JPH0339546B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Technical Field) The present invention provides hydrogenated block copolymers in a composition containing a hydrogenated block copolymer having a specific structure, polyphenylene ether, and optionally a polyolefin resin. It is an elastomer-like composition in which the weight ratio of polyphenylene ether, polyphenylene ether, and polyolefin resin is within a specific range, and it has excellent strength, heat resistance, solvent resistance, and low compression set while being soft. The present invention relates to thermoplastic elastomeric compositions having the following characteristics. (Prior art and problems) In recent years, thermoplastic elastomers (hereinafter abbreviated as TPE), which are rubber-like soft materials that do not require a vulcanization process and have moldability similar to thermoplastic resins, have been used for automobile parts, home appliance parts, It is attracting attention in fields such as electric wire coatings, handrails, toys, and miscellaneous goods. However, TPE does not reach the level of vulcanized rubber in terms of quality in terms of quality in the use of vulcanized rubber, which is one of the wide application fields for rubber, and therefore its use in the vulcanized rubber field is limited. One of the representative TPEs is styrene-butadiene block polymer and styrene-isoprene block polymer. These TPEs are highly flexible and have good rubber elasticity at room temperature. That is, the compression set at 23°C is small. It also has excellent moldability, especially injection moldability, but because the polybutadiene block or polyisoprene block in the polymer has double bonds, it has poor heat aging resistance (thermal stability) and weather resistance. There is a problem. By hydrogenating the intramolecular double bonds of a block copolymer of styrene and conjugated diene, an elastomer with improved thermal stability and orientation resistance can be obtained. However, this hydrogenation has the disadvantages of insufficient rubber elasticity at high temperatures, large deformation under heat and pressure, and large compression set at high temperatures, and there are still problems in its use in vulcanized rubber applications. In addition, it has poor processability and is difficult to mold by extrusion, injection, etc. if it is used as it is. Furthermore, styrene-based hydrogenated block copolymers have poor oil resistance, and in this respect, their field of application is severely limited. The composition of the present invention greatly improves these drawbacks and provides an elastomer that is highly flexible, has high high temperature tensile strength, excellent compression set at high temperatures, and has excellent oil resistance. Regarding the technology for improving the heat resistance of styrene resins, as is already well known in the industry, by combining polystyrene with polyphenylene ether, the heat resistance of polystyrene can be changed depending on the blending ratio. I can do it. Regarding the combination of styrene hydrogenated block copolymer and polyphenylene ether, for example, in JP-A-54-88960, polyphenylene ether, A
A ternary composition of a -B-A type styrenic block copolymer or its hydrogenated product and a polyolefin resin is described. This patent relates to a resin composition for the purpose of improving the impact resistance of styrenic resins, and the claims state that the total content of the styrenic block copolymer or its hydrogenated product and the polyolefin component is the total content of the composition. The content is limited to 5-30% by weight. JP-A-59-100159 describes a ternary composition of a polyphenylene ether, an olefin resin, a diblock copolymer of an AB type alkenyl aromatic compound and a conjugated diene, or a hydrogenated product thereof. As stated in the claims of the present invention, polyolefin resins, diblock copolymers of A-B type alkenyl aromatic compounds and conjugated dienes, or hydrogenated products thereof are effective as property improving agents for polyphenylene ether resins. It is described that it is particularly effective in improving the impact resistance and processability of polyphenylene ether. Further, Japanese Patent Publication No. 57-56941 describes a composition of polyphenylene ether or a blend of styrene resin and polyphenylene ether and an ABA type hydrogenated block copolymer. This invention also describes that the A-B-A type hydrogenated block copolymer is effective in improving the processability and impact resistance of polyphenylene ether or a blend of styrene resin and polyphenylene ether. It is something. The present invention is essentially different from the invention of the patent cited as a reference. That is, although the above-mentioned inventions are all aimed at modifying resins, the composition obtained by the present invention is a rubber-like soft material that does not require a vulcanization process and is similar to thermoplastic resins. It is a thermoplastic elastomer with excellent moldability. (Means and Effects for Solving Problems) The present invention is surprisingly effective when a limited amount of polyphenylene ether is added to a hydrogenated block copolymer, which is an elastomer elastic body having a specific structure. This is based on the discovery that compression set, which is a characteristic characteristic, is significantly improved. It is completely surprising that a resin such as polyphenylene ether, which does not have very rubbery properties, has such an effect. That is, the present invention has (a) two or more polymer blocks A mainly composed of a vinyl-substituted aromatic compound, two or more polymer blocks B mainly composed of a conjugated diene compound, and at least By hydrogenating a block copolymer of substantially uniform composition among the polymer chains, the copolymer is located at the end of the polymer chain and has a content of 10 to 50% by weight of bound vinyl-substituted aromatic compound. Polymer block B
consisting of a hydrogenated block copolymer obtained by saturating at least 70% of the double bonds of (b) a polyphenylene ether resin, and the weight ratio of components (a) and (b) is (b)/( an elastomeric composition, characterized in that it satisfies the following: a) = 0.03 to 2.0; )/(a)=0.05 to 0.50 to provide an elastomeric composition. The technical scope of the present invention covers the above components (a), (b) or (a),
It includes not only compositions consisting only of (b) and (c) but also various embodiments described below or all compositions utilizing the gist of the present invention. Hydrogenated block copolymer (a) used in the present invention
has two or more polymer blocks A mainly composed of a vinyl-substituted aromatic compound and at least two or more polymer blocks B mainly composed of a conjugated diene compound, and has at least one polymer block B at the end of the polymer chain. It is a hydrogenated block copolymer obtained by hydrogenating a block copolymer having a substantially uniform structure between polymer chains.Some examples are expressed by the general formula: B(-A-B) _o n≧2 B-A(-B-A) _o n≧1 B(-A-B)- _n X(-B-A) _o m, n≧1 m+n=2~ 4 B-A(-B-A) _-n X(-A-B) _-o A-B m, n≧1, m+n=2~4 B-A(-B-A) _-n X-(B -A) _o m, n≧1, m+n=2 to 4 (where X represents a coupling agent) The vinyl-substituted aromatic compound polymer block A is:
It is a polymer made of styrene, α-methylstyrene, P-ethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, or a mixture thereof. Conjugated diel polymer block B is 1,3-butadiene isoprene, 1,3-pentadiene, 2,
3-dimethyl, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,
A polymer consisting of 3-octadiene, 4-ethyl-1,3-hexadiene or a mixture thereof, or a polymer consisting of a mixture of the above conjugated diene and a vinyl-substituted aromatic compound. and preferably a conjugated diene polymer having a 1,4-structure content of 50% by weight or more, or a vinyl-substituted aromatic compound content of 25% by weight or less,
It is a conjugated diene-vinyl substituted aromatic compound copolymer having a 1,4-structure content of 50% by weight or more. The content of the bonded vinyl-substituted aromatic compound in the block copolymer consisting of block A and block B is
It is 10-15% by weight. Bound vinyl-substituted aromatic compound content is 10% by weight
If it is less than this, the compatibility between the hydrogenated block copolymer and the polyphenylene ether will be insufficient, and it is not preferable.
If it exceeds 50% by weight, the composition becomes too hard and does not meet the purpose of the present invention. In the block copolymer represented by the above general formula, the block B disposed at the end of the polymer chain preferably ranges from 3 to 25% of the bound polybutadiene in the block copolymer, and more preferably from 7 to 22%. The composition of the present invention provides a composition with lower hardness than a composition using, for example, an A-B-A type hydrogenated block copolymer which does not have polybutadiene block B at the terminal end. decrease. When comparing compositions with a constant hardness, it is possible to increase the content of the bound vinyl-substituted aromatic compound in the hydrogenated block copolymer, and it is possible to obtain a composition with high compatibility with polyphenylene ether. I can do it. When comparing compositions with a constant hardness, it is possible to increase the amount of polyphenylene ether in the composition, resulting in a composition that is more heat resistant and has excellent physical properties with less compression set. give. Furthermore, the block copolymer represented by the above general formula may be a so-called complete block polymer or a gradually decreasing block copolymer, and the specific manufacturing method is such that the composition between the polymer chains is substantially uniform. Any conventionally known method may be used as long as it yields the desired result. The molecular weight of the block copolymer is not particularly limited, but is generally 5,000 to 1,000,000.
It is. The method for producing the hydrogenated block copolymer is not particularly limited, and any known method may be employed. For example, it can also be obtained by hydrogenating a block copolymer represented by the above general formula using a nickel compound-organoaluminum compound as a catalyst, as described in Japanese Patent Publication No. 8704/1983. It can also be obtained by hydrogenation using a Ti-based catalyst as described in JP-A-59-133203. In the hydrogenated block copolymer of the present invention, 70% or more of the double bonds of component B are saturated.
If it is less than %, the resulting composition will have poor heat aging resistance and weather resistance, which is not preferred. The polyphenylene ether resin (b) used in the present invention has a bonding unit of the formula (Here, R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen,
Represents a substituent selected from the group consisting of halogen and hydrocarbon groups, and may be the same or different. ) is a homopolymer and/or copolymer consisting of
The reduced viscosity measured at 30% in a 0.5 g/dl chloroform solution is in the range of 0.15 to 0.70, more preferably in the range of 0.20 to 0.60. As this polyphenylene ether resin, known ones can be used. Specific examples include poly(2,6-dimethyl-1,4 phenylene ether), poly(2-methyl-6ethyl-1,4 phenylene ether), poly(2,6-diphenyl-1, 4-phenylene ether), poly(2-methyl-6-phenyl-
1,4-phenylene ether), poly(2,6-
dichloro-1,4-phenylene ether), and combinations of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Also included are polyphenylene ether copolymers such as polymers. Among these polyphenylene ethers, 2,6-dimethyl-1,4-phenylene ether is preferably used in the present invention. The polyphenylene ether used in the present invention is 2,
0.5 g/dl for 6-dimethyl-1,4-phenylene ether, 30°C in chloroform solution
Those having a reduced viscosity measured in the range of 0.15 to 0.70 are used, and those having a reduced viscosity of 0.20 to 0.60 are more preferably used. As shown in the Examples below, when the reduced viscosity of 2,6-dimethyl-1,4-phenylene ether used in the present composition is in the range of 0.20 to 0.70, the lower the molecular weight, the higher the tensile strength and the higher the transparency. It also has the characteristic of being of good quality. The amount of polyphenylene ether added is in the range of 3 to 200% by weight based on the hydrogenated block copolymer. If the amount of polyphenylene ether added to the hydrogenated block copolymer is less than 3% by weight, the improvement in heat resistance is insufficient, and the improvement in high temperature tensile strength and compression set is insufficient. Furthermore, the addition of polyphenylene ether exceeding 200% by weight to the hydrogenated block copolymer means that the hydrogen content of the vinyl-substituted aromatic compound polymer block A used in the composition of the present invention is less than 50% by weight. Additive block copolymers are not preferred because they do not have sufficient compatibility with polyphenylene ether and also have high hardness. The composition of the present invention may contain (c) a polyolefin resin, if necessary. By adding the polyolefin resin, the oil resistance and tensile strength of the composition are improved, as well as the processability. The polyolefin resin used in the present invention is α
- Any resin obtained by polymerizing olefins may be used, such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, carboxylated modified resins thereof, or mixtures thereof. Particularly preferred are polyethylene and polypropylene. The polyolefin resin has good compatibility with the hydrogenated block copolymer, and a composition having good compatibility can also be obtained by adding the polyolefin resin within the scope of the present invention. The amount of polyolefin resin added is in the range of 5 to 50% by weight, more preferably in the range of 10 to 45% by weight, based on the hydrogenated block copolymer. If less than 5% by weight is added, oil resistance and tensile strength will not be improved sufficiently, and if more than 50% by weight is added, the properties of the resulting composition will be too close to resin-like and the hardness will increase, which is not preferable. As an embodiment of the present invention, for example, (1) non-aromatic rubber softening oil is added in a range of 30 to 250 parts by weight to 100 parts by weight of the composition described in claim 1 or 2. (2) An elastomer obtained by adding 10 to 250 parts by weight of a non-aromatic rubber softening oil to 100 parts by weight of the composition according to claim 1 or 2. One or two inorganic fillers selected from calcium carbonate, magnesium hydroxide, talc, white carbon, carbon black, mica, and barium sulfate per 100 parts by weight of the composition.
To provide an elastomeric composition containing 10 to 500 parts by weight of a species or more. That is, the present invention is defined in claim 1.
The composition described in item 2 or item 2 contains a non-aromatic rubber softening oil and, if necessary, calcium carbonate, magnesium hydroxide, talc, white carbon,
An inorganic filler selected from carbon black, mica, and barium sulfate can be added. Addition of a non-aromatic rubber softening oil to the elastomeric composition increases flexibility and greatly increases economic efficiency without significantly impairing the heat resistance of the composition. Rubber softeners are generally used for the purpose of softening, increasing the volume of rubber, improving processability, etc., and are mineral oils called process oils or extender oils. These mineral oils include those called aromatic, naphthenic, and paraffinic oils, and naphthenic or paraffinic oils are preferred in the present invention. The preferred amount of oil added is the elastomeric composition according to claim 1 or 2 of the present invention.
The amount is 10 to 250 parts by weight per 100 parts by weight. If it exceeds 250 parts by weight, the oil may bleed out and the mechanical strength of the composition will be reduced, which is not preferable. Addition of less than 10 parts by weight of oil poses no practical problem, but the improvement in economical efficiency is insufficient. Furthermore, one or more inorganic fillers selected from calcium carbonate, magnesium hydroxide, talc, white carbon, carbon black, mica, and barium sulfate can be added to the composition of the present invention, if necessary. Addition of these inorganic fillers can significantly reduce product costs. An elastomeric composition in which the inorganic filler is added in an amount of 10 to 250 parts by weight of a non-aromatic rubber softening oil per 100 parts by weight of the composition according to claim 1 or 2. The amount is 10 to 500 parts by weight per 100 parts by weight of the product. Addition of less than 10 parts by weight of an inorganic filler causes no practical problems, but the improvement in economical efficiency is insufficient, and addition of more than 500 parts by weight is preferable because the mechanical strength of the composition decreases markedly and the hardness increases. do not have. As a method for compounding, all methods generally used for manufacturing ordinary rubber compositions can be employed. Basically, it is a mechanical melt-kneading method, and a single-screw extruder, a twin-screw extruder, a Banbury mixer, various kneaders, etc. are used. Flame retardants, glass fibers, carbon fibers, antioxidants, heat stabilizers, ultraviolet absorbers, hindered amine light stabilizers, colorants, etc. can be suitably added to the composition obtained in the present invention, if necessary. . EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Reference example 1 4 kg of cyclohexane in 10 autoclaves,
Add 130 g of 1,3-butadiene monomer, 1.5 g of n-butyllithium, and tetrahydrofuran at a molar ratio of n-BuLi/THF = 1/40, and heat at 70°C.
Polymerization was carried out for 45 minutes, then 200 g of styrene monomer was added for 30 minutes, and then 1,3-butadiene monomer was added.
470 g was added and polymerized for 75 minutes, and finally 200 g of styrene monomer was added and polymerized for 30 minutes to synthesize a butadiene-styrene-butadiene-styrene type living block polymer (B-A-B-A). This product contains 40% bound styrene, 33% blocked styrene, and 1,2-butadiene units.
It had a vinyl bond content of 35% (30% based on total polymer), a number average molecular weight of about 60,000, and a living lithium content of 1.65 mmol per 100 g of living polymer. The block copolymer thus obtained is
The molecular weight distribution was measured by GPC using a refractometer as a detector, and at the same time, the differential styrene content in the developing solution was determined using an ultraviolet absorption photometer as a detector. GPC is Shimadzu LC-1 type, Karam is
HSG30, 50, 60, developing solution is tetrahydrofuran,
Measurements were made at a temperature of 40°C. From the obtained GPC chart, the difference in styrene content in the remaining components after removing 10% by weight of each of the low molecular weight components and high molecular weight components was determined, and it was only 2.8% by weight, indicating a substantially uniform composition. It turned out that. Reference Example 2 4 kg of cyclohexane, 180 g of styrene monomer, and 1.1 g of n-butyllithium were added to an autoclave, and polymerized at 60°C for 3 hours. Then, 540 g of 1,3-butadiene monomer was added, and polymerized at 60°C for 3 hours. Finally, add 180g of styrene monomer and
After polymerization for 3 hours at ℃, the number average molecular weight was approximately 60,000, with a bound styrene content of 40%, a blocked styrene content of 38.5%, and a 1,2-vinyl bond content of butadiene units of 13% (9% in terms of total polymer). Styrene is
A butadiene-styrene living block copolymer (A-B-A type) was obtained. The living lithium in this polymer was 1.65 mmol/100 g of polymer. Reference Example 3 Each living polymer solution obtained in Reference Example was diluted with purified and dried cyclohexane, adjusted to a living polymer concentration of 5% by weight, and subjected to a hydrogenation reaction. Place 10 kg of the above living polymer solution (amount of living polymer) in a sufficiently dry autoclave equipped with a stirrer.
500g) was charged, degassed under reduced pressure, replaced with hydrogen, and maintained at 40°C with stirring. Then the concentration as hydrogenation catalyst
1.0 mmol/100 ml of toluene solution of bis(cyclepentadienyl)titanium dichloride 200
ml (catalytic amount: 2.0 mmol) was charged into an autoclave, 5.0 Kg/cm ² of dry gaseous hydrogen was supplied, and a hydrogenation reaction was carried out for 2 hours with stirring. both
Substantial hydrogen absorption was completed within 30 minutes, and the reaction solution was a homogeneous, low-viscosity solution with a slightly black to gray-black color. The reaction solution was returned to normal temperature and pressure and taken out from the autoclave, and a large amount of methanol was added to precipitate the polymer, which was separated and dried to obtain a white hydrogenated polymer. The hydrogenation rate of the conjugated diene unit was 99%, and the material was in the form of a flexible thermoplastic elastomer. (Samples of Example 1 and Comparative Example 1) Examples 1 to 5, Comparative Examples 1 and 2 Crumb-like material of hydrogenated B-A-B-A block copolymer obtained in Reference Example 3 and reduced viscosity (30℃, 0.5g/dl chloroform solution) 0.37 2,
Powder of 6-dimethyl-1,4-phenylene ether (hereinafter referred to as PPE), Irganox 1010 as a heat stabilizer, tetrakis [methylene-3-(3',
5'-di-tert-butyl-4'-hydroxyphenyl)
propionate] methane After sufficient dry blending at 0.2 phr with the composition shown in Table 1, the mixture was press-pelletized using a twin-screw press at a resin temperature of 240°C. The pellets were kneaded at 250°C using a Brabender, and then compression molded into test pieces. Hardness (JISA) of this item, tensile strength at room temperature, 70
°C tensile strength and compression set test (JISK6301)
The results are shown in Table 1. As Comparative Example 1, the physical properties of a B-A-B-A hydrogenated block polymer are shown. Comparative Example 2: Hydrogenated block polymer and PPE
The physical properties of a product with a weight ratio of 70/30 are shown.

[Table] As is clear from the results, within the scope of the present invention
As the amount of PPE added increases, the tensile strength and compression set at 70°C are significantly improved. The test piece of Comparative Example 2 was made of hydrogenated block copolymer and
It was clear from visual observation that the PPE had insufficient compatibility. Examples 6 to 9 B-A-B-A type polymer obtained in Reference Example 3
Example 1 was repeated using 15 parts by weight of PPE powder with reduced viscosities of 0.28, 0.34, 0.49, and 0.70 (30° C., 0.5 g/dl chloroform solution). Table 2 shows the results.
Shows.

[Table] As is clear from the results of Examples 6 to 9, PPE
As the molecular weight increases, the tensile strength at room temperature tends to decrease. Example 10, Comparative Examples 3 and 4 The number average molecular weight was approximately 6 using almost the same method as in Reference Example 1.
A B-A-B-A type block polymer was obtained having a 40% bound styrene content and a terminal block of 8.5 bound polybutadiene. Hydrogenate this material,
A hydrogenated block copolymer in which 99% of the conjugated diene units were hydrogenated was obtained. As a sample for Comparative Example 3, an A-B-A type hydrogenated block copolymer was prepared by hydrogenating the A-B-A type block copolymer prepared in Reference Example 2. As a sample for Comparative Example 4, a sample with a number average molecular weight of 58,000 and a bound styrene content was prepared in the same manner as in Reference Example 1.
A 40% AB type block polymer was synthesized and hydrogenated to obtain an AB type hydrogenated block copolymer in which 99% of the conjugated diene units were hydrogenated. Hydrogenated block copolymers with different block patterns synthesized in this way and PPE with reduced viscosity of 0.49
A test piece having a composition of hydrogenated block copolymer/PPE=72/28 was prepared in the same manner as in Example 1. Table 2 shows the hardness and compression set of these compositions.

[Table] As is clear from Examples and Comparative Examples, when comparing the hardness of compositions using hydrogenated blocks with different block types and with the same bound styrene content, the hydrogenated block copolymer with terminal blocks has lower hardness. A composition is obtained. Further, the AB type hydrogenated block copolymer has no rubber elasticity and has extremely poor compression set. Examples 11 and 12 A B-A-B block copolymer was prepared in the same manner as in Reference Example 1, and a radial block copolymer (B
-A-B) ₄ Si was synthesized. This one has a molecular weight of 12
The bound styrene content was 32%, and the terminal B block was 10% of the bound polybutadiene. This material is hydrogenated to contain 99% conjugated diene units.
A hydrogenated radial type hydrogenated block copolymer was obtained. A composition was prepared in the same manner as in Example 1 by adding 80 parts by weight of this hydrogenated block copolymer, 10 parts by weight of high-density polyethylene (Santech 241 manufactured by Asahi Kasei), 10 parts by weight of PPE with a reduced viscosity of 0.28, and 0.2 phr of Irganox 1010. Physical properties were measured on the compression-molded piece (Example 11). This item has a hardness of 87, a tensile strength at room temperature of 280Kg/cm,
Elongation 600% 70℃, tensile strength 132Kg/cm ² , elongation 300%,
The compression set was particularly excellent with a compression set of 32%. Example 11 was repeated except that the high density polyethylene of Example 5 was replaced with random polypropylene (Asahi Kasei M3500, ethylene content 5%). (Example 12). This item has a hardness of 90, a tensile strength at room temperature of 305Kg/ ^cm2 ,
Elongation 600% 70℃, tensile strength 135Kg/cm ² , elongation 300%,
The compression set was 34. Examples 13 to 16, Example 5 Table 4 was prepared using the B-A-B-A type block copolymer additive used in Example 1, random polypropylene (Asahi Kasei M3500), and PPE with a reduced viscosity of 0.34.
A composition having the above composition was prepared in the same manner as in Example 11.

[Oil resistance test method]

A test piece (W ₁ ), which was weighed according to JIS K6301, was immersed in No. 3 test oil (lubricated bone oil) at 70°C for 2 hours, then taken out, and immersed in Ascent. Take it out quickly, wipe it lightly with filter paper, and weigh it to find the weight (W ₂ ): ΔW=W ₂ −W ₁ /W ₁ ×10 ² .

[Table] As seen in Examples 13 to 16, as the content of polypropylene in the composition increases, the oil resistance improves. As shown in Comparative Example 5, when the amount of polypropylene in the composition is outside the range of the present invention, the hardness becomes high. Examples 17-19 The number average molecular weight was 14.7 using almost the same method as in Reference Example 1.
A B-A-B-A type block polymer containing 29% of the conjugated styrene content and 8.0% of the terminal block-linked polybutadiene was obtained, and this was hydrogenated to form a block copolymer in which 99% of the conjugated diene units were hydrogenated. A polymer was obtained. This high molecular weight B-A-B-A type hydrogenated block copolymer, PPE with a reduced viscosity of 0.50, random polypropylene (Asahi Kasei M3500), paraffin oil (PW380 Idemitsu Petrochemical), and calcium carbonate (Whiten SB Shiroishi Calcium Co., Ltd.) A composition having the following composition was prepared using the following composition. Table 6 shows the physical properties of these materials. Example 17 is a hydrogenated block copolymer having the composition shown in the table,
PPE and polypropylene were pelletized by extrusion using a twin-screw extruder in the same manner as in Example 1, and kneaded again using a Brabender to form a composition. In Example 18, a hydrogenated block copolymer having the composition shown in the table, PPE, polypropylene, and paraffin oil were kneaded using a heated roll at 220°C to form a composition. In Example 19, the composition prepared in Example 18 was pulverized, dry-blended with calcium carbonate, pelletized using a press at 230°C, and then kneaded again with heated rolls at 220°C to form a composition.

[Table] Reference Example 4 A block copolymer was produced based on the description in the lower left to lower right columns of page 8 of JP-A-58-141233. First, in order to produce a living polymer of a block copolymer having a polymer structure of B-A-Li, 20% of purified and dried butadiene was placed in a stainless steel polymerization vessel equipped with a stirrer and internally purged with nitrogen gas.
An n-hexane solution containing a concentration of % by weight was charged, and then n-butyllithium was added as a catalyst and polymerization was carried out at 70% for 90 minutes. Then add 20 styrene
A n-hexane solution containing a concentration of % by weight was added, and the polymerization was continued at 50° C. for 2 hours. The amount of added monomer and catalyst is such that n of the polystyrene block of the block copolymer is approximately 13,000 and the styrene content is
The content was adjusted to 62.5% by weight. The w/n of the polystyrene block was approximately 1.25. The polymerization vessel used here was used as a storage tank in the next continuous polymerization process. In the continuous polymerization process, a stainless steel polymerization vessel with a stirrer with an L/D of approximately 4 is used as the first polymerization vessel R-
A polymerizer having an L/D of about 8 was used as the second polymerizer R-2. After internal purge with nitrogen gas in advance, the living polymer of the block copolymer and butadiene were placed in the polymerization vessel R-1, which had been heated to a predetermined temperature, and styrene was placed in the polymerization vessel R-2 in weight ratios. It was fed continuously at a ratio of 32:48:20. Butadiene and styrene were each supplied as a 20% by weight solution in n-hexane.
The average residence time in the polymerization vessel R-1 and polymerization vessel R-2 was about 45 minutes and about 35 minutes, respectively, and the polymerization temperature was set at an average of about 80°C and about 75°C, respectively, for continuous polymerization. Under these conditions, the conversion rate of butadiene or styrene at the outlet of each polymerization vessel was about 95% or more. In this way, a block copolymer was synthesized which had a non-uniform composition in which the amount of bound styrene varied between polymer chains by about 30% by weight, and the average amount of bound styrene was 40% by weight. Next, the copolymer was hydrogenated by the method of Reference Example 3 to obtain a hydrogenated block copolymer. Reference Example 5 A modified block copolymer was produced based on the description in the lower left to lower right columns of page 10 of JP-A-58-27740. 3 parts by weight of maleic anhydride and 0.1 part by weight per 100 parts by weight of the hydrogenated B-A-B-A type block copolymer obtained in Reference Example 3.
After uniformly mixing 25B (manufactured by NOF Corporation), it was fed to a screw type extruder (single screw, screw diameter 20 mm, L/D 24, full light type screw) under a nitrogen atmosphere, and converted into mylene at a cylinder temperature of 250 °C. The reaction was carried out. Unreacted maleic anhydride was removed from the obtained modified block copolymer by heating under reduced pressure. The amount of maleic anhydride added was determined by titration using sodium methyler and was 1.3% by weight.
It was hot. In this way, a modified hydrogenated block copolymer was obtained. Comparative Example 6 The hydrogenated block copolymer with non-uniform composition between polymer chains obtained in Reference Example 4 was prepared by using PPE with reduced viscosity = 0.49 in the same manner as in Example 10 to form hydrogenated block copolymer/PPE. A test piece was prepared by kneading with a composition of =72/28. The hardness of this composition was 88, giving it a soft, rubber-like feel, but the compression set was 82, which was extremely poor. In this way, when a uniform hydrogenated block copolymer whose composition changes between polymer chains is used, although it has excellent rubber-like flexibility, it has poor compression set, and a desirable composition cannot be obtained. I found out. Example 20, Comparative Example 7 The following was added to the B-A-B-A type block copolymer obtained in Reference Example 3 and the modified hydrogenated block copolymer obtained in Reference Example 5. , and extruded in the same manner as in Example 1. <Composition> ● (Modified) hydrogenated block copolymer 100 parts by weight ● PPE (reduced viscosity = 0.37) 30℃, 0.5 g/dl Chloroform 50 parts by weight ● Paraffin oil PW-380 (manufactured by Idemitsu Kosan)
50 parts by weight ●Titanium oxide 1 part by weight ●Stabilizer Irganox 1010 ^* 0.3 parts by weight *Tetrakis [methylene-3-(3',5'-di-tert)
-Butyl-4'-hydroxyphenyl)propionate]methane After the obtained composition was left to stand for one week, injection moldability was evaluated using an injection molding machine, and test pieces were cut out from the obtained molded product and physical properties were evaluated. was measured.
The obtained results are summarized in Table 11. As is clear from Table 11, when the modified hydrogenated block copolymer is used, although it has excellent flexibility, the hygroscopicity of the composition increases, so silver appears on the molded product, and the mold It was found that the composition had poor releasability from the mold and was not a desirable composition. The composition of the present invention was found to be a desirable composition since there were no problems with the quality of the molded product or the mold releasability.

【table】

Claims (1)

[Scope of Claims] 1 (a) Two or more polymer blocks A mainly composed of a vinyl-substituted aromatic compound and two or more polymer blocks B mainly composed of a conjugated diene compound, A block copolymer having at least one B disposed at the end of a polymer chain and having a content of 10 to 50% by weight of bound vinyl-substituted aromatic compound and having a substantially uniform composition among the polymer chains is hydrogenated. a hydrogenated block copolymer obtained by adding saturated at least 70% of the double bonds of polymer block B, and (b) a polyphenylene ether resin, and component (a), An elastomeric composition characterized in that the weight ratio of (b) satisfies the formula (b)/(a)=0.03 to 2.0. 2 (a) It has two or more polymer blocks A mainly composed of a vinyl-substituted aromatic compound and two or more polymer blocks B mainly composed of a conjugated diene compound, and at least one of the polymer blocks B is a polymer. By hydrogenating a block copolymer of substantially uniform composition between the polymer chains, which is located at the chain end and has a bound vinyl-substituted aromatic content of 10 to 50% by weight. A hydrogenated block copolymer obtained by saturating at least 70% of the double bonds of polymer block B, consisting of (b) a polyphenylene ether resin, and (c) a polyolefin resin, and comprising component (a), (b),
An elastomeric composition characterized in that the weight ratio of (c) satisfies the following formula: (b)/(a)=0.03-2.0 (c)/(a)=0.05-0.50.