JPH0149424B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) 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. (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 appliance parts, 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-58-132032, JP-A-58-145751, JP-A-58-25103, JP-A-Sho.
No. 59-6236, JP-A-59-53548, JP-A-59-
No. 131613 proposes a crosslinked composition of a hydrogenated block copolymer. Japanese Unexamined Patent Publication 1983-
No. 132032 discloses a crosslinkable composition using an unsaturated silane compound consisting of a hydrogenated block copolymer/hydrocarbon oil/olefinic resin/inorganic filler, and JP-A-58-145751 contains hydrogenated block copolymer/oil/polypropylene/stabilizer/
A crosslinkable resin composition comprising a crosslinking auxiliary agent is disclosed, and Japanese Patent Application Laid-Open No. 58-225103 discloses a composition comprising a hydrogenated block copolymer and a silane having radical reactivity in the presence of an organic peroxide. A method for crosslinking thermoplastic resins in which a compound is reacted and then further reacted in the presence of a silanol catalyst is disclosed, and JP-A No. 59-6236 discloses a method for crosslinking a hydrogenated block copolymer/peroxide crosslinked olefin. A method for producing a partially crosslinked elastomeric composition comprising a peroxide-based copolymer rubber/peroxide non-crosslinked hydrocarbon rubbery material/softener for non-aromatic rubber/peroxide decomposed olefin resin/inorganic filler is provided. In addition, JP-A-59-53548 discloses a reaction product of a composition comprising a hydrogenated block copolymer/radical-degradable polymer with an organic peroxide; No. 131,613 discloses a method for producing a partially crosslinked elastomeric composition comprising a hydrogenated block copolymer/a non-aromatic rubber softener/a peroxide-decomposed olefinic resin/an inorganic filler. However, the crosslinked compositions of hydrogenated block copolymers disclosed in these proposals still have insufficient compression set at high temperatures, especially at 100°C, which is conventionally required for vulcanized rubber applications. The current situation is that the performance level has not been reached. Furthermore, the compositions obtained by these proposals have a sticky surface due to the decomposition of the peroxide-decomposed polymer in the formulation due to the use of organic peroxides, making them unsuitable for practical use. The current situation is that it includes many undesirable problems. (Means for Solving the Problems) The present invention was made to solve the problems that were difficult to solve with the conventional elastomer molding materials described above, and in particular, the processability of thermoplastic elastomers and the ease of recycling This was created based on the desire for a new molding material that has properties that have never been achieved in terms of rubber elasticity and high-temperature rubber elasticity (compression set at 100°C), and has less stickiness on the molding surface. It has been discovered that this desire can be satisfactorily achieved by an elastomeric composition comprising a specific formulation, and furthermore, it has been discovered that the composition is a practically useful composition. That is, the present invention provides (1) (a) a polymer block A consisting mainly of at least two vinyl aromatic compounds and a polymer block B consisting mainly of at least one conjugated diene compound; Hydrogenated block copolymer a obtained by hydrogenating a polymer
100 parts by weight (b) Softener for non-aromatic rubber 10-300 parts by weight (c) 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 has a reduced viscosity (0.5 g/dl chloroform Polyphenylene ether resin c, which is a homopolymer and/or copolymer having a solution (measured at 30°C) in the range of 0.15 to 0.70, has a/c = 90/
A hydrogenated block copolymer composition with excellent elasticity obtained by modifying a blend consisting of 10 to 30/70 (weight ratio) in the presence of an organic peroxide, and furthermore, (2) the above (1). A blend consisting of 5 to 100 parts by weight of polyolefin resin and/or polystyrene resin (a), (b), (c) and (d) described above,
To provide a hydrogenated block copolymer composition having excellent elasticity which is modified in the presence of an organic peroxide. 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 according to JIS-K6301, compression ratio 25%).
gives elastomer compositions exhibiting very good performance, with values of, for example, 29-59% (according to 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 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 50% by weight of vinyl aromatic compounds.
Regarding the block structure, the polymer block A mainly composed of a vinyl aromatic compound is a vinyl aromatic compound polymer block or a vinyl aromatic compound containing more than 50% by weight, preferably 70% by weight or more. It has a structure of a copolymer block of a vinyl aromatic compound and a hydrogenated conjugated diene compound, and further,
Polymer block B mainly composed of a hydrogenated conjugated diene compound contains more than 50% by weight, preferably 70% by weight or more of a hydrogenated conjugated diene compound polymer block, or a hydrogenated conjugated diene compound. It has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound. In addition, polymer block A mainly composed of these vinyl aromatic compounds and polymer block B mainly composed of hydrogenated conjugated diene compounds are composed of hydrogenated conjugated diene in the molecular chain of each polymer block. The distribution of the compound or vinyl aromatic compound may be random, tapered (monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof; When there are two or more polymer blocks mainly consisting of a compound and two or more polymer blocks mainly consisting of the hydrogenated conjugated diene compound, each polymer block may have the same structure, or may have a different structure. It may be. 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 Publication No. 8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Application Publication No. 133203-1983,
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. In this case, the number of aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least 80.
% can be hydrogenated to morphologically convert a polymer block mainly composed of a conjugated diene compound 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. The rubber softener used as component (b) in the present invention is an essential component for making the resulting composition into a flexible rubber-like composition, and is made of non-aromatic mineral oil, liquid or low molecular weight synthetic 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 carbon are called paraffinic, and those in which the number of carbon atoms in the naphthene ring is 30 to 45% are called naphthenic, or those in which the number of aromatic carbons is 30%.
Those with a larger amount are considered aromatic. Components of the invention
The mineral oil rubber softener used as (b) is preferably a naphthene type or paraffin type in the above category, and an aromatic type having 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 500 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 (b)) is 10 to 300 parts by weight, preferably 20 parts by weight, per 100 parts by weight of component (a).
~250 parts by weight. If the amount exceeds 300 parts by weight, the softener tends to bleed out, which may cause stickiness in the final product, and may also reduce mechanical properties. If the amount is less than 10 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 (C) 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
a homopolymer and/or copolymer selected from the group consisting of hydrogen, halogen, and hydrocarbon groups, which may be the same or different;
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, 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,
Polyphenols such as copolymers of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) may be mentioned. Nylene ether copolymers may also be mentioned. Among them, poly(2,6-dimethyl-
Copolymers of 1,4-phenylene) ether, 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and 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 (c) to be blended should be selected so that the weight ratio of component (a) hydrogenated block copolymer/component (c) polyphenylene ether is in the range of 90/10 to 30/70. Can be done. If the weight ratio is less than 30/70, the hardness of the resulting elastomeric composition will be too high, resulting in a loss of flexibility and a resinous composition, which will not only fail to provide a product with a rubbery feel. Rubber elasticity at high temperatures [compression set (100℃ x 22 hours)] is poor,
Undesirable. 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 and/or polystyrene resin used as component (d) of the present invention is effective in improving the processability and/or heat resistance of the resulting composition. Polypropylene and copolymers of propylene and small amounts of other α-olefins, such as propylene-ethylene copolymers, propylene/4-methyl-1-pentene copolymers, and poly-4-methyl-1-pentene, polybutene- I can list the first prize. When using isotactic polypropylene or its copolymer as the polyolefin resin, its MFR (ASTM-D1238-L conditions, 230°C) is 0.1.
~50g/10 minutes, particularly 0.5~30g/10 minutes, can be suitably used. Further, polystyrene resin can be suitably used by either radical polymerization or ionic polymerization as long as it can be obtained by a known manufacturing method, and its number average molecular weight is 5000 to 500000, preferably 10000 to 10000.
The molecular weight distribution [ratio (w)/(n) of weight average molecular weight (w) to number average molecular weight (n)] is preferably 5 or less. The blending amount of component (d) 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 undesirable. Furthermore, when the amount is less than 5 parts by weight, the polyolefin resin and/or polystyrene resin exhibits processability equivalent to that of the composition of the present invention to which no polystyrene resin is added. In addition to the above-mentioned components (a) to (d), 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.). As an inorganic filler,
Examples include calcium carbonate, carbon black, talc, clay, magnesium hydroxide, mica, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, etc. Carbon blacks include 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). Next, the organic peroxide used in the present invention is, for example, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, dicumyl peroxide, 2,5-dimethyl-2,5 -di(benzoylperoxy)-hexane, t-butylperoxybenzoate, cumene hydroperoxide, cyclohexanone peroxide,
Benzoyl peroxide, diisopropyl benzohydroperoxide, 2,5-dimethyl-
2,5-di(t-butylperoxy)hexyne-
3,1,1-bis(t-butylperoxy)3,
Examples include 3,5-trimethylcyclohexane, and one or more organic peroxides are useful. The amount of organic peroxide used here is suitably selected in the range of 0.05 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the composition consisting of components (a) to (d). Can be done. If the amount of organic peroxide is less than 0.05 parts by weight, a preferable modified state cannot be obtained, and if it exceeds 3 parts by weight, excessive crosslinking of the resulting composition may occur.
Excessive molecular chain scission occurs, resulting in poor fluidity during processing and undesirable stickiness on the surface of the molded product. In addition, as a crosslinking aid to be used in combination with the above-mentioned organic peroxide if necessary, for example, trimethylolpropane triacrylate, divinylbenzene, unsaturated silane compounds (such as vinyltrimethoxysilane, vinyltriethoxysilane, etc.) are useful. In particular, when an unsaturated silane compound is used in combination, crosslinking can be further progressed by contacting with moisture in the presence of a silanol condensation catalyst. The amount of crosslinking aid used in combination with organic peroxide depends on the ingredients.
It can be suitably selected from 0.1 to 10 parts by weight per 100 parts by weight of the composition consisting of (a) to (d). The hydrogenated block copolymer composition of the present invention having excellent elasticity can be obtained by combining the above-mentioned components, and may also contain flame retardants, glass fibers, carbon fibers, and antioxidants as required. , heat stabilizers, ultraviolet absorbers, hindered amine light stabilizers, and colorants can be added. As a method for compounding the hydrogenated block copolymer composition of the present invention with excellent elasticity, a method used in the production of ordinary resin compositions or rubber compositions can be adopted. The temperature at which organic peroxide decomposes, generally 150~
Single screw extruder, twin screw extruder, Banbury mixer, heating roll, Brabender, under the temperature condition of 250℃.
Composites can be made using melt kneaders such as various kneaders. In order to obtain the composition of the present invention, it is not necessarily necessary to combine each component and modify it with an organic peroxide at the same time, and it is also possible to perform the modification with an organic peroxide after combining the components in advance. Furthermore, in order to obtain the composition of the present invention, the blending amount of each component during modification does not necessarily have to be the final blending amount, but any blending ratio of components (a) to (d) can be selected, and organic After denaturation with peroxide, further (a)
- (d) components can be blended according to the purpose to form a final blend. The composition of the present invention obtained in this way can be molded using a commonly used thermoplastic resin molding machine, and can be molded by compression molding, injection molding, extrusion molding,
Various molding methods such as blow molding and calendar molding are applicable. (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 properties. As for the field of use, it can be suitably molded and used for various electric wire coatings (insulation, sheath), home appliance parts, automobile parts, and various industrial parts by taking advantage of its high rubber elasticity. Specific examples include various gaskets, flexible tubes, hose coverings, weather strips, flexible bumpers, side bumpers, aero parts, moldings, filler panels, lamp housings, wire cable coverings, air intake hoses, and shoes. There are sion panels, curl cords, 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-K6301 A type (2) Tensile strength [Kg/cm ² ] and tensile elongation [%] JIS-K6301. Type 3. (3) Compression set [%] JIS-K6301, 70℃ and 100℃ 22 hours, 25%
Modification In addition, the ingredients blended are as follows. (1) <Component (a-1)> Polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 18%, number average molecular weight 182000, molecular weight distribution
1.05, a hydrogenated block copolymer with a 1,2 bond content of polybutadiene before hydrogenation of 34% and a hydrogenation rate of 99% was synthesized using a Ti-based hydrogenation catalyst described in JP-A-59-133203. This was used as component (a-1). <Component (a-2)> It has a hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure, with a bound styrene content of 28%, a number average molecular weight of 155,000, a molecular weight distribution of 1.03, and a polybutadiene content before hydrogenation. 1,2 bond amount is 27%, hydrogenation rate is 99
% of hydrogenated block copolymer was published in JP-A-59-133203.
Component (a-2) was synthesized using the Ti-based hydrogenation catalyst described in the publication. <Component (a-3)> Polystyrene (hydrogenated polybutadiene) has a structure of ₄ Si, with a bound styrene content of 36%,
A hydrogenated block copolymer with a number average molecular weight of 341,000, a molecular weight distribution of 1.47, a 1,2 bond content of polybutadiene before hydrogenation of 32%, and a hydrogenation rate of 99% was produced in JP-A-59-
Component (a-3) was synthesized using the Ti-based hydrogenation catalyst described in Publication No. 133203. <Component (a-4)> It has a hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure, with a bound styrene content of 30%, a number average molecular weight of 84000, a molecular weight distribution of 1.04, and a polybutadiene content before hydrogenation. 1,2 bond amount is 28%, hydrogenation rate is 99
% of hydrogenated block copolymer was published in JP-A-59-133203.
Component (a-4) was synthesized using the Ti-based hydrogenation catalyst described in the publication. <Ingredient (a-5)> KRATON-G1651 manufactured by Ciel Chemical Co., Ltd. <Ingredient (a-6)> KRATON-G1650 manufactured by Ciel Chemical Company (2) Ingredient (b) Diana Process Oil PW manufactured by Idemitsu Kosan Co., Ltd.
380 [paraffinic, kinematic viscosity; 381.6cst (40℃),
30.1cst (100℃), average molecular weight 46, ring analysis; C _N =
27%, C _P = 73%] (3) <Component (C-1)> As polyphenylene ether resin, poly(2,6-dimethyl-1,4-phenylene) ether (reduced viscosity: 0.34, 0.60) was synthesized and designated as component (c-1). <Component (c-2)> As a polyphenylene ether resin, 2,
2, containing 5% 3,6-trimethylphenol
A 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer (reduced viscosity 0.57) was synthesized from 6-dimethylphenol and used as component (c-2). (4) <Component (d-1)> As a polyolefin resin, polypropylene M-1300 (MFR; 4 g/10 min) manufactured by Asahi Kasei Co., Ltd. was used as component (d-1). <Component (d-2)> As a polystyrene resin, Styron 685 (number average molecular weight 78000) manufactured by Asahi Kasei Co., Ltd. was used as the polystyrene resin (d-2).
2). (5) Organic peroxide; manufactured by Nippon Oil & Fats Corporation, Perhexa 25B〈2,5-dimethyl-2,5-di(t
-butylperoxy)hexane> (6) Crosslinking aid; trimethylolpropane triacrylate (abbreviated as TMP), vinyltrimethoxysilane (abbreviated as VMS) (7) Inorganic filler; calcium carbonate. Examples 1 to 4 Component (a-1) as a hydrogenated block copolymer,
Using (a-2), (a-3), and (a-5), each component shown in Table 1 is mixed in advance with a Henschel mixer,
Blended at 240℃ using a 50mm diameter twin-screw extruder,
For 100 parts by weight of the resulting composite pellets, 0.2 parts by weight of organic peroxide, 0.35 parts by weight of TMP as a crosslinking aid, and antioxidant; Irgano
1010 (manufactured by Ciba Geigy) was added and mixed in a Henschel mixer, followed by a modification reaction at 240°C in a 50 mm diameter twin screw extruder to obtain thermoplastic elastomer pellets. This was injection molded to make a test piece and evaluated. The results are listed in Table 1. From this result, the molded product obtained by the present invention is
The compression set at 100°C was 50% or less, the rubber elasticity at high temperatures was excellent, and the surface had good stickiness.

[Table] Examples 5 and 6 Component (a-1) as a hydrogenated block copolymer,
(a-2) was added to 100 parts by weight of each of the organic peroxide-modified pellets obtained in Examples 1 and 2,
100 parts by weight of the corresponding unmodified organic peroxide pellets obtained in Examples 1 and 2 were mixed in a Henschel mixer, and then compounded in a 50 mm diameter twin screw extruder at 240°C to obtain pellets. The obtained pellets were then injection molded and their physical properties were evaluated. The composition consisting of Example 1 organic peroxide modified product/Example 1 organic peroxide unmodified product had a hardness of 50, a tensile strength of 86 Kg/cm ² , and an elongation. The compression set (100°C x 22HRS) was 47%, and no stickiness of the molded product was observed. Further, the composition consisting of Example 2 organic peroxide modified product/Example 2 organic peroxide unmodified product had a hardness of 60,
Tensile strength 94Kg/ ^cm2 , elongation 700%, compression set (100
x 22 hours) 35%, and no stickiness of the molded product was observed. Example 7 Component (a-1) which is a hydrogenated block copolymer
38 wt% of component (b), 46 wt% of component (b), <component (c-1), reduced viscosity 0.06> 8 wt%, and 8 wt% of component (d-1) are mixed in a Henschel mixer,
The mixture was then pelletized using a 30 mm diameter twin-screw extruder at a temperature of 240°C. 2 parts by weight of VMS (vinyltrimethoxysilane) per 100 parts by weight of pellets of this composition.
and 0.2 parts by weight of organic peroxide (Perhexa 25B), and using a 30 mm diameter twin screw extruder.
The pellets were denatured at 240°C to obtain silane-modified pellets. To 100 parts by weight of the silane-modified pellets, 50 parts by weight of unmodified silane pellets having the same composition as above and 0.06 parts by weight of dibutyltin dilaurate were compounded using a 30 mm diameter twin-screw extruder.
The obtained pellets were immersed in warm water at 85°C for 24 hours to obtain the composition of the present invention. When this final composition was injection molded and evaluated, the hardness was 58 and the tensile strength was 102 kg/
^cm2 elongation 680%, compression set (100℃×22HRS) 38
It was %. As described above, the composition of the present invention can be injection molded even after silanol crosslinking, and has excellent rubber elasticity at high temperatures. Examples 8 to 11 Component (a-4) as a hydrogenated block copolymer,
Using (a-6), the components shown in Table 2 were mixed in advance in a Henschel mixer to obtain composite pellets using the same method and conditions as in Examples 1 to 4. 0.5 parts by weight of organic peroxide per 100 parts by weight of this pellet.
0.8 parts by weight of TMP, a crosslinking aid, and 0.2 parts by weight of an antioxidant, Irgano
A modification reaction was carried out at 240°C using a mm-diameter twin-screw extruder to obtain thermoplastic elastomer pellets. This pellet was injection molded to make test pieces and evaluated. The results are listed in Table 2. Example 12 Polystyrene-poly(styrene/butadiene=
10/90% by weight) - poly(styrene/butadiene =
10/90% by weight) - poly(styrene/butadiene =
10/90% by weight) - has a polystyrene structure, and has three tapered blocks in which styrene gradually increases in the poly(styrene/butadiene = 10/90% by weight) part, with a total bound styrene content of 37% and a block styrene content of 30%. %, number average molecular weight 167000, molecular weight distribution 1.05,
A block copolymer with a 1,2 bond content of 36% was synthesized, and was further described in JP-A-59-133203.
A hydrogenation reaction is carried out using a Ti-based hydrogenation catalyst, and the hydrogenation rate is
A 99% hydrogenated block copolymer was obtained. 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 56, and the tensile strength was 60 kg/
^cm2 , elongation 600%, compression set (100℃×22HRS)
A composition with a property of 51% was obtained.

[Table] Comparative Examples 1 to 4 Component (a-1) as a hydrogenated block copolymer,
Using (a-5), each component shown in Table 3 was pelletized in the same manner and under the same conditions as in Examples. Note that the obtained pellets were not modified with organic peroxide. The evaluation results of the test pieces are listed in Table 3. These results revealed that compositions outside the scope of the present invention had poor rubber elasticity (compression set) at high temperatures.

【table】

【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
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) Softener for non-aromatic rubber 10-300 parts by weight (c) Bonding unit [Formula] (Here, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, carbonized, respectively) (selected from the group consisting of hydrogen groups) and has a reduced viscosity (0.5 g/dl chloroform solution, measured at 30°C).
Polyphenylene ether resin c, which is a homopolymer and/or copolymer in the range of 0.15 to 0.70, has a/c = 90/10 to 30/70 to the above a.
Hydrogenated block copolymer composition 2 with excellent elasticity obtained by modifying a blend consisting of (weight ratio) in the presence of an organic peroxide (a) A polymer mainly composed of at least two vinyl aromatic compounds block 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) Softener for non-aromatic rubber 10-300 parts by weight (c) Bonding unit [Formula] (Here, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, carbonized, respectively) selected from the group consisting of hydrogen) and has a reduced viscosity (0.5g/dl chloroform solution, measured at 30℃).
Polyphenylene ether resin c, which is a homopolymer and/or copolymer in the range of 0.15 to 0.7, has a/c = 90/10 to 30/70 to the above a.
(Weight ratio) (d) A hydrogenated block copolymer composition with excellent elasticity obtained by modifying a blend of 5 to 100 parts by weight of a polyolefin resin and/or a polystyrene resin in the presence of an organic peroxide.