, (c) ingredient and (d) ingredient.
After mixing the components and these hydrogenated block copolymers, the dynamic vulcanization of the present invention may be performed. The amount of these unmodified hydrogenated block copolymers to be blended is not particularly limited, but is preferably 300 parts by weight or less per 100 parts by weight of the modified hydrogenated block copolymer of component (a). If the amount exceeds 300 parts by weight, the heat resistance and oil resistance of the composition of the present invention may deteriorate. The composition of the present invention may also contain fillers, such as calcium carbonate, calcium silicate,
carbon black, talc, clay, kaolin,
Silica, magnesium hydroxide, mica, barium sulfate, natural silicic acid, titanium oxide, magnesium oxide, zinc oxide, diatomaceous earth, etc. can be blended. In addition, the composition of the present invention may contain antioxidants, flame retardants, ultraviolet absorbers, light stabilizers,
A lubricant, glass fiber, carbon fiber, nylon fiber, etc. can be blended. Furthermore, the composition of the present invention can be made into a new composite by forming it into a composition with various thermoplastic resins. Examples of thermoplastic resins include polyethylene (low density, medium density, high density), polypropylene. , polybutene ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer, polyolefin polymers such as chlorinated polyethylene, polystyrene (general use, impact resistant use), ABS
Resins, polystyrene polymers such as AS resins and MBS resins, polyvinyl chloride polymers, polyamide polymers, thermoplastic polyester polymers, polyphenylene sulfide polymers, polyphenylene ether polymers, Examples include polycarbonate polymers, polyacetal polymers, polyurethane polymers, and the like. The dynamically vulcanized modified hydrogenated block copolymer of the present invention can be molded using commonly used thermoplastic resin molding machines, including injection molding, extrusion molding, blow molding, and calendar molding. Various molding methods such as [Effects of the Invention] The dynamically vulcanized modified hydrogenated block copolymer composition obtained by the present invention is a thermoplastic elastomer composition with excellent mechanical strength, and has excellent heat-resistant creep performance and high temperature resistance. Because it has excellent heat resistance and oil resistance, such as compression set, it can be suitably used for automobile parts, home appliances, wire coatings, various industrial parts, etc., and can also be used for leisure goods, miscellaneous goods, etc. (Example) Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. In addition, evaluation of various basic physical properties in Examples was performed by the following method. [Method for measuring basic physical properties] (1) Tensile properties: JIS K-6301, a 2 mm thick injected sheet was used as the sample, and a No. 3 dumbbell was used as the test piece. (2) Hardness: JIS A type as described in JIS K-6301 (3) Compression set: JIS K-6301, 25% compression at 100°C for 22 hours (4) Oil resistance: No. 3 as described in JIS K-6301 Using oil, test specimens of 50mm x 50mm x 2mm thick were heated at 70℃ for 2 hours.
It was immersed in oil for a time No. 3, and the weight change before and after immersion was determined. Reference Example A Production of hydrogenated block copolymer (A-1); Polybutadiene-polystyrene-hydrogenated by the method described in Japanese Patent Publication No. 63-4841
Has a hydrogenated polybutadiene-polystyrene structure, with a bound styrene content of 28% and a number average molecular weight.
A hydrogenated block copolymer was obtained with a molecular weight distribution of 1.04, a 1,2-vinyl bond content of 37% in the polybutadiene portion before hydrogenation, and a hydrogenation rate of 99% in the polybutadiene portion. (A-2); Similar to (A-1), it has a polystyrene-hydrogenated polybutadiene-polystyrene structure, with a bound styrene content of 22%, a number average molecular weight of 64,000, a molecular weight distribution of 1.03, and a A hydrogenated block copolymer was obtained in which the amount of 1,2-vinyl bonds in the polybutadiene portion was 55% and the hydrogenation rate in the polybutadiene portion was 100%. (A-3); Similar to (A-1), it has the structure of (polystyrene hydrogenated polybutadiene-polystyrene) _-4Si , the amount of bound styrene is 45%, the number average molecular weight is 109000, the molecular weight distribution is 1.44, 1,2-vinyl bond amount in polybutadiene part before hydrogenation 22
%, and a hydrogenated block copolymer with a hydrogenation rate of 100% in the polybutadiene portion was obtained. Reference Example B Production of modified hydrogenated block copolymer (B-1); 2.0 parts by weight of maleic anhydride, 2,5-dimethyl per 100 parts by weight of the hydrogenated block copolymer obtained in (A-1). - Mixing 0.2 parts by weight of 2,5-di(tert-butylperoxy)hexane,
Addition modification reaction was carried out at a temperature of 250°C in a twin-screw extruder with a diameter of 30 mm. The obtained modified hydrogenated block copolymer contained 1.5 parts by weight of maleic anhydride per 100 parts by weight of the polymer. (B-2); 2.5 parts by weight of maleic anhydride and 0.25 parts by weight of dicumyl peroxide were mixed per 100 parts by weight of the hydrogenated block copolymer obtained in (A-2), and the mixture was twin-screw extruded to a diameter of 30 mm. The addition modification reaction was carried out at a temperature of 250°C in a machine with forced venting (740 mmHg vacuum). The obtained modified hydrogenated block copolymer contained 1.8 parts by weight of maleic anhydride per 100 parts by weight of the polymer. (B-3); 4.0 parts by weight of maleic anhydride and 0.6 parts by weight of dicumyl peroxide were mixed per 100 parts by weight of the hydrogenated block copolymer obtained in (A-3), and the mixture was twin-screw extruded to a diameter of 45 mm. The addition modification reaction was carried out in a machine at a temperature of 240°C with forced venting (740 mmHg vacuum). The obtained modified hydrogenated block copolymer contained 2.6 parts by weight of maleic anhydride per 100 parts by weight of the polymer. Examples 1 to 7, Comparative Examples 1 to 4 (B-1) obtained in Reference Example B as component (a)
, Asahi Kasei Co., Ltd. polypropylene as component (b),
E1100 (MFR (230℃, L) = 0.5g/10min), (c)
EPDM manufactured by Japan EP Rubber Co., Ltd. as an ingredient,
EP57P, (ML ₁₊₄ (100℃) = 88, iodine value = 15)
and Tackirol, a heat-reactive alkylphenol/formaldehyde resin manufactured by Sumitomo Chemical Co., Ltd., as component (b).
-201 was used, and stannous chloride (SnCl ₂ .2H ₂ O) was used as a vulcanization accelerator. Idemitsu Kosan Co., Ltd. is also used as a rubber softener to adjust hardness and fluidity.
Diana Process Oil PW380 (paraffin oil) was used. Components (a) to (c) and a rubber softener are mixed in advance in a Herschel mixer, and then melt-kneaded in a 30 mmφ diameter twin-screw extruder at a temperature of 210°C to produce denatured water before dynamic vulcanization. A block copolymer composition was obtained.
Component (d) and a vulcanization accelerator were blended in predetermined amounts to 100 parts by weight of this composition, and the mixture was melt-kneaded again at a temperature of 210°C in a twin-screw extruder with a diameter of 30 mm to perform dynamic vulcanization. A block copolymer was obtained. These compositions were injection molded and their basic physical properties were measured. The composition of Comparative Example 2 had poor moldability and poor surface condition. The composition of Comparative Example 3 could not be injection molded, so it was compression molded and its physical properties were measured. The results are shown in Table 1. As is clear from Table 1, the compositions within the scope of the present invention not only have elastomeric properties such as strength and elongation, but also have better heat resistance (compression set at 100°C) than compositions outside the scope of the present invention. Excellent oil resistance and moldability. Examples 8 to 12, Comparative Examples 5 to 10 (B-2) obtained in Reference Example B as component (a)
, Asahi Kasei Co., Ltd. polypropylene as component (b),
Using M1300 (MFR (230℃, L) = 4g/10 minutes)
The same components as in Examples 1 to 7 were used as component (c), component (d), vulcanization accelerator, and rubber softener.

【table】

[Table] Modified hydrogenated block copolymer compositions dynamically vulcanized in the same manner as in Examples 1 to 7 were obtained, injection molded, and their physical properties were measured. In addition, in Comparative Examples 7 to 10, Reference Example A was used as the component (a).
An unmodified hydrogenated block copolymer (A
-2), dynamically vulcanized using 2.0 parts by weight of organic peroxide (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane) and 6 parts by weight of divinylbenzyl (DVB). The procedure was the same as in the example except for the following. The above results are shown in Table 2. From Table 2, it was found that compositions within the scope of the present invention not only have superior elastomer properties such as mechanical strength and elongation, but also superior heat resistance and oil resistance, compared to compositions outside the scope. It is also clear that the composition of the present invention is superior in mechanical strength and oil resistance, even when compared to compositions dynamically vulcanized with known organic peroxides.

【table】

[Table] Examples 13 to 16, Comparative Example 11 (B-3) obtained in Reference Example B was used as component (a).
Component (d) is a heat-reactive brominated alkylphenol/formaldehyde resin manufactured by Sumitomo Chemical Co., Ltd.
Tackirol 250- was used and no vulcanization accelerator was used. The same components as in Examples 1 to 7 were used as the component (b) and the component (c). The same rubber softener as in Examples 1 to 7 was used, but in Example 16, the rubber softener (A-3) obtained in Experimental Example A was used instead of the rubber softener. All components other than component (d) were mixed in a Henschel mixer, and a modified hydrogenated block copolymer composition before dynamic vulcanization was obtained in the same manner as in Examples 1 to 7.
Modified hydrogenated block copolymer compositions were dynamically vulcanized in the same manner as in Examples 1 to 7, injection molded, and their physical properties were measured. The results are shown in Table 3. Table 3 reveals that dynamic vulcanization using a brominated alkylphenol/formaldehyde resin also provides a composition with excellent mechanical strength, heat resistance, and oil resistance.

[Table] Example 17 (B-1) obtained in Reference Example B was used as the (a) component.
100 parts by weight, 100 parts by weight of polypropylene and E1100 manufactured by Asahi Kasei Corporation as component (b), 100 parts by weight of EPDM and EP57P manufactured by Japan EP Rubber Co., Ltd. as component (c),
As a rubber softener, 200 parts by weight of Diana Process Oil PW380 manufactured by Idemitsu Kosan Co., Ltd. (a) to (c) and the softener were mixed in a Henschel mixer, and the mixture was heated to 220°C in a twin screw extruder with a diameter of 30 mm. A modified hydrogenated block copolymer composition prior to dynamic vulcanization was obtained by melt-kneading at a high temperature. Per 100 parts by weight of this composition, 8 parts by weight of heat-reactive alkylphenol/formaldehyde resin Tackirol-201 manufactured by Sumitomo Chemical Co., Ltd. and 2 parts by weight of aluminum trifluoride (AlF ₃ ) were used as component (d).
was added and melt-kneaded again at a temperature of 230° C. in the extruder described above to obtain a dynamically vulcanized modified hydrogenated block copolymer composition. When the physical properties of this composition were measured, the hardness was 80;
The tensile strength was 196 Kg/cm ² , the elongation was 650%, the compression set at 100°C was 42%, and the oil resistance was 10%.

Claims (1)

[Claims] 1 (a) A block copolymer consisting of at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A modified hydrogenated block copolymer in which a molecular unit containing a carboxylic acid group or its derivative group is bonded to a hydrogenated block copolymer obtained by hydrogenating
(b) 20 to 500 parts by weight of polyolefin resin, and (c) 5 to 150 parts by weight of olefin copolymer rubber. A modified hydrogenated block copolymer composition obtained by blending 0.5 to 30 parts by weight of formaldehyde resin, kneading it under heating and melting, and dynamically vulcanizing it.