JPH10195241A - Dynamically cross-linked composition and thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dynamically cross-linked composition capable of providing a thermoplastic elastomer composition good in abrasion resistance, tensile strength and tear strength and excellent in appearance of the molded product, and further to obtain the thermoplastic elastomer composition having before properties. SOLUTION: This dynamically cross-linked composition is obtained by adding a cross-linking agent of (A) a cross-linkable diene-based rubber and/or a cross- linkable thermoplastic elastomer, to 10-80wt.% component A, (B) 20-80wt.% aromatic vinyl compound-based thermoplastic resin, and (C) 0-40wt.% plasticizer (with the proviso that (A)+(B)+(C)=100wt.%) and melting and kneading the cross-linking agent-added components A, B and C, and has 30-100% gelling rate. The thermoplastic elastomer composition consists essentially of (D) 1-50wt.% before dynamically cross-linked composition and (E) 99-50wt.% thermoplastic elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dynamically crosslinked composition which provides a thermoplastic elastomer composition having excellent abrasion resistance, tensile strength and tear strength. Further, the present invention relates to a thermoplastic elastomer composition which is excellent in abrasion resistance, tensile strength, and tear strength using the above-mentioned dynamic crosslinking composition as one component of the composition, and is suitable for electric, industrial, footwear, and sports parts. More specifically, it can be molded with a resin processing machine (injection molding machine, extrusion molding machine, blow molding machine, vacuum molding machine) while using a dynamically crosslinked composition as a component, and has the same performance as a crosslinked product. The present invention relates to a thermoplastic elastomer composition having good appearance.

[0002]

2. Description of the Related Art In recent years, there has been a growing demand in the electric, industrial, footwear and sports parts fields for materials capable of forming molded articles having good appearance with a resin processing machine and having the same performance as crosslinked rubber. Conventionally, styrene-based, olefin-based, urethane-based, and ester-based thermoplastic elastomers have been studied in this field, but the former two lack molded appearance and abrasion resistance, tensile strength, and tear strength. The two are high-priced and hard materials that cannot meet demand. Among them, a thermoplastic elastomer composition comprising a styrene-butadiene block copolymer exhibits high rubber elasticity without vulcanization, and can be processed with a normal thermoplastic resin molding machine. However, this material has a problem in that the appearance of the molded product is poor, such as the surface of the molded product at the time of extrusion molding is rough and the weld is conspicuous. On the other hand, crosslinked rubber has excellent tensile strength and tear strength, but cannot be molded by a resin processing machine, has poor productivity, and has a problem that it cannot meet demand.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been intensively studied in order to solve the above-mentioned problems of the prior art, and has excellent heat resistance, tensile strength, tear strength and excellent appearance in molding. It is an object of the present invention to provide a dynamically crosslinked composition which gives a thermoplastic elastomer composition, and a thermoplastic elastomer composition having the above-mentioned performance.

[0004]

The present invention relates to (A) a crosslinkable diene rubber and / or a crosslinkable thermoplastic elastomer (hereinafter also referred to as "component (A)").
% By weight, (B) 20 to 80% by weight of an aromatic vinyl compound-based thermoplastic resin (hereinafter also referred to as “component (B)”), and 0 to (C) plasticizer (hereinafter also referred to as “component (C)”). 4
0% by weight (provided that (A) + (B) + (C) = 100% by weight) is added with a crosslinking agent of the component (A), and the mixture is melt-kneaded to obtain a gel of the component (A). The present invention provides a dynamically crosslinked composition having a ratio of 30 to 100% (hereinafter, also referred to as a “dynamically crosslinked composition”). Further, the present invention provides (D) 1 to 50% by weight of the above-mentioned dynamic cross-linking composition (hereinafter also referred to as “component (D)”), and (E) a thermoplastic elastomer (hereinafter also referred to as “component (E)”). The present invention provides a thermoplastic elastomer composition containing 99 to 50% by weight [(D) + (E) = 100% by weight] as a main component (hereinafter, also referred to as “thermoplastic elastomer composition”).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the crosslinkable diene rubber used in the component (A) of the dynamically crosslinked composition include natural rubber (NR), high cis and low cis butadiene rubber (BR), and high cis isoprene. Rubber (IR),
Emulsion polymerization and solution polymerization styrene-butadiene rubber (S
BR), acrylonitrile-butadiene rubber (NBR)
And the like. The crosslinkable thermoplastic elastomer used as the component (A) includes styrene-
Butadiene block copolymer or styrene-isoprene block copolymer and hydrogenated products thereof. The 1,2-vinyl bond content is 70% or more, preferably 80% or more, the crystallinity is 5% to 50%, preferably 10 to 35%, and the intrinsic viscosity [η] (3
0.5 dl / g or more, preferably 0.6 dl / g or more.
dl / g or more of 1,2 polybutadiene (RB) can also be used. Of these, preferred are NR, IR, S
BR, BR, RB and styrene-butadiene block copolymers. Particularly preferred is BR, which includes BR having a cis-type, trans-type, vinyl-type, or a mixture thereof, and modified (carboxy, epoxy, etc.) forms thereof, and their molecular weights are selected over a wide range. Is possible. These can be used alone or in combination of two or more.

The amount of (A) the crosslinkable diene rubber and / or the crosslinkable thermoplastic elastomer is from 10 to 80% by weight, preferably from 30 to 70% by weight, from the viewpoint of crosslinkability and kneading properties. . If the amount is less than 10% by weight, the crosslinking property is impaired, and the effect of improving the abrasion resistance of the target composition is not exhibited, which is not preferable. On the other hand, if it exceeds 80% by weight, the kneading property is impaired due to heat generation, poor dispersion of the cross-linking agent occurs, and the effect of improving the abrasion resistance of the target composition is not exhibited.

[0007] Next, the component (B) comprises at least one aromatic compound selected from (co) polymers obtained by (co) polymerizing an aromatic vinyl compound in the presence or absence of a rubbery polymer. It is an aromatic vinyl compound-based thermoplastic resin. The content of the rubbery polymer is preferably 0 to 20% by weight, more preferably 0 to 10% by weight. The structure is linear,
Any of a branched shape and a mesh shape may be used, and there is no particular limitation. Examples of the rubbery polymer include BR, IR,
SBR, a styrene-isoprene copolymer, an ethylene-propylene-non-conjugated diene terpolymer (EPDM), and the like. Of these, BR and SBR are preferred.

[0008] The aromatic vinyl compound includes:
Styrene, α-methylstyrene, p-methylstyrene,
Vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and the like,
Used alone or in combination of two or more. Of these, styrene is particularly preferred. (B)
The molecular weight of the aromatic vinyl compound-based thermoplastic resin is a weight average molecular weight in terms of polystyrene, and is preferably 10,000.
0 to 150,000.

(B) The amount of the aromatic vinyl compound-based thermoplastic resin used is from 20 to 8 from the viewpoints of crosslinkability, kneading properties and the like.
0% by weight, preferably 30 to 70% by weight. If the amount is less than 20% by weight, the kneading property is impaired due to heat generation and poor dispersion of the crosslinking agent occurs, and the effect of improving the abrasion resistance of the target composition is not exhibited, which is not preferable. On the other hand, if it exceeds 80% by weight, the crosslinking property is impaired, and the effect of improving the abrasion resistance of the target composition is not exhibited, which is not preferable.

Next, as the plasticizer (C), for example, petroleum softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petrolatum, and coal tar softeners such as coal tar and coal tar pitch ,
Fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, and coconut oil, waxes such as tall oil, sub oil or beeswax, carnauba wax, lanolin, ricinoleic acid, palmitic acid, stearic acid, barium stearate, and stear Fatty acids and fatty acid salts such as calcium phosphate, barium lanolinate and zinc lanolinate, and synthetic high-molecular substances such as petroleum resins are exemplified. Further, phthalic acid ester type, adipic acid ester type, sebacic acid ester type, phosphoric acid ester type plasticizer and the like can be mentioned. The use amount of the component (C) is 0 to 40% by weight, preferably 5 to 30% by weight, and more preferably 5 to 20% by weight from the viewpoint of kneading properties and dispersibility of the crosslinked product. If it exceeds 40% by weight, the kneading property and the dispersing property are poor, and the gelation rate is lowered.

As the crosslinking agent used for crosslinking the component (A), in the case of an organic peroxide, ketone peroxides,
Examples include peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. Among them, dialkyl peroxides include dicumyl peroxide, 1,3-bis- (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxide). Oxy) hexane, 2,5-dimethyl-2,5-di (t-
Examples of peroxyketals such as butylperoxy) hexyne-3 include 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, and 1,1-bis Hydroperoxides such as (t-butylperoxy) cyclododecane include p-menthane hydroperoxide and the like.
Examples of the diacyl peroxides include benzoperoxide, and examples of the peroxyesters include t-butylperoxymaleic acid, t-butylperoxybenzoate, and t-butylperoxyacetate.

As the crosslinking agent for the component (A), sulfur can also be used. As the sulfur, powdered sulfur, precipitated sulfur, insoluble sulfur, colloidal sulfur, surface-treated sulfur, and the like can be used. As a compound that generates sulfur by heating, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and the like can be used. Further, sulfur mixed in the bituminous substance can be used. Examples of the vulcanization accelerator used in combination with sulfur or a compound that generates sulfur by heating include tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), and N-oxydiethylene-2-benzothiazolyl sulfenamide. (O
BS), N-cyclohexylyl-2-benzothiazolyl sulfenamide (CBS), dibensothiazyl sulfide (MBTS), 2-mercaptobenzothiazole (MBT), zinc di-n-butyl dicarbite (Z
nBDC), zinc dimethyldithiocarbite (ZnM
DC) and the like. As the crosslinking agent, use of an organic peroxide is preferable from the viewpoint of abrasion resistance.

In the case of an organic peroxide, the amount of the cross-linking agent is usually 100 parts by weight of the components (A) to (C).
The amount is 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight. If the amount is less than 0.01 part by weight, crosslinking is insufficient, and the desired gelation ratio is not reached. 5
If the amount is more than the weight part, the amount of heat generated by crosslinking increases, and it is difficult to control the kneading temperature.

In the crosslinking reaction in the dynamic crosslinking composition of the present invention, the above components (A) and (B), and if necessary, the component (C) and the crosslinking agent component are reacted under the following reaction conditions. Can be obtained by melt-kneading.
The gelation rate can be adjusted to the desired gelation rate by appropriately adjusting the type and amount of the crosslinking agent, the kneading temperature, and the kneading time. The gelation ratio of the component (A) is 30 to 100%, preferably 50 to 100%, and more preferably 80 to 100%.
It is. If it is less than 30%, wear resistance and tensile strength are insufficient, which is not preferable.

Thermoplastic Elastomer Composition The thermoplastic elastomer composition comprises (D) 1 to 50% by weight of the above-mentioned dynamic cross-linking composition and (E) 99 to 50% by weight of the thermoplastic elastomer. Things. The amount of the component (D) used in the thermoplastic elastomer composition is 1 to 50% by weight, preferably 5 to 30% by weight. If the content is less than 1% by weight, the desired wear resistance is not exhibited, which is not preferable. On the other hand, if it exceeds 50% by weight,
The fluidity, molded appearance, and abrasion resistance of the thermoplastic elastomer composition are undesirably impaired.

The thermoplastic elastomer (E) used in the thermoplastic elastomer composition composition includes styrene elastomers, olefin elastomers, urethane elastomers, ester elastomers, polyvinyl chloride elastomers, and 1,2-polybutadiene. Fluorinated resin-based elastomers, ion-crosslinked elastomers (ionomers) and the like. Among these, preferred thermoplastic elastomers are styrene-based elastomers and 1,2-polybutadiene. The styrene-based elastomer is, specifically, an aromatic vinyl compound-conjugated diene block copolymer containing at least one polymer block of an aromatic vinyl compound and at least one polymer block of a conjugated diene compound. And may be a linear type or a radial type. Further, the conjugated diene block may be a random copolymer with a small amount of an aromatic vinyl compound, or may be a so-called tapered block in which the content of the aromatic vinyl compound gradually increases.

The structure of the block copolymer is not particularly limited, and any of (AB) _n type, (AB) _n -A type, and (AB) _n -C type can be used. Where:
A is a polymer block of an aromatic vinyl compound, B is a conjugated diene polymer block, C is a residue of a coupling agent, n
Represents an integer of 1 or more. In the above block copolymer, it is of course possible to use a block copolymer in which the conjugated diene portion is hydrogenated.

The aromatic vinyl compound of the aromatic vinyl compound-conjugated diene block copolymer used in the present invention includes styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl Examples include xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, pt-butylstyrene, ethylstyrene, and vinylnaphthalene, which are used alone or in combination of two or more. . Of these, styrene is particularly preferred.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 2-methyl-1,3-butadiene, 2,3-diethyl-butadiene, 2-neopentyl-1,3-butadiene, and 2-chloro-diene. Examples include 1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugated hexadienes, and the like. Of these, particularly preferred are 1,
3-butadiene, isoprene and 2-methyl-1,3-butadiene. The weight average molecular weight of the block copolymer is preferably from 10,000 to 800,000, and more preferably from 20,000 to 500,000. Further, the content of the aromatic vinyl compound in the block copolymer is preferably 5 to 60% by weight, more preferably 20% by weight.
５０50% by weight. As the block copolymer, not only one kind but also one having a different structure and a different aromatic vinyl compound content may be used in combination.

1,2-polybutadiene has a 1,2-vinyl bond content of 70% or more, preferably 80% or more, a crystallinity of 5 to 50%, preferably 10 to 35%, and an intrinsic viscosity [η]. 0.5 dl (measured in toluene at 30 ° C.)
/ G or more, preferably 0.6 dl / g or more. Further, they can be used even if they are mixed.

The amount of the thermoplastic elastomer (E) used in the thermoplastic elastomer composition is 99 to 50% by weight, preferably 95 to 70% by weight. If the content is less than 50% by weight, the fluidity, molded appearance and abrasion resistance of the composition are undesirably impaired. On the other hand, if it exceeds 99% by weight, the desired wear resistance is not exhibited, which is not preferable.

The thermoplastic elastomer composition of the present invention may contain known thermoplastic resins, rubbers, or additives. For example, as a thermoplastic resin,
Examples include polystyrene resin, polyethylene resin, polypropylene resin, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyamide resin, thermoplastic polyester resin, polyacetal resin, and polycarbonate resin. As rubber, SBR,
NBR, BR, ethylene propylene rubber, IR, NR,
Chloroprene rubber, butyl rubber and the like can be mentioned.

Examples of the additives include glass fiber, surface chemically treated glass fiber, carbon fiber, graphite, metal fiber, fibrous filler such as titanium oxide, and hollow such as glass balloon, fly ash balloon and silica balloon. Fillers, light calcium carbonate, heavy calcium carbonate, various surface-treated calcium carbonates, inorganic fillers such as talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicon, synthetic silicon, and carbon black, process oils , Lubricating oil, paraffin, liquid paraffin petroleum asphalt, petroleum softener such as petrolatum, castor oil, linseed oil, rapeseed oil, fatty oil softener such as coconut oil, tall oil, sub oil or beeswax, carnauba wax, lanolin Waxes, ricinoleic acid, palmitic acid, stearin Fatty acids and fatty acid salts such as barium stearate, calcium stearate, barium lanolinate and zinc lanolinate; synthetic high molecular substances such as petroleum resins; phthalate esters, adipates, sebacates, phosphates And the like.

Examples of the tackifier include coumarone indene resin, terpene / phenol resin, and xylene / formalin resin. Examples of the coloring agent include inorganic and organic pigments, and examples of the blowing agent include sodium bicarbonate, ammonium carbonate, N, N'-dinitrosopentamethylenetetramine, azocarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, and the like. Foaming aids such as toluenesulfonyl hydrazide, calcium amide, and p-toluenesulfonyl amide include, for example, salicylic acid, phthalic acid, and urea. Other examples include antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, and the like, and mixtures thereof. These are added, if necessary, in a range of 300 parts by weight or less based on 100 parts by weight of the thermoplastic elastomer composition of the present invention.

Dynamic crosslinkable composition / thermoplastic elastomer group
Preparation and use of the composition There is no particular limitation on the mixing method for producing the composition of the present invention, and ordinary resins, rolls used during rubber processing, kneaders, Banbury mixers, screw extruders, feeder ruder extruders and the like are used. Can be mixed and melt-kneaded. The thermoplastic elastomer composition can be mixed using a tumbler or a Henschel mixer. When preparing the dynamic cross-linking composition, the temperature of peroxide addition during the melt-kneading process is set to a peroxide decomposition half-life of 1
It is preferable to carry out the reaction at a temperature of 20 to 30 ° C. or lower from the temperature of the kneaded material, taking into account the rise due to shear heat generation of the kneaded material. If kneading is carried out at a temperature of 1 minute for decomposition, the system is in a form of poor dispersion, which is not preferable. After the addition of the peroxide, it is preferable to confirm an increase in the kneading torque.

The dynamic cross-linking composition of the present invention is excellent in kneadability and dispersibility. By blending this composition with a thermoplastic elastomer, the processability and the appearance of the molded product (flow mark, gasket, sink mark, etc.) are good. In addition, the thermoplastic elastomer composition of the present invention having excellent abrasion resistance, tensile strength, tear strength, bending resistance, and ozone resistance can be obtained. Further, the thermoplastic elastomer composition of the present invention has physical properties not found in resins and productivity not found in crosslinked rubber. The thermoplastic elastomer composition of the present invention is an excellent one that can easily form a foam, and can be used in combination with a peroxide and sulfur to achieve a cross-linking balance. As described above, the thermoplastic elastomer composition of the present invention can be applied to a wide range of applications from the non-crosslinked field to the crosslinked field, and can be used for industrial products, home appliances, O.D. It is suitably used for A articles, footwear soles (men's shoes, women's shoe soles, casual shoe soles, sports shoe soles), automobile supplies, cushioning materials, housing construction, conveyor belts, packaging materials, and the like.

[0027]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited by these unless the gist of the present invention is exceeded. Parts and% in the examples are on a weight basis. In addition, test pieces and evaluation items used for various physical properties are as follows.

(1) Test pieces of abrasion resistance, hardness, tensile strength and tear strength were formed at 150 ° C. by a resin press. (2) A flat plate was formed under the following conditions, and the appearance of the formed plate was evaluated. <Molding conditions> Molding machine: Inline screw type injection molding machine Mold: 3 × 70 × 150 mm direct gate flat plate Molding temperature: 150 ° C. Injection pressure: 660 kg / cm ² Flow control: Medium Injection: 10 seconds Cooling: 50 Second mold temperature: 30 ℃

<Evaluation method> (1) Gelation ratio: (toluene-insoluble matter) A solution prepared by dissolving 0.25 g of a sample in 50 ml of toluene was filtered through a 400-mesh metal gauze, dried, weighed accurately, and the following formula was used. The gelation ratio was calculated by the following. Gelation rate (%) = [(AB) / C] × D × 100 where A: weight of wire mesh + toluene-insoluble component (g) B: weight of wire mesh (g) C: sample weight (g) D % Of crosslinkable diene rubber and thermoplastic elastomer component in sample x 0.01 [Judgment] 80 to 100%; ３０ 30 to 79%; △ Less than 30%; ×

(2) Workability: Kneadability: Kneadability of the compositions shown in Examples and Comparative Examples in Tables 1 and 2 [Judgment] Kneading can be easily performed without rotor idling or excessive heat generation;
○ It is very difficult to knead the rotor due to idling or excessive heat generation;
× Dispersibility; JSR pancake method (poor dispersion of rubber component and cross-linking agent) (Note: hot-press the sample into a thin plate with a resin press,
How to check the distribution status. [Judgment] No dispersion failure; ○ Dispersion failure; ×

(3) Abrasion resistance: Complies with DIN 53516. Grain size 60, drum rotation 40 rpm, load 10 N, moving distance 40 m, unit (mm ³ ) [judgment] 200 (mm ³ ) or less; ○ [especially, 150 (mm ³ ) or less was evaluated as〕] 201 (mm ³ ) X: The smaller the value, the better the wear amount is measured.

(4) Fluidity: According to JIS K7210 Conditions: 150 ° C. × 5 kg [Determination] 3.0 (g / 10 min) or more; ○ Less than 3.0 (g / 10 min); ×

(5) Tensile strength: based on JIS K6301. [Judgment] 100 (kgf / cm ² ) or more; ○ Less than 100 (kgf / cm ² ); × (6) Tear strength: JIS K6301. [Determination] 30 (kgf / cm) or more; ○ Less than 30 (kgf / cm); ×

(7) Hardness: compliant with JIS K6301 (Type A) (8) Appearance of molded article: Flow mark, rough surface, brushing, silver streak, blooming, etc. on the molded article surface were visually evaluated. [Judgment] Excellent; ○ acceptable; △ not acceptable; ×

Examples 1 to 6 Examples 1 to 6 are examples of preparation of a dynamically crosslinked composition. That is, the components (A) to (C) shown in Table 1 were kneaded by a pressure kneader (starting at a temperature of 120 ° C., the crosslinking was completed by a shear temperature; detected by torque), and an antioxidant was added. Next, the obtained mixture was extruded with an extruder (feeder-ruder type; hereinafter abbreviated as “FR”) and pelletized to obtain a dynamically crosslinked composition. There was no problem with kneading and dispersing properties, and those having a gelation ratio of the component A of 96 to 99% could be obtained.

Comparative Examples 1-4 Kneading and pelletizing were carried out in the same manner as in Example 1 to obtain the dynamically crosslinked composition. Table 2 shows the results. Comparative Example 1
Nos. To 3 are compositions in which the components (A) to (C) in Table 2 are out of the range of the dynamic crosslinking composition of the present invention. There were problems in kneading and dispersibility, and in Comparative Examples 2 and 3, a decrease in the gelation rate was also observed. Comparative Example 4 has no problem in kneading property and dispersibility,
The gelation ratio of the component (A) is out of the range of the dynamic crosslinking composition of the present invention.

Examples 7 to 17 Examples 7 to 17 are examples of preparation of a thermoplastic elastomer composition using a dynamically crosslinked composition. That is, Tables 3 and 4
Kneading the components (D) and (E) shown in (1) at 100 to 150 ° C. (extruder type or pressure kneader, FR)
Then, pelletization was performed to obtain a thermoplastic elastomer composition. Here, the component (D) used in Examples 1 to 6 ((D) component name; (1) to (6)) was used. The obtained thermoplastic elastomer composition was molded using a resin press. In these examples, a composition excellent in the abrasion resistance, tensile strength, tear strength, and appearance of the molded product aimed at by the present invention was obtained. In particular, the wear resistance is 6
0 to 140 and (mm ³⁾ (Examples 1 to 16) showed high wear. In addition, Example 17 exhibited abrasion resistance of 190 (mm ³ ) despite high addition of PW90, an inorganic filler and Super S, which adversely affect abrasion resistance.

Comparative Examples 5 to 13 Kneading and pelletizing were carried out in the same manner as in Example 7 to obtain the thermoplastic elastomer composition. Table 5-6 shows the results.
Shown in Comparative Examples 5 to 8 are compositions in which the component (D) is not blended in the thermoplastic elastomer composition of the present invention.
The wear resistance is remarkably inferior to the examples. Comparative Examples 9-1
2 are Comparative Examples 1 to which do not correspond to the dynamically crosslinked composition of the present invention.
4 is a composition obtained by blending a thermoplastic elastomer with the composition prepared in Example 4, and is significantly inferior in wear resistance.
11 is also inferior in molding appearance. In Comparative Example 13, as the (D) component, the dynamically crosslinked composition of the present invention [(D) component name; (3)]
However, this is an example in which the compounding amount is large beyond the range of the present invention, and the abrasion resistance, tensile strength, tear strength, and appearance of the molded object, which are the objects of the present invention, are remarkably inferior.

The contents of the main materials used in this example and comparative examples are shown below. (1) BR butadiene rubber, cis 1,4-bond 94%, Mooney viscosity (ML _{1 + 4} , 100 ° C.) 28, weight average molecular weight 40
000 (GPC method) (2) RB830 1,2-polybutadiene, crystallinity 28%, manufactured by Nippon Synthetic Rubber Co., Ltd. (3) RB835 1,2-polybutadiene, crystallinity 32%, Japan Synthetic Rubber ( (4) TR2000 styrene-butadiene block polymer, 40% bound styrene, Nippon Synthetic Rubber Co., Ltd. (5) TR2825 styrene-butadiene block polymer, 23% bound styrene, Nippon Synthetic Rubber Co., Ltd. ( 6) TR2787 Styrene-butadiene block polymer, bound styrene content 24%, manufactured by Nippon Synthetic Rubber Co., Ltd.

(7) PS-1 polystyrene, weight average molecular weight 46,000, softening point 1
28 ° C (JIS K2531) (8) PS-2 polystyrene, weight average molecular weight 100,000, MFR
= 30g / 10min (200 ° C, 5,000g), Vicat softening temperature 86 ° C (5,000g, JISK720
6) (9) AR270C Styrene-based thermoplastic elastomer, manufactured by Aron Kasei Co., Ltd.

(10) Parkmill D dialkyl peroxide, half-life 1 minute temperature 171
C., manufactured by NOF Corporation (11) Antioxidant (*) Irganox 1010, manufactured by Ciba Geigy Corporation *) The antioxidant was added last after the crosslinking reaction. (12) Process oil PW-90 paraffin oil, kinematic viscosity 95.54 cSt (40
° C), manufactured by Idemitsu Kosan Co., Ltd. (13) Super S calcium carbonate, average particle size 2.7 μm (calculated from specific surface area), manufactured by Maruo Calcium Co., Ltd.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

[0048]

The dynamic crosslinking composition of the present invention has excellent kneading properties and dispersing properties. The thermoplastic elastomer composition of the present invention in which this composition is blended with the thermoplastic elastomer composition has excellent abrasion resistance, tensile strength, and tear strength, and has moldability equivalent to that of a resin by a resin molding machine. With rubber-like properties, industrial products, home appliances, O.D. A goods, footwear soles (men's, women's shoe soles, casual shoe soles, sports shoe soles), automotive supplies, cushioning materials, housing construction,
It can be suitably used for conveyor belts, packaging materials, etc., can be used over a wide range of applications, and has extremely high industrial utility value.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Takeo Nakamura 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (2)

[Claims] (A) a crosslinkable diene rubber and / or
Or 10 to 80% by weight of a crosslinkable thermoplastic elastomer, (B) an aromatic vinyl compound-based thermoplastic resin 20 to 8
0% by weight and (C) 0 to 40% by weight of a plasticizer (however, (A) + (B) + (C) = 100% by weight)
(A) a component obtained by adding a crosslinking agent and melt-kneading;
A dynamically crosslinked composition, wherein the gelation ratio of the component (A) is 30 to 100%. 2. (D) The dynamic cross-linking composition 1 according to claim 1.
-50% by weight, and (E) a thermoplastic elastomer 99
A thermoplastic elastomer composition containing 50 to 50% by weight [(D) + (E) = 100% by weight] as a main component.