JPH0578582B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a highly elastic hydrogenated block copolymer composition that is highly flexible and can be used as a material for various molded products having excellent high-temperature compression set, mechanical strength, and moldability. It is something. (Prior art) In recent years, thermoplastic elastomers, 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 appliances, electric wire coatings, and medical applications. It is useful in the fields of parts, miscellaneous goods, footwear, etc. Among such thermoplastic elastomers, there are some elastomeric compositions using hydrogenated derivatives of vinyl aromatic compound-conjugated diene compound block copolymers (hereinafter abbreviated as hydrogenated block copolymers). proposals have been made. For example, JP-A-50-14742, JP-A-52-65551, and JP-A-58-206644 disclose elastomeric compositions in which a hydrogenated block copolymer is blended with a hydrocarbon oil and an olefinic polymer. Furthermore, JP-A-59-6236 and JP-A-59-131,613 disclose an elastomeric composition in which a hydrogenated block copolymer is blended with a hydrocarbon oil, an olefinic polymer, and an inorganic filler. is partially cross-linked in the presence of an organic peroxide and a cross-linking aid,
Proposals have been made to improve the rubber elasticity (compression set) at high temperatures of the resulting elastomeric composition. Furthermore, JP-A-54-88960, JP-A-59
No. 100159 and Japanese Patent Publication No. 57-56941 disclose hydrogenated block copolymer compositions containing a hydrogenated block copolymer and polyphenylene ether as essential components and consisting of a polyolefin resin and a polystyrene resin. ing. However, these proposals are aimed at modifying the resin composition, and the resulting composition is a thermoplastic resin, which cannot be used as the thermoplastic elastomer mentioned above, and cannot be used as an elastomeric composition. It did not have rubber elasticity. (Problems to be Solved by the Invention) Although the elastomeric composition of the hydrogenated block copolymer obtained by the above-mentioned prior art proposal has excellent rubber elasticity (compression set) at 70°C, Its elasticity is poor at over 70%, and it does not reach the level of compression set at high temperatures conventionally required for vulcanized rubber applications, and it does not have the recyclability and ease of molding that are characteristic of thermoplastic elastomers. However, the rubber elasticity at high temperatures is currently still in the insufficient range, and this has been taken for granted. (Means for Solving the Problems) The present invention has been made to solve the problems that have been difficult with the conventional elastomer molding materials described above, and in particular, the processability and recyclability of thermoplastic elastomers. This request was made based on the desire for a molding material that could satisfy both performance and rubber elasticity at high temperatures (compression set at 100°C), which had not been achieved until now. It has been discovered that this can be satisfactorily achieved by the method of the present invention, and has also been found to be a practically useful composition. That is, the present invention provides (1)(a) a polymer block A mainly composed of at least two vinyl aromatic compounds;
A hydrogenated block copolymer a obtained by hydrogenating a block copolymer consisting of a polymer block B mainly composed of conjugated diene compounds
100 parts by weight (b) 5 to 100 parts by weight of polystyrene resin (c) Softener for non-aromatic rubber 20
~200 parts by weight (d) Binding unit

[Formula] (wherein R ₁ , R ₂ , R ₃ , and R ₄ are each selected from the group consisting of hydrogen, halogen, and hydrocarbon group), and has a reduced viscosity (0.5 g/dl Chloroform solution, measured at 30℃)
The polyphenylene ether resin d, which is a homopolymer and/or copolymer, is in the range of 0.15 to 0.70 to the above a/d = 90/10 to 30/70.
Highly elastic hydrogenated block copolymer composition (2) consisting of (weight ratio) (a), (b), (c), (d) described in item (1) above (where a/d= 90/10 to 40/60) and (e) polyolefin resin e5 to 100 parts by weight, and
a/(b+d+e)=82/18~37/63 (weight ratio)
A highly elastic hydrogenated block copolymer composition is provided. The present invention will be described in detail below. The present invention is a rubber elastic body with high temperature compression set (100℃ x 22 hours, compression ratio 25% according to JIS-K6301).
gives elastomer compositions exhibiting very good performance, for example values of 33 to 65% (depending on the examples). The hydrogenated block copolymer used as component (a) in the present invention consists of a polymer block A mainly composed of at least two vinyl aromatic compounds and a polymer block mainly composed of at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer consisting of B, for example, A-B-A, B
-A-B-A, (A-B) ₄ ---Si, A-B-A-B
This is a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as -A. This hydrogenated block copolymer contains 5 to 60% by weight, preferably 10 to 60% by weight of a vinyl aromatic compound.
Containing 50% by weight, and referring to the block structure, polymer block A mainly composed of a vinyl aromatic compound is a vinyl aromatic compound polymer block or contains more than 50% by weight, preferably 70% by weight of a vinyl aromatic compound. It has the structure of a copolymer block of the above-contained vinyl aromatic compound and a hydrogenated conjugated diene compound, and the polymer block B mainly consists of the hydrogenated conjugated diene compound. A hydrogenated conjugated diene compound polymer block, or a hydrogenated conjugated diene compound containing more than 50% by weight, preferably 70% by weight.
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. As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more types can be selected from, for example, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc.
Among them, styrene is preferred. Further, examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
One or more types are selected from 1,3-butadiene and the like, and among them, butadiene, isoprene, and a combination thereof are preferred. The microstructure of a polymer block mainly composed of a conjugated diene compound before hydrogenation can be arbitrarily selected; for example, in a polybutadiene block, the 1,2-microstructure is 20 to 50.
%, preferably 25-45%. Further, the number average molecular weight of the hydrogenated block copolymer used in the present invention having the above structure is 5000 to 5000.
1000000, preferably 10000 to 800000, more preferably 30000 to 500000, and the molecular weight distribution [weight average molecular weight (w) and number average molecular weight (n)]
(w/n)] is 10 or less. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof. These block copolymers may be produced by any method as long as they have the above structure. 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,
By the method described in Japanese Patent Publication No. 8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Application Publication No. 59-133203,
The hydrogenated block copolymer used in the present invention can be synthesized by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst. At that time, the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least
By hydrogenating 80% of the polymer, a polymer block mainly composed of a conjugated diene compound can be morphologically converted into an olefinic compound polymer block.
In addition, hydrogenation of aromatic double bonds based on vinyl aromatic compounds copolymerized into polymer block A mainly composed of vinyl aromatic compounds and, if necessary, polymer block B mainly composed of conjugated diene compounds. Although there is no particular restriction on the hydrogenation 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, the polystyrene resin used as component (b) of the present invention is an essential component for improving the processability of the resulting composition, and those obtained by known radical polymerization methods and ionic polymerization methods are preferable. It can be used in It is preferably 5 or less. The blending amount of component (b) is 5 parts per 100 parts by weight of component (a).
It can be suitably selected within the range of ~100 parts by weight.
If the amount exceeds 100 parts by weight, the hardness of the resulting elastomeric composition becomes too high, resulting in a loss of flexibility and a product with a rubbery feel. (distortion) becomes extremely bad, which is not desirable. Furthermore, if the amount is less than 5 parts by weight, the processability will not be improved, which is not preferable. The rubber softener used as component (c) in the present invention is an essential component for making the resulting composition into a flexible rubber-like composition, and is a non-aromatic mineral oil, liquid or low molecular weight synthetic rubber softener. Softeners are suitable. Among these, mineral oil-based rubber softeners, called process oils or extender oils, which are generally used to soften, increase volume, and improve processability of rubber, are mixtures of aromatic rings, naphthenic rings, and paraffin chains. Those in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total carbons are called paraffin series, and the number of carbon atoms in the naphthene ring is 30 to 45%.
Those are naphthenic, and the number of aromatic carbons is 30%.
Those with a larger amount are considered to be aromatic. Components of the invention
The mineral oil-based rubber softener used as (c) is preferably a naphthene-based or paraffin-based one in the above category, and an aromatic one with an aromatic carbon number of 30% or more is the same as component (a). The composition is unfavorable in terms of dispersibility and solubility. The properties of these non-aromatic rubber softeners include a kinematic viscosity of 20 to 50 cst at 37.8°C, a pour point of -10 to -15°C, and a flash point of 170 to 300°C. As the synthetic softener, polybutene, low molecular weight polybutadiene, etc. can be used, but the above-mentioned mineral oil-based softeners for rubber give better results. The amount of the softener (component (c)) is 20 to 200 parts by weight per 100 parts by weight of component (a). If the amount exceeds 200 parts by weight, the softener tends to bleed out, which may result in stickiness in the final product and may also reduce mechanical properties. If the amount is less than 20 parts by weight, the resulting composition becomes close to a resin composition, increases in hardness, loses flexibility, and is also unfavorable from an economic point of view. Next, the polyphenylene ether resin used as component (d) of the present invention is an essential component for improving the compression set of the resulting composition, and is a bonding unit.

[Formula] (where R ₁ , R ₂ , R ₃ and R ₄ are each
(selected from the group consisting of hydrogen, halogen, and hydrocarbon groups, and may be the same or different)
A homopolymer and/or copolymer consisting of
The reduced viscosity measured at 30° C. 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, 2-methyl-6ethyl-1,4-phenylene ether, and 2,6-diphenyl-1,4.
-phenylene ether, 2-methyl-6-phenyl-1,4-phenylene ether, 2,6-dichloro-1,4-phenylene ether, etc.''・6-dimethyl-1,4-phenylene)ether, poly(2
-Methyl-6-ethyl-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 2,6-dimethylphenol and other phenols (for example, 2,3,6-
Also mentioned are polyphenylene ether copolymers such as copolymers with trimethylphenol and 2-methyl-6-butylphenol. Among them, poly(2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol and 2,3,6
A copolymer with -trimethylphenol is preferable, and furthermore, a copolymer with poly(2,6-dimethyl-1,4-
(phenylene) ether is preferred. In the case of poly(2,6-dimethyl-1,4-phenylene ether), its reduced viscosity (0.5 g/dl,
(chloroform solution, measured at 30°C) preferably ranges from 0.15 to 0.70, more preferably from 0.30 to 0.70.
It is in the range of 0.60. The amount of component (d) to be blended should be selected so that the weight ratio of component (a) hydrogenated block copolymer/component (d) polyphenylene ether is in the range of 90/10 to 30/70. and 90/10 to 40/60 if component (e) is present.
can be suitably selected within the range. If the weight ratio value is less than 30/70 or if component (e) is present,
If the ratio is less than 40/60, the hardness of the resulting elastomeric composition becomes too high, resulting in a loss of flexibility and a resinous composition, which not only makes it impossible to obtain a product with a rubbery feel, but also reduces the rubber elasticity at high temperatures. Compression set (100°C x 22 hours)] is poor and unfavorable. In addition, a blend in which the weight ratio exceeds 90/10 is not preferred because no improvement in rubber elasticity (compression set) at high temperatures is observed as an effect of adding polyphenylene ether. Next, the polyolefin resin used as the component (e) of the present invention is characterized by the processability of the resulting composition,
and or effective in improving heat resistance, such as polyethylene, isotactic polypropylene, copolymers of propylene and small amounts of other α-olefins, such as propylene-ethylene copolymers,
Examples include propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, poly4-methyl-1-pentene, polybutene-1, and the like. MFR (ASTM-D-
1238-L condition, 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 component (e) is 5 parts per 100 parts by weight of component (a).
-100 parts by weight, preferably 10-70 parts by weight. If the amount exceeds 100 parts by weight, the hardness of the resulting elastomeric composition becomes too high, resulting in a loss of flexibility and a product with a rubbery feel. (distortion) becomes extremely bad, which is not desirable. Furthermore, when the amount is less than 5 parts by weight, the polyolefin resin exhibits the same processability as the composition of the present invention to which it is not added. component
If (e) exists, a/(b+d+e)=
The relationship between 82/18 and 37/63 must be satisfied.
If the ratio is less than 37/63, the resulting composition will be resin-like and have poor rubber elasticity at high temperatures, which is not preferred. In addition to the above-mentioned components (a) to (e), the composition of the present invention may further contain an inorganic filler, if necessary. This inorganic filler not only has the benefit of reducing product cost as an extender, but also has the benefit of positively affecting quality improvement (compression set, etc.). Examples of inorganic fillers include calcium carbonate, carbon black,
Talc, clay, magnesium hydroxide, mica,
Examples include barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), and titanium oxide. As carbon black, channel black, furnace black, etc. can be used. Among these inorganic fillers, talc, calcium carbonate and furnace black are economically advantageous and preferred.
It is also possible to add a conductive filler to impart conductivity; for example, conductive carbon such as ketchen black may be used. The amount of the inorganic filler to be blended can be suitably selected within the range of 1 to 300 parts by weight based on 100 parts by weight of the hydrogenated block copolymer of component (a). The highly elastic elastomeric composition of the present invention can be obtained by combining the above-mentioned components, and if necessary, it can also be obtained by adding flame retardants, glass fibers, carbon fibers, antioxidants, heat stabilizers, ultraviolet rays, etc. Absorbers, hindered amine light stabilizers, and colorants can be added. As a method for compounding the highly elastic elastomeric composition of the present invention, methods used in the production of ordinary resin compositions or rubber compositions can be adopted, such as a single screw extruder, a twin screw extruder, a Banbury mixer, Composite composition can be performed using a melt kneader such as a heating roll, Brabender, or various kneaders. At this time, there is no restriction on the order of addition of each component,
For example, all the ingredients may be premixed using a mixer such as a Henschel mixer or blender, and then melted and compounded using the above-mentioned kneading machine, or arbitrary components may be premixed and melted and compounded in a master batch, and then the remaining components are added and the remaining components are melted and compounded. Addition methods such as oxidation can be adopted. The composite composition of the present invention can be molded using a commonly used thermoplastic resin molding machine, and various molding methods such as injection molding, extrusion molding, blow molding, and calendar molding can be applied. It is possible. (Effects of the Invention) The composition obtained by the present invention has excellent flexibility, heat resistance, mechanical strength, and rubber elasticity at high temperatures, as well as excellent moldability, paintability, and electrical insulation. Its fields of use include various electric wire coatings (insulation, sheathing), making use of its high rubber elasticity,
It can be suitably molded and used for home appliance parts, automobile parts, and various industrial parts. Specific applications include various gaskets, flexible tubes, hose coverings, weather strips, flexible bumpers, side bumpers, moldings, filler panels,
Includes lamp housing, wire cable covering, air intake hose, cushion panel, etc. (Examples) The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in these Examples and Comparative Examples,
The test methods used for various evaluations are as follows. (1) Hardness [-] JIS-K-6301, A type (2) Tensile strength [Kg/cm ² ] and tensile elongation [%]
JIS-K-6301, the sample used was a 2mm thick injection sheet, and the test piece was No. 3. (3) Compression set [%] JIS-K-6301, 70℃ and 100℃ 22 hours, 25%
Transformation. In addition, the ingredients blended are as follows. (1) <Component (a-1)> Has a hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure, with bound styrene content of 36%, number average molecular weight of 128,000, molecular weight distribution of 1.04, before hydrogenation. A hydrogenated block copolymer of polybutadiene with a 1/2 bond content of 32% and a hydrogenation rate of 99% was synthesized using a Ti-based hydrogenation catalyst described in JP-A-59-133203, and the components ( a
-1). <Component (a-2)> It has a structure of polystyrene-hydrogenated polybutadiene-polystyrene, and the amount of bound styrene is 28
%, number average molecular weight 194,000, molecular weight distribution 1.08, 1/2 bond content of polybutadiene before hydrogenation is 27%, and hydrogenation rate is 99%.
Component (a-2) was synthesized using the Ti-based hydrogenation catalyst described in Publication No. 133203. <Component (a-3)> It has a hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure, with a bound styrene content of 22%, a number average molecular weight of 81000, a molecular weight distribution of 1.03, and a polybutadiene content before hydrogenation. A hydrogenated block copolymer with a 1/2 bond content of 36% and a hydrogenation rate of 99% was synthesized using a Ti-based hydrogenation catalyst described in JP-A-59-133203, and the component (a
-3). <Component (a-4)> (Polystyrene-hydrogenated polybutadiene) ₄ ---Has a structure of Si, the amount of bound styrene is 30%, the number average molecular weight is 393,000, the molecular weight distribution is 1.58, 1 of polybutadiene before hydrogenation, 2 bond amount is 30%, hydrogenation rate is 99%
A hydrogenated block copolymer of
It was referred to as component (a-4). <Component (a-5)> KRATON-G1651 manufactured by Ciel Chemical Co., Ltd. <Component (a-6)> KRATON-G1650 manufactured by Ciel Chemical Company (2) Component (b) Styron 685 manufactured by Asahi Kasei Co., Ltd. (number average molecular weight 78000) ( 3) Ingredient (c) Diana Process Oil PW− manufactured by Idemitsu Kosan Co., Ltd.
380 [paraffinic, kinematic viscosity; 381.6cst (40℃),
30.1cst (100℃), average molecular weight 746, ring analysis; C _N =
27%, C _P = 73%] (4) <Component (d-1)> As polyphenylene ether resin, poly(2,6-dimethyl-1,4-phenylene) ether (ring base viscosity: 0.37, 0.68 > was synthesized and used as component (d-1). <Component (d-2)> As polyphenylene ether resin, 2.3.
A 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer (reduced viscosity 0.53) was synthesized from 2,6-dimethylphenol containing 5% 6-trimethylphenol, and component (d-2) and did. (5) Component (e) Asahi Kasei polypropylene resin, M-1300
[MFR (230°C) 4 g/10 minutes] Examples 1 to 3 As a hydrogenated block copolymer, component (a-1),
(a-2), (a-4), and (a-5), and (d
-1) Using the ingredients shown in Table 1, mix each component with a Henschel mixer, and then use a 30 mm diameter twin screw extruder.
The mixture was melt-kneaded at 260°C to obtain elastomeric pellets with a good surface texture. The pellets were evaluated as injection molded products, and the results are listed in Table 1. From these results, it is clear that the composition of the present invention has a compression set of 50% or less at 100°C and is excellent in rubber elasticity at high temperatures. Furthermore, the surface texture of the injection molded products of these compositions was excellent in gloss and no stickiness was observed.

[Table] Comparative Examples 1 to 4 Hydrogenated block copolymers (a-1), (a-
2), (a-5) and (d-1) component with a reduced viscosity of 0.37 as polyphenylene ether, each component shown in Table 2 was composited in the same manner as in Examples 1 to 5, It was further molded and evaluated. The results are listed in Table 2. From this result, it can be seen that compositions outside the scope of the present invention have a
Although it has excellent compression set at 100°C, it has become clear that the compression set at 100°C is extremely poor and its rubber elasticity at high temperatures is poor.

[Table] Examples 4 to 7 Comparative Examples 5 and 6 Hydrogenated block copolymers (a-3) and (a-
6) and component (d-2) as the polyphenylene ether, each component shown in Table 3 was composited in the same manner as in Examples 1 to 3, and further injection molded and evaluated. The results are listed in Table 3. From this result, it is recognized that the compression set of the composition of the present invention is improved even when a polyphenylene ether copolymer is used. In addition, although Comparative Examples 5 and 6, which are outside the scope of the present invention, have deteriorated compression set at 70°C, Examples 6 to 9, which are compositions of the present invention, have deteriorated compression set at 70°C. The composition has significantly improved compression set at 100°C and has excellent rubber elasticity at high temperatures.

【table】

[Table] Example 8 Except for using component (d-1) with a reduced viscosity of 0.68 as the polyphenylene ether, the same composition as in Example 1 was used, melt-kneaded under the same conditions, and injection molded. Got a test piece. When physical properties were evaluated, hardness was 55, tensile strength was 100Kg/cm ² , and elongation was 710.
%, 70℃ compression set 26%, 100℃ compression set 35%
A hydrogenated block copolymer with excellent elasticity was obtained. When the tensile strength of this test piece was further measured at 70°C, it was 66 kg/cm ² , indicating excellent heat resistance. Example 9 Polystyrene-poly(styrene/butadiene=
10/90% by weight)-poly(styrene/butadiene=
10/90% by weight)-poly(styrene/butadiene=
10/90% by weight)-polystyrene structure, and has 3 tapered blocks in which styrene gradually increases in the poly(styrene/butadiene = 10/90% by weight) portion, total amount of bound styrene 37%, amount of block styrene 30 %, number average molecular weight 171000, molecular weight distribution 1.08,
A block copolymer with a 1,2 bond content of 38% was synthesized, and was further described in JP-A-59-133203.
A hydrogenated block copolymer with a hydrogenation rate of 99% was obtained by carrying out a hydrogenation reaction using a Ti-based hydrogenation catalyst. Except for using this hydrogenated block copolymer, it was blended with the same composition as in Example 1, kneaded and injection molded in the same manner, and evaluated. The hardness was 60, and the tensile strength was 78 kg/
^cm2 , elongation 580%, compression set (100℃×22HRS)
A composition with a property of 42% was obtained. Comparative Examples 7-8 Component (d-2) with a reduced viscosity of 0.53 as polyphenylene ether, Stylon 685 manufactured by Asahi Kasei Co. as polystyrene, M-1300 manufactured by Asahi Kasei Co. as polypropylene, Idemitsu Kosan Co. as a softener for non-aromatic rubber Diana Process Oil PW-380 manufactured by Shell Chemical Company as a hydrogenated block copolymer
KRATON-G1650 (a-6) was composited with the composition shown in Table 4 in the same manner as in Examples 1 to 5, and then injection molded to determine the Izot impact strength, tensile elongation and
Compression set at 100°C was measured. The results are also listed in Table 4. Although the compositions obtained in Comparative Examples 7 and 8 have excellent isot impact strength (Kg cm/cm notched), they have poor tensile elongation and compression set at 100°C (according to JIS-K6301). It was found that the resin composition did not have the tensile elongation as an elastomer composition and had poor rubber elasticity.

[Table] Example 10, Comparative Examples 9 to 11 The same components as in Example 7 were used for each component a, b, c, d, and e. These have the composition of the values shown in Table 5,
Composites were made in the same manner as in Examples 1 to 3, and further injection molded to determine Izot impact strength, tensile elongation, and 100°C
The compression set was measured. The results are also listed in Table 5. As is clear from these comparisons, when the amount of hydrogenated block copolymer used is smaller than the range of the present invention, the compression set (according to JIS-K6301) at 100°C of the resulting composition is It can be seen that the composition is extremely poor in rubber elasticity, and the tensile elongation at break is also low. In addition, in the region where the content of the block copolymer of the rubber component is low, as is clear from the comparison of Comparative Examples 9 and 11, even if polyphenylene ether is present, the difference is lower than when this substance is not present. However, it can be seen that the effect of improving rubber elasticity such as compression set at 100°C does not appear.

【table】

Claims (1)

[Scope of Claims] 1 (a) a polymer block A mainly composed of at least two vinyl aromatic compounds; and at least one
Hydrogenated block copolymer a obtained by hydrogenating a block copolymer consisting of a polymer block B mainly composed of conjugated diene compounds
100 parts by weight (b) Polystyrene resin 5 to 100 parts by weight (c) Softener for non-aromatic rubber 20 to 200 parts by weight (d) Bonding unit [formula] (where R ₁ , R ₂ , R ₃ , and R ₄ are each selected from the group consisting of hydrogen, halogen, and hydrocarbon group), and the reduced viscosity (0.5 g/dl chloroform solution, measured at 30°C) is
Highly elastic hydrogenated polyphenylene ether resin d, which is a homopolymer and/or copolymer in the range of 0.15 to 0.70, has a/d = 90/10 to 30/70 (weight ratio) to the above a. Block copolymer composition. 2 (a) at least two vinyl aromatic compound-based polymer blocks A and at least one
A hydrogenated block copolymer a obtained by hydrogenating a block copolymer consisting of a polymer block B mainly composed of conjugated diene compounds
100 parts by weight (b) Polystyrene resin b 5 to 100 parts by weight (c) Softening agent for non-aromatic rubber 20 to 200 parts by weight (d) Bonding unit [formula] (where R ₁ , R ₂ , R ₃ , and R ₄ are each selected from the group consisting of hydrogen, halogen, and hydrocarbon group), and the reduced viscosity (0.5 g/dl chloroform solution, measured at 30°C) is
Polyphenylene ether resin d, which is a homopolymer and/or copolymer in the range of 0.15 to 0.70, is a/d = 90/10 to 40/60 (weight ratio) to the above a. (e) Polyolefin resin e Consists of 5 to 100 parts by weight, and a/(b+d+e)=82/18 to
A highly elastic hydrogenated block copolymer composition with a weight ratio of 37/63.