JPH05171003A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in adhesion to a polar resin and in mold releasability in molding by compounding specified amts. of a specific hydrogenated block copolymer and a specific modified hydrogenated block copolymer. CONSTITUTION:The title compsn. is prepd. by compounding 100 pts.wt. hydrogenate block copolymer having a number-average mol.wt. of 80,000 or higher and prepd. by hydrogenating a block copolymer comprising a polymer block consisting main of at least one kind of vinylarom. compd. and a polymer block consisting main of at least one kind of conjugated diene compd., 10-200 pts.wt. modified hydrogenated block copolymer prepd. by bonding a compd. having a carboxyl group or its deriv. (e.g. maleic anhydride) to a hydrogentad block copolymer prepd. by the same way as above, up to 250 pts.wt. thermoplastic polyurethane elastomer as an optional component, and 100 pts.wt. hydrogenated block copolymer prepd. by the same way as above and having a number-average mol.wt. below 80,000 as another optional component.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic elastomer composition comprising a hydrogenated block copolymer having a specific number average molecular weight, a thermoplastic polyurethane elastomer and an acid-modified hydrogenated block copolymer. The present invention relates to a thermoplastic elastomer composition that firmly adheres to a resin having a polar group without using an adhesive and is excellent in oil resistance, rubber properties, and moldability.

[0002]

2. Description of the Related Art Conventionally, by adhering dissimilar materials into a laminate, the advantages of both materials are given, or the same material is sandwiched by another material to form a laminate. Attempts have been made to produce laminates that compensate for the shortcomings of one material. Particularly in recent years, attempts have been made to laminate rubber on plastics in order to improve the feeling of cheapness and the unpleasant feel of plastics. It can be said that this rubber laminated product is suitable for automobile interior parts and home electric appliance parts because it has a soft touch, a good feel, a high-grade feeling, and excellent soundproofing and vibration-proofing properties.

As the thermoplastic resin used as the material for such a laminate, polyethylene, polypropylene, ethylene-
Vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyethylene terephthalate,
Nylon, polycarbonate, polystyrene, impact-resistant polystyrene, polyvinylidene chloride, ABS resin, etc. are used.

These laminates have, as their form, a sheet.
It is used as a film, a film, or a molded product having a complicated shape. For these laminates, a method of adhering the same or different materials with an adhesive, a method of forming a laminate by a co-extrusion method or a multi-layer molding method without using an adhesive, etc. are generally performed.

However, depending on the type of materials to be laminated or a combination thereof, a sufficient adhesive effect may not be obtained, and in particular, when a laminate is obtained by a coextrusion method or a multilayer molding method without using an adhesive. , Materials that are not adhesive to each other cannot be used. Therefore, in the case of obtaining a laminate of materials that are not adhesive to each other by the coextrusion method, a method of using an adhesive material for both materials as an adhesive layer is used. For example, ethylene-vinyl acetate copolymer , Ionomer resins, styrene-butadiene block copolymers, etc. are used.

However, these resins also have problems that a sufficient adhesive effect may not always be obtained depending on the type of the material to be coextruded, the durability of the adhesive strength and the water resistance are poor. .. Furthermore, it is difficult to use an adhesive layer in the case of an injection-molded product having a complicated shape, and under the present circumstances, the multi-layer molding method can be used only in the case of a limited combination having adhesiveness.

In order to solve these problems, as a further advanced technique, a technique of using an acid-modified hydrogenated block copolymer to which a thermoplastic polymer having a polar group is added is disclosed in JP-B-62-13911. Is disclosed. The laminate described in this publication is an effective method showing excellent adhesion to polar resins, glass, metals and the like, but the fluidity may be inferior depending on the combination of compositions, and a molded article having a complicated shape may be obtained. Is difficult to obtain.

Further, JP-A-63-254156 discloses a composition in which a thermoplastic polyurethane is blended with an acid-modified hydrogenated block copolymer. However, although the composition described in this publication is a useful composition that exhibits excellent properties such as mechanical strength and adhesiveness with other resins, it may be inferior in moldability and further improvement is desired.

Further, Japanese Patent Application Laid-Open No. 64-33201 discloses a composition comprising a thermoplastic polyurethane having a specific viscosity and a non-hydrogenated block copolymer or a hydrogenated block copolymer. However, the composition described in this publication has a poor affinity between the thermoplastic polyurethane and the non-hydrogenated or hydrogenated block copolymer, so that the mechanical strength is low, and there is a problem that peeling occurs in the molded product, and further improvement is required. Is desired.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points and is excellent in moldability such as injection molding and extrusion molding, and has high adhesiveness with a resin having polarity.
The present invention also provides a thermoplastic elastomer composition having excellent rubber properties, and particularly, an object thereof is to provide a thermoplastic elastomer composition suitable for use in multilayer molding.

[0011]

The present invention comprises (a) a polymer block A containing at least one vinyl aromatic compound as a main component, and a polymer block B containing at least one conjugated diene compound as a main component. 100 parts by weight of a hydrogenated block copolymer having a number average molecular weight of 80,000 or more obtained by hydrogenating a block copolymer consisting of (b) a polymer block A mainly composed of at least one vinyl aromatic compound A molecule containing a carboxylic acid group or its derivative group in a hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of a polymer block B containing at least one conjugated diene compound as a main component. 10 to 200 parts by weight of a modified hydrogenated block copolymer having units bonded thereto, (c) 10 to 250 parts by weight of a thermoplastic polyurethane elastomer, and (d) at least one vinyl. The number average molecular weight obtained by hydrogenating a block copolymer consisting of a polymer block A mainly containing an aromatic compound and a polymer block B mainly containing at least one conjugated diene compound is less than 80,000. The present invention provides a thermoplastic elastomer composition comprising 0 to 100 parts by weight of the hydrogenated block copolymer. Hereinafter, the present invention will be described in detail.

As the block copolymer before hydrogenation of the hydrogenated block copolymer used as the components (a) and (d) of the present invention, at least one vinyl aromatic compound polymer block is preferable. Two or more, and at least one polymer block mainly composed of a conjugated diene compound is contained. In the polymer block containing a conjugated diene as a main component, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 50/50, preferably 0/100.
Polymer block having a composition range of -40 to 60/60, and the distribution of vinyl aromatic compounds in this block is random taper (monomer component increases or decreases along the molecular chain), partly It may be block-shaped or any combination thereof.

In the above block copolymer before hydrogenation,
The weight ratio of the content of the vinyl aromatic compound to the content of the conjugated diene compound is preferably in the range of 10/90 to 90/10, and 15/85 to 60 when rubber-likeness is required.
The range of / 40 is preferable.

The vinyl aromatic compound constituting the block copolymer before hydrogenation is one or two of styrene, α-methylstyrene, 1,1-diphenylethylene, paramethylstyrene, vinyltoluene and the like. One or more kinds are selected, and styrene is particularly preferable. Further, as the conjugated diene compound, butadiene, isoprene, 1,3
-Pentadiene and the like are selected from one or more kinds, and among them, butadiene and / or isoprene are particularly preferable. Furthermore, when butadiene is used as the conjugated diene compound in the block copolymer before hydrogenation of the block copolymer, the amount of 1,2 bonds in the microstructure of the butadiene portion is preferably in the range of 10 to 80%, 20
The range of up to 50% is particularly preferred.

When the block copolymer before hydrogenation contains two or more blocks mainly containing a vinyl aromatic compound block or a conjugated diene compound, each block may have the same structure, It may have a different structure. The molecular structure of the hydrogenated block copolymer may be linear, branched, radial or a combination thereof.

The number average molecular weight of the hydrogenated block copolymer used as the component (a) of the present invention is 80,000 or more, more preferably 100,000 or more. By using a hydrogenated block copolymer having a number average molecular weight of 80,000 or more, a composition having excellent physical properties such as oil resistance and compression set can be obtained. The molecular weight distribution (ratio of weight average molecular weight and number average molecular weight) is preferably 10 or less, more preferably 5 or less.

The hydrogenated block copolymer used as the component (d) of the present invention has a number average molecular weight of less than 80,000, more preferably 35,000 to 70,000. If only a hydrogenated block copolymer having a number average molecular weight of less than 80,000 is used, the physical properties of compression set will be deteriorated, but the number average molecular weight will be 8
More than 10,000 hydrogenated block copolymers (a) component and above (d)
When used in combination with the component (a) having a number average molecular weight ratio with the component of 1.5 or more, a composition having further excellent moldability can be obtained without impairing the above-mentioned physical properties.

The amount of component (d) used in the present invention is 0 to 100 parts by weight per 100 parts by weight of component (a). It is preferably 3 to 80 parts by weight. Although the moldability is improved by the addition of the component (d), on the contrary, if it is used in a large amount exceeding 100 parts by weight, the compression set is lowered and the desired composition cannot be obtained. The number average molecular weight and molecular weight distribution of the hydrogenated block copolymer can be easily determined by gel permeation chromatography or the like.

The hydrogenated block copolymer provided in the present invention may be obtained by any production method as long as it has the above-mentioned structure. For example, Japanese Patent Publication 4
According to the method described in 0-23798, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like, and then a known method, for example, JP-B-42-8704, Japanese Examined Japanese Patent Sho 63-48
By the hydrogenation in the presence of a hydrogenation catalyst in an inert solvent by the method described in each of Japanese Patent Publication No. 41 and Japanese Patent Publication No. 1-53851, the aromatic double bond of the vinyl aromatic compound block A is No more than 20% and at least 80% of the aliphatic double bonds of the conjugated diene compound block B
A hydrogenated block copolymer in which is hydrogenated is synthesized.

The unsaturation degree of block B in the present invention means
The ratio of carbon-carbon double bonds contained in block B, which is the nuclear magnetic resonance absorption spectrum (NM
R), instrumental analysis such as infrared absorption spectrum (IR), and chemical analysis such as iodine titration method.

Next, the acid-modified hydrogenated block copolymer used as the component (b) of the present invention will be described. The hydrogenated block copolymer, which is the source of the acid-modified hydrogenated block copolymer used as the component (b) of the present invention, has the same polymer structure as that of the component (a). Particularly, those having a number average molecular weight of 30,000 to 100,000, which are excellent in fluidity, and more preferably 35,000 to 70,000. By using a polymer having a number average molecular weight in such a range, the composition of the present invention has excellent moldability and physical properties in a well-balanced manner.

The component (b) of the present invention is a hydrogenated block copolymer to which a molecular unit containing a carboxylic acid group or its derivative group is bonded. Examples of the compound containing such a carboxylic acid group or a derivative group thereof include maleic acid,
Halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid and the like of these dicarboxylic acids Examples thereof include anhydrides, esters, amides, imides and the like, acrylic acid, methacrylic acid, crotonic acid and the like, and esters of these monocarboxylic acids, for example, methyl methacrylate and amide derivatives. Of these, maleic anhydride is particularly preferable.

The addition amount of the compound containing a carboxylic acid group or its derivative group is about 20 parts by weight or less,
It is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.

By using the component (b) in which the carboxylic acid group or its derivative group is introduced into the hydrogenated block copolymer, the compatibility between the component (a) and the component (c) of the present invention is remarkably improved. The adhesiveness of the composition of the present invention with a resin having a polar group is improved, and the mechanical properties are also improved, but if the addition amount of the carboxylic acid group or its derivative group is too large, the fluidity of the composition decreases. However, there arises a problem that the moldability is deteriorated. Therefore, the above-mentioned addition amount is desirable.

The amount of the component (b) used in the present invention is in the range of 10 to 200 parts by weight per 100 parts by weight of the component (a) of the present invention. If the amount of the component (b) used is less than 10 parts by weight, the effect of improving the compatibility is insufficient and the desired composition cannot be obtained. Further, even if a large amount is used in excess of 200 parts by weight, the effect of improving the compatibility reaches a ceiling, and conversely, the fluidity is markedly reduced and the composition is not desirable. Therefore, the above range is preferable. A more desirable range is 20 to 100 parts by weight.

Next, the thermoplastic polyurethane elastomer used as the component (c) of the present invention will be described.
The thermoplastic polyurethane elastomer used as the component (c) of the present invention is obtained by addition-polymerizing a long-chain glycol and a short-chain glycol having active hydrogen at both ends using a diisocyanate compound. .. There are no particular restrictions on the compound used, but typical long-chain glycols are polyesters, polyethers, polycarbonates and the like.

In the polyester system, dehydration condensates of adipic acid and various glycols,
For example, poly (ethylene adipate), poly (diethylene adipate), poly (1,4-butylene adipate),
Poly (1,6-hexane adipate) and the like. Polyether systems in which polycaprolactone and the like can also be used include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (propylene glycol / Examples thereof include ethylene glycol), and examples of the polycarbonate type include poly (1,6-hexamethylene glycol carbonate). Polyolefin-based glycols are also useful, and polybutadienediol, polyisoprene diol, and hydrogenated products thereof can be preferably used.

Aliphatic glycol is used as the short-chain glycol.
Representative examples of such compounds include aromatic glycol-containing compounds, and aromatic compound-containing compounds such as ethylene glycol, 1,3-propylene glycol, and the like.
1,4-butane glycol, 1,3-butane glycol
Examples thereof include 1,5-pentane glycol, 1,6-hexane glycol, and the like. Examples of aromatic glycol-containing systems include bisphenol A, hydroquinone diethyl ether, and bisphenol A. / Ethylene glycol etc. can be illustrated.

Examples of the diisocyanate include aromatic, alicyclic and aliphatic ones. For example, tolylene diisocyanate, xylylene diisocyanate and 4,4'-diphenylmethane diisocyanate. , 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like, and further xylylene diisocyanate and 4,4'-diphenylmethane diisocyanate. The hydrogenated products and the like are also exemplified.

The thermoplastic polyurethane elastomer used as the component (c) of the present invention has the following synthesis conditions.
It is classified into a complete thermoplastic type and an incomplete thermoplastic type. These were determined by the molar ratio of the OH group of the bifunctional long-chain glycol and the short-chain glycol of the raw material and the NCO group of the diisocyanate, and were synthesized at about 0.95 <NCO / OH ≦ 1. Is a completely thermoplastic type, and the one synthesized at about 1 <NCO / OH <1.1 is an incomplete thermoplastic type. Either of these can be used as the component (c) of the present invention.

The amount of component (c) used in the present invention is 10 to 250 parts by weight per 100 parts by weight of component (a). 10
If the amount used is less than parts by weight, the adhesiveness with the resin having a polar group will be unsatisfactory. Conversely, if the amount used exceeds 250 parts by weight, the improvement in the adhesiveness will reach a ceiling, and conversely compression set Therefore, it becomes impossible to obtain a desired composition due to the deterioration of physical properties such as the above, deterioration of water absorption and increase of cost. A more desirable amount used is in the range of 40 to 150 parts by weight.

Oils can be preferably added to the composition of the present invention in addition to the above-mentioned essential components. Oil is a useful additive for imparting flexibility and processability to the resulting composition and improving economy. The oil used in the present invention is a non-aromatic oil for rubber, for example, a diluting oil for rubber which is generally classified as a mineral oil-based softening agent and is classified into a paraffin-based and a naphthene-based oil. Of these, paraffinic oils are preferable, and among paraffinic oils, 5% or less of the aromatic ring component is desirable. The amount of oil used should be kept within the range where the physical properties of the thermoplastic elastomer composition obtained are not impaired, but as a rough guideline, it is 0 to 2 per 100 parts by weight of the hydrogenated block copolymer.
It is about 100 parts by weight.

A thermoplastic resin, preferably a polyolefin resin, may be added to the composition of the present invention.
The polyolefin resin is useful for improving the processability and mechanical strength of the thermoplastic elastomer composition. Examples of the polyolefin resin include polyethylene, polypropylene, polybutene resin, propylene and ethylene, 1
-A block copolymer with an α-olefin such as butene or a random copolymer can be used.

The amount of the polyolefin resin used should be within the range in which the flexibility of the resulting thermoplastic elastomer composition is not lost, but as a guideline, it is approximately 100 parts by weight of the hydrogenated block copolymer. 0 to 15
It is about 0 parts by weight. Further, the composition of the present invention may contain an inorganic filler. The inorganic filler is useful for increasing the hardness of the resulting thermoplastic elastomer composition and improving the economical efficiency as a filler.

Examples of the inorganic filler include calcium carbonate, talc, clay, synthetic silicon, titanium oxide, and car
Bonblack, barium sulfate, etc. can be used. The amount of the inorganic filler used should be kept within the range in which the flexibility of the thermoplastic elastomer obtained is not impaired, but as a rough guideline, it is 0 to 100 parts by weight based on 100 parts by weight of the hydrogenated block copolymer. It is about a part. Further, in addition to the components described above, a lubricant, a light stabilizer, a pigment, a flame retardant, an antistatic agent, a silicone oil, an antiblocking agent, an ultraviolet absorber, an antioxidant, etc. may be added to the composition of the present invention as appropriate. ..

As a method for kneading the composition of the present invention, a method used for kneading ordinary rubber such as an extruder, a roll, a Banbury mixer, etc. can be used.
Processing methods such as extrusion molding, injection molding and blow molding can be applied.

The thermoplastic elastomer composition obtained by the present invention is a resin having a polar group, for example, polyester resin, polyamide resin, polycarbonate resin, polyphenylene sulfide resin, polyacrylate.
Adhesive with epoxy resin, polymethacrylate resin, polyether resin, acrylonitrile / styrene resin, acrylonitrile / styrene / butadiene resin, vinyl chloride resin, vinylidene chloride resin, phenol resin, epoxy resin, etc. Since it has properties and is excellent in molding processability, oil resistance, mechanical properties, heat resistance, etc., it can be widely used for applications such as a material for processing a multilayer molded body.

[0038]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties used in Examples and Comparative Examples were measured by the following test methods.

(1) Peel strength (kg / 25 mm) Based on 180 degree peel described in JIS-K-6854.

(2) Immersion test (wt%) Based on JIS-K-6301, the weight change after 2 hours at 70 ° C. in JIS-3 oil was measured.

(3) Hardness JIS-K-6301 A type.

(4) Tensile strength (kg / cm ² ) As a sample, a 2 mm thick injection sheet was used, and JI
The No. 3 test piece described in SK-6301 was used. Measurement is JI
Conforms to SK-6301.

(5) Elongation (%) According to JIS-K-6301.

(6) Permanent compression set (%) Measured according to JIS-K-6301 under the conditions of 70 ° C. and 22 hours.

(7) Quality of molded product The molded product was visually observed and evaluated according to the following scale. ◯: The entire surface of the molded product is smooth and smooth. Δ: Flow marks are generated on a part of the surface of the molded product, and there is a part which is not smooth. X: Flow marks are generated on the entire surface of the molded product and the surface is rough.

Further, the hydrogenated block copolymers, thermoplastic urethane elastomers, modified hydrogenated block copolymers and polar resins used in Examples and Comparative Examples are collectively shown in Tables 1 to 4. The number average molecular weight and the weight average molecular weight were measured using gel permeation chromatography with standard polystyrene as a reference.

Examples 1 to 4 and Comparative Examples 1 to 3 Tables 5 and 6 show hydrogenated block copolymers, thermoplastic polyurethane elastomers and modified hydrogenated block copolymers selected from Tables 1 to 3. Mixed in an amount of PW-380 (made by Idemitsu Kosan Co., Ltd.) as paraffin oil.
Was added in an amount described in Tables 5 and 6 to impregnate the mixture, and further 0.2 parts by weight of Irganox 1010 (manufactured by Ciba-Geigy Co., Ltd.), calcium stearate 0. 3 parts and 0.3 parts of polyethylene wax were added.

Next, this was milled with a twin-screw extruder PCM-30 (manufactured by Ikegai Tekko Co., Ltd.), and then an injection pressure of 50 kg / cm ² and an injection temperature of 170 to 190 were applied using an in-line screw type injection molding machine. 20 under conditions of ℃, mold temperature 55 ℃
A flat plate sample having a thickness of 0 mm × 200 mm × 4 mm was prepared.
A 150 mm × 25 mm × 2 mm thick test piece of an ABS resin selected from Table 4 as a resin having a polar group was previously fixed in the mold, and after the injection was completed, a multilayer sample was obtained from the obtained flat plate sample. The molded piece was cut out and used as a test piece for peel strength measurement. 150mm under the same injection condition
A flat plate sample having a thickness of × 150 mm × 2 mm was formed into a test piece for measuring physical properties. Various physical properties were measured by predetermined methods, and the results are shown in Tables 5 and 6.

As is clear from Examples 1 to 4 and Comparative Examples 1 and 2, when only hydrogenated block copolymers having a number average molecular weight of less than 80,000 were used, the resulting compositions had a compression set. The distortion is significantly worse, which is not desirable. Further, as shown in Comparative Example 3, when the hydrogenated block copolymer having the number average molecular weight of 80,000 or more, which is the component (a) of the present invention, is not used, the composition obtained has poor moldability and is further compressed. It turns out that the permanent distortion is also extremely bad.

Examples 5 to 10 and Comparative Examples 4 to 7 PW-380 (Idemitsu Kosan) as a paraffin oil was added to hydrogenated block copolymers, thermoplastic polyurethanes and modified hydrogenated block copolymers selected from Tables 1 to 3. (Manufactured by corporation),
As polypropylene, Asahi Polypro E-1100 (manufactured by Asahi Kasei Corp.) and calcium carbonate were mixed in the amounts shown in Tables 7 and 8, and the adhesion to the ABS resin was evaluated in the same manner as in Example 1 below. The measurement results are summarized in Tables 7 and 8. As is clear from Examples 5 to 7 and Comparative Examples 4 and 5, the composition of the present invention using an appropriate amount of the thermoplastic polyurethane elastomer has desirable physical properties such as oil resistance, compression set and moldability. It turns out to be a composition. On the other hand, when the thermoplastic polyurethane elastomer is not used (Comparative Example 4), the physical properties such as adhesion to ABS resin and oil resistance are inferior, and conversely when it is used in a too large amount (Comparative Example 5), compression permanent It can be seen that this is not desirable because it leads to deterioration of physical properties such as distortion and deterioration of the quality of the molded product.

Further, as is clear from Examples 8 and 9 and Comparative Examples 6 and 7, the composition of the present invention using an appropriate amount of the modified hydrogenated block copolymer, the quality of the molded article, the adhesiveness and the compression property. It can be seen that this is a desirable composition having excellent properties such as permanent set. On the other hand, when the modified hydrogenated block copolymer is not used (Comparative Example 6), the dispersibility of the composition is poor and peeling occurs in the molded product, and further the adhesiveness to the ABS resin is lowered, which is a desirable composition. On the contrary, when it is used in an excessively large amount (Comparative Example 7), physical properties such as compression set of the obtained composition are deteriorated and the quality of the molded product is extremely deteriorated. It turned out to be a less desirable composition.

Examples 11-15, Comparative Examples 8-12 Similar to Example 1 using the composition of Example 6 as Examples 11-15, while using the composition of Comparative Example 4 as Comparative Examples 8-12. Was tested. Various resins having a polar group fixed in the mold were tested, and the peel strength measurement results are shown in Table 9. As is clear from the comparison between Examples 11 to 15 and Comparative Examples 8 to 12, it can be seen that the composition of the present invention is a desirable composition having significantly improved adhesive strength to resins having various polar groups.

Examples 16 to 18 and Comparative Examples 13 to 14 PW-380 (Idemitsu Kosan) as a paraffin oil was added to a hydrogenated block copolymer, a thermoplastic polyurethane, or a modified hydrogenated block copolymer selected from Tables 1 to 3. (Manufactured by corporation),
Asahi Polypro E-1100 (manufactured by Asahi Kasei Corp.) as polypropylene and calcium carbonate were mixed in the amounts shown in Tables 10 and 11, and then ABS was mixed in the same manner as in Example 1 below.
The adhesiveness to the resin was evaluated. The measurement results are summarized in Tables 10 and 11.

As is apparent from Examples 16 to 18 and Comparative Examples 13 and 14, a hydrogenated block copolymer having a number average molecular weight of less than 80,000 was added to a hydrogenated block copolymer having a number average molecular weight of 80,000 or more. It can be seen that the composition of the present invention used by adding an appropriate amount is a desirable composition excellent in physical properties such as oil resistance, compression set and moldability. On the other hand, when a large amount of hydrogenated block copolymer having a number average molecular weight of less than 80,000 is used (Comparative Example 13), the hydrogenated block copolymer having a number average molecular weight of 80,000 or more and the number average molecular weight of 80,000 are used. When the molecular weight ratio of the hydrogenated block copolymer of less than 1.4 is less than 1.4 (Comparative Example 14), the compression set and the quality of the molded product are deteriorated, which is not desirable.

Examples 19-23, Comparative Examples 16-20 Similar to Example 1 using the composition of Example 17 as Examples 19-23, while using the composition of Comparative Example 15 as Comparative Examples 16-20. Was tested. Various resins having polar groups to be fixed in the mold were tested, and the peel strength measurement results are shown in Table 12.

As is clear from the comparison between Examples 19 to 23 and Comparative Examples 16 to 20, it can be seen that the composition of the present invention is a desirable composition having significantly improved adhesive strength to resins having various polar groups. ..

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

[Table 8]

[0065]

[Table 9]

[0066]

[Table 10]

[0067]

[Table 11]

[0068]

[Table 12]

[0069]

Industrial Applicability The elastomer composition of the present invention has excellent adhesiveness to a resin having a polar group, and has low adhesiveness to a mold or the like during molding and excellent releasability. It can be used very effectively in the fields of two-layer extrusion, multi-layer molding and the like. For this reason, automobile interior parts, home appliance parts,
It is widely used for sports goods and miscellaneous goods, and its industrial significance is great.

Claims (1)

[Claims] 1. A hydrogen-containing block copolymer comprising (a) a polymer block A mainly containing at least one vinyl aromatic compound and a polymer block B mainly containing at least one conjugated diene compound. 100 parts by weight of a hydrogenated block copolymer having a number average molecular weight of 80,000 or more obtained by the addition, (b) at least one vinyl aromatic compound-based polymer block A, and at least one conjugated diene Modified hydrogenated block in which a molecular unit containing a carboxylic acid group or its derivative group is bonded to a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block B containing a compound as a main component Copolymer 10-200
Parts by weight and (c) thermoplastic polyurethane elastomer-1
0 to 250 parts by weight and (d) a polymer block A mainly composed of at least one vinyl aromatic compound, and a polymer block B mainly composed of at least one conjugated diene compound.
Hydrogenated block copolymers having a number average molecular weight of less than 80,000 obtained by hydrogenating a block copolymer consisting of
A thermoplastic elastomer composition comprising 0 parts by weight.