JPH0674367B2 - Thermoplastic elastomer molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silicone-containing thermoplastic elastomer molding having excellent heat distortion resistance and no stickiness on the surface.

[Prior Art] In recent years, thermoplastic elastomers have been used as rubbers that do not require vulcanization in fields such as automobile parts, home electric appliance parts, footwear, electric wire coatings, and sundries.

Of these, styrene saturated thermoplastic elastomers such as styrene-butadiene block copolymer and styrene-
Hydrogenated isoprene block copolymer is highly flexible, has good rubber elasticity at room temperature, and has heat aging resistance,
Due to its excellent weather resistance, it is also widely used in compounds such as adhesives, sealants and thermoplastic resins.

Polyolefin such as polypropylene and softening agent for rubber such as oil are added to this styrene saturated thermoplastic elastomer.
A method for further improving flexibility and rubber elasticity by blending an inorganic filler or the like is known, but the present inventors have found that at 40 ° C.
A styrene-saturated thermoplastic elastomer composition containing a relatively high-viscosity non-aromatic rubber softening agent having a kinematic viscosity of 0 to 450 centistokes has a composition having a small compression set and a high thermal deformation resistance. I found that.

However, such a relatively high-viscosity softening agent for non-aromatic rubbers easily bleeds, and a molded article made of a composition containing such a softening agent has a drawback that the surface is sticky.

Conventionally, as a method for modifying and improving the surface of a styrene-based thermoplastic elastomer, known methods include adding waxes, higher fatty acids and salts thereof, esters, amides, alkylammonium salts, lubricants such as polyglycol, and surfactants. There is a method and a method of adding a silicone polymer described in JP-A-49-344, JP-A-54-130656, and JP-B-60-26508.

[Problems to be Solved by the Invention]

However, the method of adding a lubricant, a surfactant and the like requires a relatively large amount of addition in order to solve the stickiness of the surface of the thermoplastic elastomer molding. Moreover, the effect occurs only when the additive bleeds to the surface, but at that time, the smoothness of the surface is lost in the case where the additive is a solid, and the sliminess occurs in the surface when the additive is a liquid,
In any case, the feel of the surface is extremely deteriorated.

On the other hand, the composition comprising the thermoplastic elastomer and silicone oil disclosed in JP-A-49-344 and JP-B-60-26508 has improved surface smoothness, processability and releasability. . However, the former composition has a drawback that it is inferior in heat resistance and weather resistance because it uses a non-hydrogenated block copolymer. In the latter composition, 18 barium sulfate was added.
Although a composition added by weight is disclosed, it has a drawback that the breaking strength of the composition is lowered by adding silicone oil. Further, JP-A-54-130656 discloses a medical-use silicone-containing thermoplastic polymer, which is a composition comprising a styrene-based thermoplastic elastomer, a crosslinkable silicone gum, etc. in order to maintain processability. It has a drawback that it is necessary to add an ethylene-based polymer to.

[Means for Solving the Problem] The inventors of the present invention have earnestly sought to obtain a thermoplastic elastomer molding having heat aging resistance, weather resistance and heat deformation resistance, improved surface characteristics, and no reduction in strength. As a result of examination, it is composed of a styrene saturated thermoplastic elastomer, a relatively high viscosity softening agent for non-aromatic rubber, a silicone oil and a relatively large amount of an inorganic filler, and a pure water contact angle is 105 ° or more. The present inventors have found that the thermoplastic elastomer molded article is a molded article having improved surface stickiness and no decrease in breaking strength due to addition of silicone oil, and has reached the present invention.

That is, the present invention is to hydrogenate a block copolymer consisting of a) a polymer block A mainly containing at least two vinyl aromatic compounds and a polymer block B mainly containing at least one conjugated diene compound. 100 parts by weight of the hydrogenated block copolymer modified product containing the hydrogenated block copolymer and / or the carboxylic acid group or its derivative group
b) 30 to 200 parts by weight of inorganic filler c) Polyolefin 10
To 100 parts by weight d) A softening agent for non-aromatic rubber having a kinematic viscosity of 150 to 450 centistokes at 40 ° C. 70 parts by weight or more and less than 150 parts by weight (I) 100 parts by weight and room temperature The present invention relates to a thermoplastic elastomer molded product which is composed of 0.5 to 30 parts by weight of polysiloxane (II) having a kinematic viscosity of 50 to 500 centistokes and has a contact angle of pure water of 105 ° or more.

Hereinafter, the present invention will be described in detail.

The hydrogenated block copolymer that can be used as one of the components (I) -a) includes at least two polymer blocks A mainly containing a vinyl aromatic compound, and at least one polymer block A.
It is preferably obtained by hydrogenating a block copolymer having a structure composed of a polymer block B mainly composed of two or more conjugated diene compounds, for example: A- (BA) _n , A- (BA ) _N- B, B- (AB) _{n + 1} , [(AB) _n ] _m X, [(AB) _n -A] _m X, [(BA) _n ] _m X, [(BA) _n -B] _m X (n ≧ 1, m = integer of 2 to 10, X is a residue of a coupling agent or a polyfunctional initiator) and a hydrogenated hydrogenated block copolymer of a mixture thereof. Further, this hydrogenated block copolymer contains 5 to 95% by weight of a vinyl aromatic compound. The hydrogenated block copolymer preferably has a vinyl aromatic compound content.
When it is 10 to 60% by weight, more preferably 15 to 45% by weight, it exhibits excellent properties as a thermoplastic elastomer. Further referring to the block structure, the polymer block A mainly composed of a vinyl aromatic compound is a vinyl aromatic compound polymer block and / or a vinyl aromatic compound.
It has a structure of a copolymer block of a vinyl aromatic compound and a hydrogenated conjugated diene compound containing more than 50% by weight, preferably 70% by weight or more, and further,
The polymer block B composed mainly of a hydrogenated conjugated diene compound is a hydrogenated conjugated diene compound polymer block and / 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 an amount of more than 50% by weight, preferably 70% by weight or more. Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing the hydrogenated conjugated diene compound are the hydrogenated conjugated diene in the molecular chain of each polymer block. The distribution of the compound or vinyl aromatic compound may be random, tapered (increasing or decreasing monomer distribution along the molecular chain), partially blocky or any combination thereof,
The polymer block A mainly composed of two or more vinyl aromatic compounds and the polymer block B mainly composed of two or more hydrogenated conjugated diene compounds may have the same structure. , May have different structures.

The vinyl aromatic compound constituting the hydrogenated block copolymer, for example, styrene, α-methylstyrene, 4-methylstyrene, vinyltoluene, 4-tert-butylstyrene,
1 or 2 from 1,1'-diphenylethylene
One or more kinds can be selected, and styrene is preferable. Also,
Examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include, for example, one of butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene, or Two or more kinds can be selected, and among them, butadiene, isoprene and a combination thereof are preferable. The polymer block B mainly composed of the conjugated diene compound before hydrogenation can have any microstructure in the block, but in order to have good rubber elasticity, for example, polybutadiene block is used. In the 1,2-vinyl bond amount is 10 to 80%, preferably,
25-45%.

The hydrogenated block copolymer has a number average molecular weight of 5,000 to 1,0.
00,000, preferably 10,000 to 800,000, from the viewpoint of maintaining the balance between the physical properties and processability of the composition of the present invention.
A more preferable range is 30,000 to 300,000, and the molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)] is generally 10 or less. Further, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial or any combination thereof.

Hydrogenated block copolymers having a polymer block B mainly composed of a conjugated diene compound at at least one end have the same vinyl aromatic compound content, microstructure,
Compared with a hydrogenated block copolymer having a molecular weight and a molecular weight distribution and a polymer block A mainly composed of a vinyl aromatic compound at both ends, it has advantages such as low melt viscosity and large elongation. .

The hydrogenated block copolymer may be produced by any method as long as it has the above-mentioned structure. For example, a vinyl aromatic compound-conjugated diene compound block copolymer was synthesized in an inert solvent using a lithium catalyst or the like by the method described in JP-B-40-23798, and then, for example, JP-B-42- 870
No. 4, the method described in JP-B-43-6636, particularly preferably by the method described in JP-B-63-4841 and JP-B-63-5401, hydrogenation in an inert solvent Hydrogenation can be carried out in the presence of a catalyst to synthesize the hydrogenated block copolymer used in the present invention. At this time, at least 80% of the aliphatic double bonds based on the conjugated diene compound in the vinyl aromatic compound-conjugated diene compound block copolymer
Is hydrogenated to form a polymer block containing a conjugated diene compound as a main component in the form of an olefinic compound polymer block B.
Convert to. Further, hydrogen of an aromatic double bond based on a vinyl aromatic compound copolymerized with a polymer block A mainly containing a vinyl aromatic compound and a polymer block B mainly containing a conjugated diene compound, if necessary. The addition rate is not particularly limited, but the hydrogen addition rate is preferably 20% or less.

The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus or the like.

On the other hand, the modified hydrogenated block copolymer that can be used as another component (I) -a) has a molecular unit containing a carboxylic acid group or its derivative group in the hydrogenated block copolymer. It is a combination. The hydrogenated block copolymer modified product is obtained by adding an unsaturated carboxylic acid or a derivative thereof to the above hydrogenated block copolymer in a solution state or a molten state without using a radical initiator or by using it. Obtained by As the hydrogenated block copolymer that can be used for such addition modification, any of those defined above can be used, and as an example of the unsaturated carboxylic acid or its derivative to be added to the hydrogenated block copolymer. Is maleic acid, halogenated maleic acid,
Itaconic acid, fumaric acid, citraconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo- [2,2,1] -5-heptene-2,3-dicarboxylic acid and their dicarboxylic acids Acid anhydrides, esters, amides, imides and the like, and acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, mesaconic acid, anseric acid and the like and esters of these monocarboxylic acids, such as methyl methacrylate, glycidyl methacrylate and amides, Derivatives of ether, nitrile, thiol and the like can be mentioned, of which maleic anhydride or glycidyl methacrylate is particularly preferable.

The method for producing these hydrogenated block copolymer modified products is not particularly limited in the present invention, but the obtained hydrogenated block copolymer modified product contains an unfavorable component such as gel, and its melt viscosity. Is significantly increased and workability deteriorates, which is not preferable. A preferred method is, for example, in an extruder in the presence of a radical initiator,
There is a method of reacting a hydrogenated block copolymer with an unsaturated carboxylic acid or its derivative.

The addition amount of the unsaturated carboxylic acid or its derivative to the hydrogenated block copolymer is 20 parts by weight or less per 100 parts by weight of the hydrogenated block copolymer, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. It is a department. Even if the addition amount exceeds 20 parts by weight, the modification effect is not increased as compared with the addition amount less than 20 parts by weight. The unsaturated carboxylic acid or derivative thereof used in the present invention can be used not only in one kind but also in a mixture of two or more kinds.

The inorganic filler used as the component (I) -b) in the present invention is indispensable for preventing the reduction of the breaking strength of the molded product due to the addition of polysiloxane, and examples thereof include calcium carbonate, Examples thereof include talc, carbon black, titanium oxide, white carbon, magnesium carbonate, clay, barium sulfate, glass or metal powder. Of these, calcium carbonate is preferred. The amount of the inorganic filler used is 30 to 200 parts by weight, preferably 45 to 95 parts by weight, with respect to 100 parts by weight of the hydrogenated block copolymer, and less than 30 parts by weight, the breaking strength due to the addition of polysiloxane. If the amount exceeds 200 parts by weight, the hardness of the molded article becomes too high and the flexibility is lost, which is not preferable. The preferred particle size of the inorganic filler is 1 to
The thickness is 10 μm, more preferably 1.5 to 2.5 μm. If it is less than 1 μm, the effect of improving stickiness due to polysiloxane is insufficient, and if it exceeds 10 μm, the mixing property is deteriorated, which is not preferable.

Examples of the polyolefin used as the component (I) -c) in the present invention include polyethylene, polypropylene, and a copolymer of polypropylene and ethylene or an α-olefin such as 1-butene.
Polypropylene and block copolymers of propylene and ethylene are preferred. The amount of the polyolefin used is, relative to 100 parts by weight of the hydrogenated block copolymer, 10 to 100 parts by weight, preferably 20 to 75 parts by weight. Below 10 parts by weight, heat resistance, breaking strength, processability, etc. When the amount exceeds 100 parts by weight, the hardness of the molded article becomes too high and the flexibility is lost, which is not preferable.

The non-aromatic softening agent for rubber used as the component (I) -d) in the present invention has a kinematic viscosity at 40 ° C. of 150 to 450 centistokes, preferably 250 to 400 centistokes. It is not particularly limited as long as it is, and examples thereof include mineral oil-based softening agents generally called paraffin-based or naphthene-based oils, and paraffin-based oils are particularly preferable. The amount of the non-aromatic softening agent for rubber used is 70 parts by weight or more and less than 150 parts by weight with respect to 100 parts by weight of the hydrogenated block copolymer. If the kinematic viscosity at 40 ° C. is less than 150 centistokes, the heat distortion resistance of molding is not sufficient, and if it exceeds 450 centistokes, bleeding from the molded body occurs, and the effect of improving stickiness by polysiloxane is deteriorated, which is preferable. Absent. On the other hand, if the amount used is less than 70 parts by weight, the hardness of the molded product becomes too high and the flexibility is lost, and if it is 150 parts by weight or more, bleeding from the molded product still occurs, and the effect of improving stickiness by polysiloxane is improved. At the same time, the breaking strength also deteriorates, which is not preferable.

The polysiloxane used as the component (II) in the present invention is an important component for improving the stickiness of the surface of the molded body, and is 50 to 500 centistokes at room temperature, preferably 70 to 500 centistokes, Preferably 100
There is no particular limitation as long as it has a kinematic viscosity of 300 centistokes. Among them, polyorganosiloxane represented by the general formula:-{RR'SiO} n- (R, R '= alkyl group, aryl group, n = integer) is preferable, and specifically, polydimethylsiloxane, polymethylsiloxane. Examples thereof include phenyl siloxane and polydimethyl-diphenyl siloxane, which may be a mixture of two or more of these.
Polydimethylsiloxane is particularly preferred. The amount of the polysiloxane used is 0.5 to 30 parts by weight with respect to 100 parts by weight of the composition comprising the hydrogenated block copolymer, the inorganic filler, the polyolefin, and the softening agent for the non-aromatic rubber as described above. The amount is preferably 1 to 15 parts by weight, more preferably 2 to 8 parts by weight. When the kinematic viscosity at room temperature is less than 50 centistokes, there is a risk of volatilization, foaming, etc. during processing, and when it exceeds 500 centistokes, the effect of improving the stickiness of the surface of the molded article is lost, which is not preferable. On the other hand, if the amount used is less than 0.5 parts by weight, there is no effect of improving the stickiness of the surface of the molded product, and if it exceeds 30 parts by weight, the polysiloxane bleeds to the surface of the molded product excessively and slimes, resulting in an extreme surface feel. It is not preferable because it deteriorates and molding becomes difficult.

The molded product of the present invention comprising the above components has a contact angle of pure water with respect to the molded product of 105 °, preferably 110 ° or more. When the contact angle is less than 105 °, the surface modification effect of polysiloxane is not exhibited on the surface of the molded product, and stickiness remains. For the method of measuring the contact angle on the surface of the molded product,
There are methods such as those described in "Polymer Engineering Course 14 Polymer Material Testing Method" (edited by The Polymer Society of Japan, Jinshokan (1963)) and are not particularly limited, but the contact angle is measured by directly observing the droplets on the surface. The droplet shape method is preferable in terms of ease of measurement.

The molded article of the present invention may include general-purpose thermoplastic resins such as polystyrene, high-impact polystyrene, AS resin, ABS resin, MMA resin, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, etc. .

Further, the molded body of the present invention, if necessary, polyamide,
A thermoplastic engineering resin such as polyester, polycarbonate, polyphenylene oxide may be included. For example, a molded product containing polyamide can be expected to have improved heat resistance and oil resistance, and a molded product containing polyphenylene oxide can be expected to have improved thermal deformation resistance.

In addition, the molded article of the present invention, as is done in the usual resin molded article, if necessary, a pigment, a heat stabilizer,
It is also possible to add an antioxidant, an ultraviolet absorber or the like.

The means for obtaining the molded product of the present invention is not particularly limited, but a mechanical mixing method which is usually used, for example, a mixing method using a roll, a Brabender, an extruder or the like and a thermoplastic resin molding method, for example, A combination of injection molding, extrusion molding, blow molding, calender molding and the like is preferable.

The molded body of the present invention, the use is not particularly limited, among them,
Automotive interior parts, which require rubber-likeness and good feel,
It can be used very suitably for various grip coatings, various eye caps, etc.

EFFECTS OF THE INVENTION According to the present invention, a composition comprising a hydrogenated block copolymer excellent in rubber elasticity, mechanical properties, weather resistance, and heat distortion resistance, an inorganic filler, a polyolefin, and a paraffin oil having a relatively high viscosity. It is possible to obtain a thermoplastic elastomer molded product in which the stickiness of the product is improved by polysiloxane.

[Examples] Hereinafter, the present invention will be described more specifically with reference to Examples.
It is not limited to these examples.

Reference Example 1 Synthesis of Hydrogenated Block Copolymer (1-1) By the method described in Japanese Patent Publication No. 63-4841, it has a structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene, Bonded styrene content 30%, polybutadiene part before hydrogenation 35% 1,2-vinyl bond, number average molecular weight 172,000, molecular weight distribution 1.0
4. Hydrogenated block copolymer with 99% hydrogenation of polybutadiene was synthesized.

(1-2) In the same manner as (1-1), having a structure of polystyrene-hydrogenated polybutadiene-polystyrene, the amount of bound styrene is 32%, the polybutadiene portion before hydrogenation is 1,
A hydrogenated block copolymer having a 2-vinyl bond content of 31%, a number average molecular weight of 150,000, a molecular weight distribution of 1.06 and a hydrogenation rate of 99% in the polybutadiene part was synthesized.

(1-3) having the structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene in the same manner as (1-1), with a bound styrene content of 33% and hydrogenation 35% of 1,2-vinyl bond in the previous polybutadiene part, number average molecular weight 180,00
0, molecular weight distribution 1.07, hydrogenation rate of polybutadiene 98
% Hydrogenated block copolymer was synthesized.

(1-4) Similar to (1-1), having a structure of (hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene) ₄ Si, bound styrene content 30%, polybutadiene portion before hydrogenation Of 1,2-vinyl bond of 35%, number average molecular weight of 170,000, molecular weight distribution of 1.08 and hydrogenation rate of 97% of polybutadiene part were synthesized.

Reference Example 2 Synthesis of Modified Hydrogenated Block Copolymer (2-1) 2 parts by weight of maleic anhydride and 2,5-dimethyl-per 100 parts by weight of the hydrogenated block copolymer obtained in (1-1)
0.2 parts by weight of 2,5-di (tertiary butylperoxy) hexane was mixed, and the addition modification reaction was performed with a 50 mmφ diameter twin-screw extruder set at 250 ° C. The modified hydrogenated block copolymer thus obtained had 0.75 parts by weight of maleic anhydride added.

(2-2) 2.5 parts by weight of glycidyl methacrylate, 100 parts by weight of the hydrogenated block copolymer obtained in (1-1), di-
0.5 parts by weight of tert-butyl peroxide was mixed, and the modification reaction was performed while forcedly venting (pressure reduction degree: 750 mmHgG) using a vacuum pump with a 45 mmφ vented twin-screw extruder set at 190 ° C. The modified hydrogenated block copolymer obtained was one in which 1.5 parts by weight of glycidyl methacrylate was added.

Examples 1 to 28 and Comparative Examples 1 to 14 The respective components having the compounding ratios shown in Tables 1 to 5 were kneaded in a 30 mmφ twin-screw extruder set at 220 ° C. to obtain a sheet having a thickness of about 2 mm and 180
After compression molding at ℃, it was subjected to the following tests.

(1) Hardness (-): JIS K 6301 "Physical test method for vulcanized rubber" Spring hardness test (A type).

(2) Breaking strength (kg / cm ² ) and breaking elongation (%): JIS K 6301 “Physical test method for vulcanized rubber” Tensile test. The measurement temperature is 25 ° C, and the test piece is type 3.

(3) Heat distortion resistance (%): In accordance with JIS K 6301 "Physical test method for vulcanized rubber", 6 sheets of the above compression-molded sheets punched into a disk with a diameter of 30 mm were stacked and subjected to a compression set test. I went.

(4) Contact angle (°): At 15 ° C., 10 μl of pure water was dropped on a compression-molded sheet, and the contact angle was measured by directly observing the shape of the droplet through a lens from the side.

(5) Stickiness (-): "No stickiness" is determined by judging the feel of the compression molded sheet.
Was marked with “○”, and “sticky” was marked with “X”.

In the molded product obtained by adding 1.5 to 7 parts by weight of 200 to 400 centistokes polysiloxane to 100 parts by weight of the composition mainly composed of the hydrogenated block copolymer of Reference Example (1-1), the stickiness on the surface was improved. (Examples 1 to 7). Similar results were obtained with molded products having different block structures of hydrogenated block copolymers (Examples 8 to 14). Also, the molded products using the modified product of the hydrogenated block copolymer were similarly improved in stickiness (Examples 15 to 28).

However, in a molded product having a polysiloxane content or viscosity outside the range of the present invention, the stickiness of the surface is not improved (Comparative Examples 1, 3 to 4, 7, 9 to 11, 13 to 14), or It became impossible (Comparative Examples 2, 8, 12).

Further, in the molded article using the rubber softener having a viscosity higher than the range of the present invention, the stickiness of the surface was not improved (Comparative Example 6), and the rubber softener having a viscosity lower than the range of the present invention was used. In the molded product, the stickiness of the surface was improved, but the compression set was deteriorated (Comparative Example 5).

Table footnote 1): Elastomer synthesized in Reference Example 2): Whiten SB Shiraishi Calcium (average particle size 1.8μ) 3): Asahi Kasei Polypro M-1600 Asahi Kasei 4): (A) Diana Process Oil PW- 380 Idemitsu Kosan (Kinematic viscosity (40 ° C) 381.6 centistokes) (B) Diana Process Oil PW-90 Idemitsu Kosan (Kinematic viscosity (40 ° C) 95.5 centistokes) (C) Idemitsu Polybutene 15H Idemitsu Petrochemical (Dynamic) Viscosity (37.8 ℃) 580 centistokes 5): (A) KF96-200 manufactured by Shin-Etsu Chemical (kinematic viscosity (25 ℃) 200 centistokes) (B) KF54 Shin-Etsu Chemical (kinematic viscosity (25 ℃) 400 centistokes) (C) KF96-20 manufactured by Shin-Etsu Chemical (kinematic viscosity (25 ° C) 20 centistokes) (D) KF96-3000 manufactured by Shin-Etsu Chemical (kinematic viscosity (25 ° C) 3000 centistokes) Comparative Example 15 The same method as in Example 3 Using the composition of the following composition Create a test piece, and evaluate the performance.

Hydrogenated block copolymer (Reference Example 1-1) 100 parts by weight, calcium carbonate (2) 85 parts by weight, polypropylene (3) 55
3 parts by weight of polysiloxane (5-A) per 100 parts by weight of rubber softening agent (4-A), hydrogenated block copolymer, calcium carbonate, polypropylene, rubber softening agent. The test piece prepared with the compounding composition of the part has a hardness of 54, a breaking strength of 65 kg / cm ² , an elongation at break of 800%, and a compression set of 6
It was 0%, the contact angle was 100 degrees, and the stickiness was x.

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Claims (1)

[Claims] 1. A hydrogenated block copolymer comprising a) a polymer block A mainly containing at least two vinyl aromatic compounds and a polymer block B mainly containing at least one conjugated diene compound. 100 parts by weight of the hydrogenated block copolymer and / or modified product of the hydrogenated block copolymer containing a carboxylic acid group or its derivative group obtained b) Inorganic filler 30 to 200 parts by weight c) Polyolefin 10 to 100 Parts by weight d) a composition containing 70 parts by weight or more and less than 150 parts by weight of a softening agent for non-aromatic rubber having a kinematic viscosity of 150 to 450 centistokes at 40 ° C. (I) 100 parts by weight 50 to 500 at room temperature A thermoplastic elastomer molding comprising 0.5 to 30 parts by weight of polysiloxane (II) having a kinematic viscosity of centistokes and having a contact angle of pure water of 105 ° or more.