JP3130471B2 - Thermoplastic elastomer resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel thermoplastic elastomer resin composition which is rich in flexibility, excellent in heat deformation properties, mechanical strength and moldability, and particularly excellent in oil resistance and stain resistance. The present invention relates to a method for producing the composition. The resin composition of the present invention is also a thermoplastic elastomer provided with flexibility. Further, the resin composition of the present invention can be added to a thermoplastic elastomer (polyester resin, polyolefin resin, polyurethane resin, vinyl aromatic resin, polyamide resin) as a flexibility imparting agent.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomer resins, which are rubber-like materials and do not require a vulcanization step and have the same moldability as thermoplastic resins, have been used in automobile parts, home appliance parts, wire coatings, footwear. , Has been attracting attention in the field of miscellaneous goods.

[0003] Various types of polymers such as polyolefins, polyurethanes, polyesters, polystyrenes, polyvinyl chlorides and polyamides have been developed and commercially available as such thermoplastic elastomer resins.

Among them, styrene-butadiene-
Polystyrene-based thermoplastic elastomer resins such as block copolymer (SBS) and styrene-isoprene-block polymer (SIS) are rich in flexibility, have good rubber elasticity at room temperature, and are obtained from them. The composition is excellent in processability.

However, these polymers have a double bond as a conjugated diene block in the molecule, and therefore have a problem in heat aging resistance (thermal stability) and weather resistance.

[0006] In order to solve this problem, an elastomer resin composition having improved thermal stability can be obtained by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene.

Several thermoplastic elastomer resin compositions using these hydrogenated products have been proposed. For example, Japanese Patent Application Laid-Open Nos. 50-14742 and 52-72 have been proposed.
No. 26551, and the like. And
For example, Japanese Patent Application Laid-Open No. 58-13203 discloses such improved methods.
No. 2, JP-A-58-145751, JP-A-58-145751,
JP-A-9-53548 and JP-A-62-48757 disclose a composition comprising a hydrogenated styrene / conjugated diene-block copolymer and a hydrocarbon and an α-olefin polymer resin, or a method for producing the same. It has been disclosed. However, conventional thermoplastic elastomer resin compositions using these hydrogenated block copolymers have a problem in rubber-like properties, for example, deformation under heating and compression (compression set) and rubber elasticity at high temperatures.

To improve this point, a crosslinkable composition obtained by subjecting a composition containing such a hydrogenated derivative of a block copolymer to silane modification, or a hydrogenated derivative of such a block copolymer is used. In the presence of an organic peroxide, there has been proposed a crosslinked product obtained by crosslinking in the presence of an organic peroxide. For example, JP-A-59-6236, JP-A-62-57662, and Japanese Patent Publication No. Hei. 49
927, Japanese Patent Publication 3-11291, Japanese Patent Publication 6-13628
Is shown in

However, the crosslinked compositions of hydrogenated block copolymers disclosed by these proposals still have insufficient compression set at high temperatures, especially at 100 ° C. Therefore, at present, it has not yet reached the performance level required for vulcanized rubber applications. For example,
Good workability cannot be obtained, and mechanical strength decreases.

[0010] In order to improve this point, a polymer obtained by copolymerizing or grafting a component comprising a carboxylic acid derivative and / or an epoxy derivative to a composition containing a hydrogenated derivative of such a block copolymer, or a copolymer of the same. A crosslinked product obtained by adding a polymer in which another polymer is grafted or block-shaped to the coalesced or a polyamide-based polymer and / or a polyester-based polymer and then crosslinking in the presence of an organic peroxide is obtained. It has been proposed, for example, in Japanese Patent Application Laid-Open No. Hei 4-20549. However, the disclosed crosslinked composition of a hydrogenated block copolymer has a problem that the compression set is large at a high temperature, particularly at 100 ° C. or higher, and the characteristic balance between the compression set and the hardness is poor. In addition, in the case of adding a polyamide-based polymer, a polyester-based polymer or a polyurethane-based polymer, the hardness becomes HSA85 or more, and there is no much difference from the polyamide-based polymer, the polyester-based polymer, and the polyurethane-based polymer alone. I will.

In addition, a modified polystyrene resin and / or a modified polyolefin resin containing an epoxy group, an acid anhydride group or an oxazoline group is added to a composition containing a hydrogenated derivative of a block copolymer and a polyester resin. Accordingly, a composition having improved compatibility, excellent flexibility, heat resistance, and chemical resistance has been proposed, and is disclosed in, for example, JP-A-5-214209. However, the disclosed crosslinked composition of a hydrogenated block copolymer has a problem that the compression set is large at a high temperature, particularly at 100 ° C. or higher, and the characteristic balance between the compression set and the hardness is poor. Furthermore, since the soft segment of the hydrogenated block copolymer has not been subjected to a treatment such as cross-linking, even if the initial chemical resistance is excellent, it can be considerably immersed for a long time or in an environment of 100 ° C. or more. Swells and loses its shape.

[0012]

DISCLOSURE OF THE INVENTION The present invention provides a novel heat-resistant composition which is free from the above-mentioned disadvantages, has high flexibility, is excellent in heat-resistant deformation characteristics, mechanical strength and moldability, and is particularly excellent in oil resistance and stain resistance. An object of the present invention is to provide a plastic elastomer resin composition.

[0013]

In order to solve the above-mentioned problems, the present invention provides a method of blending the above-mentioned components (a) to (e) and, if necessary, further a component (f) in a specific ratio. It is characterized by. Further, the present invention relates to the above components (a) to (e),
An excellent thermoplastic elastomer resin composition which solves the above-mentioned problems is provided by further blending the component (f) by a method as set forth in claim 6 if necessary.

[0014]

Preferred embodiments of the present invention include: (1) (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and a polymer block B mainly composed of a conjugated diene compound; And / or a hydrogenated block copolymer obtained by hydrogenating the copolymer. 100 parts by weight (b) Softener for non-aromatic rubber 20 to 300 parts by weight (c) ) Carboxyl group, acid anhydride, epoxy group or oxo
Peroxide-crosslinked modified olefin resin modified by sazonyl group , and / or copolymer rubber containing the same 1.0 to 150 parts by weight (d) peroxide decomposed olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing the same (e) at least one selected from the group consisting of polyester-based polymers and copolymers, polyamide-based polymers and copolymers, and polyurethane-based polymers and copolymers A thermoplastic elastomer resin composition containing 1.0 to 1200 parts by weight of one polymer; (2) the thermoplastic elastomer resin composition according to the above (1), further containing (f) 100 parts by weight or less of a hydrogenated petroleum resin; 3) The thermoplastic elastomer resin composition according to the above (1) or (2), further comprising (g) an inorganic filler in an amount of 0 to 100 parts by weight, and (4) a crosslinking aid which is a monomer having an ethylenically unsaturated group. Above (1) to 0.1 to 10 parts by weight
The thermoplastic elastomer resin composition according to any one of (3).

In a preferred embodiment of the present invention, (5) (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least two polymer blocks B mainly composed of a conjugated diene compound; One block copolymer and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 100 parts by weight (b) Softener for non-aromatic rubber 20 to 300 parts by weight (c) Carboxyl Group, acid anhydride, epoxy group or oxy group
Peroxide-crosslinked modified olefin resin modified by sazonyl group , and / or copolymer rubber containing the same 1.0 to 150 parts by weight (d) peroxide decomposed olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing the same (e) at least one selected from the group consisting of polyester-based polymers and copolymers, polyamide-based polymers and copolymers, and polyurethane-based polymers and copolymers A method for producing a thermoplastic elastomer resin composition containing 1.0 to 1200 parts by weight of one polymer, wherein at least one of component (a), component (b) and component (c), and at least one of component (d) Part and at least a part of the component (e) are heat-treated in the presence of an organic peroxide to crosslink, and then the crosslinked product is mixed with the components (c), (d) and (e).
(6) a method for producing a thermoplastic elastomer resin composition, which comprises compounding the remainder, if any, with (b) mixing (f) 100 parts by weight or less of a hydrogenated petroleum resin before the heat treatment; (7) The method for producing a thermoplastic elastomer resin composition according to (5), (7) the thermoplastic elastomer resin composition according to (5) or (6), wherein (g) 100 parts by weight or less of an inorganic filler is added at an optional stage. (8) wherein at least 3 parts by weight of component (d) is subjected to a heat treatment in the presence of an organic peroxide, and at least 5 parts by weight are blended after the heat treatment.
(7) The method for producing a thermoplastic elastomer resin composition according to any one of (7), (9) the above (5) to (8), wherein at least 1 part by weight of the component (c) is subjected to the heat treatment. Any one of the above (5) to (9), wherein at least 10 parts by weight of the component (e) is subjected to the heat treatment. (11) The method for producing a thermoplastic elastomer resin composition according to any one of (11) to (11), wherein the crosslinking is further performed in the presence of a crosslinking aid which is a monomer having an ethylenically unsaturated group.
(10) The method for producing a thermoplastic elastomer resin composition according to any one of (10), (12) wherein the organic peroxide is 0.1 to 4.
The method for producing a thermoplastic elastomer according to any one of the above (5) to (11), which is 0 parts by weight, can be mentioned.

According to the present invention, there is provided a resin composition having excellent rubber properties and mechanical strength as compared with conventional thermoplastic elastomer resin compositions, and particularly excellent in oil resistance and stain resistance, by the above method. Is what you do. The molded article obtained from the resin composition of the present invention has excellent appearance.

Hereinafter, each component will be described in detail. (A) Component Block Copolymer Component (a) of the present invention comprises at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. Or a mixture obtained by hydrogenating the block copolymer, or a mixture thereof.
A vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as -BA, BABA, ABABA, or a hydrogenated product thereof; Can be mentioned. (Hydrogenated) block copolymer (hereinafter, (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer)
Contains 5 to 60% by weight, preferably 20 to 50% by weight of a vinyl aromatic compound. The polymer block A based on vinylaromatics preferably consists of vinylaromatics alone or with more than 50% by weight, preferably more than 70% by weight, of conjugated dienes (hydrogenated). It is a copolymer block with a compound (hereinafter, the (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound). The polymer block B based on (hydrogenated) conjugated diene compounds preferably consists only of (hydrogenated) conjugated diene compounds or comprises more than 50% by weight of (hydrogenated) conjugated diene compounds, Preferably, it is a copolymer block of 70% by weight or more and a vinyl aromatic compound. In each of the polymer block A mainly containing the vinyl aromatic compound and the polymer block B mainly containing the (hydrogenated) conjugated diene compound, the vinyl compound in the molecular chain or the (hydrogenated)
The distribution of the conjugated diene compound is random, tapered (the monomer component increases or decreases along the molecular chain),
It may be partially block-shaped or any combination thereof. When there are two or more polymer blocks A mainly containing a vinyl aromatic compound or two or more polymer blocks B mainly containing a (hydrogenated) conjugated diene compound, they have different structures even if they have the same structure. There may be.

(Hydrogenated) As the vinyl aromatic compound constituting the block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like are selected. Of which styrene is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
Isoprene and combinations thereof are preferred.

The microstructure of the polymer block B mainly composed of a conjugated diene compound can be arbitrarily selected.
In the butadiene block, the 1,2-microstructure is preferably from 20 to 50%, particularly preferably from 25 to 45%. In the polyisoprene block, 70% of the isoprene compound
-100% by weight has a 1,4-microstructure and at least 9 aliphatic double bonds based on the isoprene compound.
Those in which 0% is hydrogenated are preferred.

The weight average molecular weight of the (hydrogenated) block copolymer of the present invention having the above-mentioned structure is preferably 5,000 to 1,500,000, more preferably 1 to 1.
0000 to 550,000, more preferably 10
0000 to 550,000, particularly preferably 100,
The range is from 000 to 400,000. Molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (M
w / Mn)) is preferably 10 or less, more preferably 5 or less.
Or less, more preferably 2 or less. The molecular structure of the (hydrogenated) block copolymer may be linear, branched, radial, or any combination thereof.

Numerous methods have been proposed as methods for producing these block copolymers. Representative methods include, for example, a method described in Japanese Patent Publication No. 40-23798, which uses a lithium catalyst or a Ziegler catalyst. It can be obtained by performing block polymerization in an inert solvent using a type catalyst. By hydrogenating the block copolymer obtained by the above method in the presence of a hydrogenation catalyst in an inert solvent, a hydrogenated block copolymer is obtained.

Specific examples of the (hydrogenated) block copolymer include SBS, SIS, SEBS, and SEPS. In the present invention, a particularly preferred (hydrogenated) block copolymer is a polymer block A mainly composed of styrene, and mainly composed of isoprene, and 70 to 100% by weight of isoprene has a 1,4-micro structure, And at least 90 of aliphatic double bonds based on the isoprene
% Is a hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 and a polymer block B to which hydrogen has been added. More preferably, 90 to 100% by weight of isoprene is the above hydrogenated block copolymer having a 1,4-microstructure.

(B) Component Softener for Non-Aromatic Rubber As the component (b) of the present invention, a non-aromatic mineral oil or a liquid or low molecular weight synthetic softener can be used. The mineral oil softener used for rubber is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms. Those having 30 to 40% of naphthenic ring carbons are called naphthenics, and those having 30% or more aromatic carbons are called aromatics.

The mineral oil-based rubber softener used as the component (b) of the present invention is a paraffin-based or naphthene-based softener in the above category. The use of an aromatic softening agent is not preferred because its use makes the component (a) soluble and inhibits the cross-linking reaction, so that the physical properties of the obtained composition cannot be improved.
The component (b) is preferably a paraffinic one,
Further, among paraffins, those having a small amount of aromatic ring components are particularly preferable.

These non-aromatic rubber softeners have a dynamic viscosity at 37.8 ° C. of 20 to 500 cS.
t, pour point is -10 to -15 ° C, flash point (COC) is 1
Indicates 70 to 300 ° C.

The amount of component (b) is 100 parts
20 to 300 parts by weight, preferably 4 parts by weight,
The amount is 0 to 300 parts by weight, more preferably 80 to 200 parts by weight, and even more preferably 100 to 170 parts by weight. 30
If the amount exceeds 0 parts by weight, the softener tends to bleed out, which may give tackiness to the final product, and also deteriorates the mechanical properties. If the amount is less than 20 parts by weight, the moldability of the obtained composition will be lost. Part of component (b) can be added after heat treatment in the presence of peroxide, but this is not preferred because it causes bleed-out. Component (b) preferably has a weight average molecular weight of 100 to 2,000.

Component (c) Peroxide crosslinked type modified e
Refining resin and / or copolymer rubber containing the same As the component (c) of the present invention, a crosslinking reaction is mainly caused by heat treatment in the presence of a peroxide, and further, a polyester-based polymer of the component (e) A compound which reacts with a hydroxyl group, a carboxylic acid group, or an amino group at the terminal of the coalesced terminal, the terminal of the polyamide-based polymer, or the terminal of the polyurethane-based polymer to reduce its fluidity can be used.
For example, polyethylene having a polymer density in the range of 0.88 to 0.94 g / cm ³ , such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene, or ethylene-propylene copolymer Maleic anhydride-modified, glycidyl methacrylate-modified, allyl glycidyl ether-modified amorphous olefin-based random copolymers such as coalesced rubbers and ethylene-propylene-non-conjugated diene copolymer rubbers object,
Oxazolyl methacrylate modified products, allyl oxazolyl ether modified products, carboxyl methacrylate modified products, allyl carboxyl ether modified products, polymethyl methacrylate graft products and the like. Among them, the above-mentioned modified products of polyethylene or ethylene-propylene copolymer rubber are preferable, and among them, the polyester-based polymer of the component (e) includes an ethylene-glycidyl methacrylate copolymer or the component (e). Polyamide-based copolymers include maleic anhydride-modified ethylene-glycidyl methacrylate.
Copolymers are particularly preferred in that an appropriate crosslinked structure and compatibility can be obtained. In the present invention, by using a peroxide-crosslinked type of modified olefin polymer,
Since the interaction between the functional group of the main chain and the component (e) occurs, an effect of improving tensile properties is produced. In the present invention, the surface of the molded product does not peel off.

For example, when the component (c) is a rubber, the Mooney viscosity and ML1 + 4 (100 ° C.) are preferably 10 to 10.
120, more preferably 40-100. If the Mooney viscosity is less than 10, rubber properties of the obtained elastomer composition are inferior. On the other hand, when the amount exceeds 120, the moldability deteriorates, and particularly, the appearance of the molded product deteriorates. Ethylene content in the copolymer is 5-5
0% by weight is suitable. Preferably it is 6 to 20% by weight, more preferably 10 to 15% by weight. When the ethylene content is less than 5% by weight, the flexibility of the obtained elastomer composition is insufficient, and when it is more than 50% by weight, the mechanical strength is reduced.

The weight average molecular weight of the peroxide crosslinked modified olefin resin and / or copolymer rubber containing the same is in the range of 50,000 to 1,000,000, and more preferably 70,000 to 500,000. preferable.
When a peroxide crosslinked type modified olefin resin having a weight average molecular weight of less than 50,000 and / or a copolymer rubber containing the same is used, the obtained elastomer composition has poor rubber-like properties. Further, the weight average molecular weight is 1,000
When the amount exceeds 000, the molding processability is deteriorated, and the appearance of the molded product is particularly deteriorated.

The amount of component (c) is 100 parts (a).
1.0 to 150 parts by weight, preferably 3.
0 to 50 parts by weight. When the amount is less than 1.0 part by weight, the compatibility of the obtained elastomer composition is insufficient, so that the mechanical properties are reduced. If it exceeds 100 parts by weight, the compression set of the obtained elastomer composition is deteriorated. Preferably, at least 1 part by weight of the amount of component (d) is blended before heat treatment in the presence of peroxide.

(D) Component Peroxide-decomposable olefin
Ingredient Resin and / or Copolymer Containing It The component (d) of the present invention has an effect of improving the rubber dispersion in the obtained composition and improving the appearance of a molded article. The amount of component (d) is 10 to 150 parts by weight, preferably 25 to 100 parts by weight, per 100 parts by weight of component (a). When the amount is less than 10 parts by weight, the moldability of the obtained elastomer composition is deteriorated, and when it exceeds 150 parts by weight, the flexibility and rubber elasticity of the obtained elastomer composition are deteriorated.

The peroxide-decomposable olefin resin suitable as the component (d) of the present invention has a rrrr / l-mm in pentad fraction by ¹³ C-nuclear magnetic resonance absorption method.
mm is 20% or more, and the melting peak temperature (Tm) determined by differential scanning calorimetry is 150 ° C. or more and the melting enthalpy (ΔHm) is 100 J / g or less. Preferably, Tm is 150 ° C to 167 ° C, ΔH
m is in the range of 25 mJ / mg to 83 mJ / mg. The crystallinity can be estimated from Tm and ΔHm. When Tm and ΔHm are out of the above ranges, the rubber elasticity of the obtained elastomer composition at 100 ° C. or higher is not improved.

The peroxide decomposable olefin resin is preferably used in combination of the following two types. The peroxide-decomposable olefin-based resin to be added before the crosslinking reaction is a high-molecular-weight homopolypropylene, for example, isotactic polypropylene or propylene, and another small amount of α-olefin, for example, ethylene, 1-butene, 1-hexene, A copolymer with -methyl-1-pentene or the like is preferred. The MFR of the resin (ASTM-D-1238, L
Condition, 230 ° C.) is preferably 0.1 to 10 g / 10
Min, more preferably 3 to 8 g / 10 min.

The peroxide-decomposable olefin resin to be added after the crosslinking reaction may be at least one of block, random, and homo-type PP having good fluidity, such as isotactic polypropylene, or propylene and a small amount of other α-olefin such as ethylene. , 1-butene, 1-hexene,
Copolymers with 4-methyl-1-pentene and the like are preferred.
The MFR of the resin is preferably 5 to 200 g / 10 minutes,
It is more preferably from 8 to 150 g / 10 minutes, and still more preferably from 10 to 100 g / 10 minutes.

If the MFR of the peroxide-decomposable olefin-based resin is less than 0.1 g / 10 minutes, the moldability of the obtained elastomer is reduced.
When the FR exceeds 10 g / 10 minutes, the rubber elasticity of the obtained elastomer composition deteriorates, which is not preferable.

When blended after the crosslinking reaction, if the MFR of the peroxide-decomposable olefin-based resin is less than 5 g / 10 minutes, the moldability of the obtained elastomer is reduced and the MFR is reduced.
If it exceeds 200 g / 10 minutes, the rubber elasticity of the obtained elastomer composition is undesirably deteriorated.

In addition, the number average molecular weight (Mn) is 25,
A boiling heptane-soluble polypropylene having a weight-average molecular weight (Mw) and a number-average molecular weight (Mn) of 7 or less and a melt index of 0.1 or less.
A peroxide-decomposable olefin resin composed of boiling heptane-insoluble polypropylene of 1 to 4 g / 10 min, a boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more, and an intrinsic viscosity [η] of 0.5 to 0.5 9.0d
A peroxide-decomposable olefin-based resin consisting of 1 / g of boiling heptane-insoluble polypropylene can also be used.

In the present invention, at least a part, preferably at least 3 parts by weight, of component (d) is subjected to a heat treatment in the presence of an organic peroxide, and the remainder of component (d), preferably at least 5 parts by weight, It is desirable to be blended after the heat treatment. By dividing and adding the component (d) in this way, each component is uniformly dispersed, so that the stickiness on the surface of the molded article is eliminated and the moldability is improved.

The ratio of the amount (X) to be added before the crosslinking reaction and the amount (Y) to be added after the crosslinking reaction is preferably set to satisfy X <Y because a resin having more excellent rubber elasticity can be obtained. The above addition ratios X and Y can be determined by respective final molding methods such as injection molding and extrusion molding.

(E) Component Polyester-based polymer and
Polymer, polyamide-based polymer and copolymer, or polyurethane
Rethane-based polymer and copolymer Polyester-based polymer and copolymer, polyamide-based polymer and copolymer, or polyurethane-based polymer and copolymer that can be used as component (e) of the present invention include:
There is no particular limitation, and any polymer or copolymer can be used satisfactorily. The copolymer may be a block copolymer or a graft copolymer. It preferably has elastomeric properties. Commercially available polymers mentioned above can also be used satisfactorily. Particularly preferred are the above-mentioned copolymers. Further, the above polymers or copolymers may be used alone or in combination. For example, as the polyester-based polymer and copolymer, the hard component is an aromatic polyester, the soft component is an aliphatic polyether, the hard component is an aromatic polyester, the soft component is an aliphatic polyester, and the hard component is polybutylene naphthalate. The (co) polymer whose soft component is composed of an aliphatic polyether can be mentioned. Examples of the polyamide polymer and the copolymer include 6-nylon and 6,6.
6-nylon, 4,6-nylon, 6,10-nylon or 6,12-nylon and a hard component of polyamide and a soft component of polyether or a hard component of polyamide and a soft component of polyetherester (polyamide 6 -Amide-based or 12-amide-based polyamide), and the polyurethane-based polymer and copolymer include lactone-based, ester-based, or ether-based (co) polymer. Can be.

The amount of component (e) is 100 parts (a)
1.0 to 1200 parts by weight, preferably 1 part by weight
It is 00 to 500 parts by weight. When the amount exceeds 1200 parts by weight, the flexibility of the obtained elastomer composition is reduced, and there is no much difference from a polyester-based polymer, a polyamide-based polymer or a polyurethane-based polymer alone. The oil resistance and stain resistance of the resulting elastomer composition are dramatically improved.

(F) Component Hydrogenated Petroleum Resin A hydrogenated petroleum resin can be blended if necessary. When a hydrogenated petroleum resin is blended, there is an effect that the flexibility and stickiness are well-balanced, and although there is flexibility, there is no stickiness. As the hydrogenated petroleum resin used in the present invention, hydrogenated petroleum resin, for example, hydrogenated aliphatic petroleum resin, hydrogenated aromatic petroleum resin, hydrogenated copolymer petroleum resin and hydrogenated alicyclic petroleum resin, And hydrogenated terpene-based resins. The hydrogenated petroleum resin is obtained by hydrogenating a petroleum resin produced by a conventional method by a conventional method. The petroleum resin is a petroleum refinery, a resinous substance obtained in various steps of the petrochemical industry, or those steps, particularly by copolymerizing an unsaturated hydrocarbon obtained in a naphtha decomposition step as a raw material. The obtained resin is referred to. Include, for example, aliphatic petroleum resins to the C ₅ fraction as a main raw material, aromatic petroleum resin a C ₉ fraction as a main raw material, those copolymerized petroleum resins, and alicyclic petroleum resin be able to. Preferred hydrogenated petroleum resins are hydrogenated alicyclic petroleum resins, and among them, those obtained by copolymerizing a cyclopentadiene compound and a vinyl aromatic compound and hydrogenating them are particularly preferable.

The hydrogenated petroleum resin used in the present invention is preferably completely hydrogenated. Those partially hydrogenated tend to be inferior in thermal stability and weather resistance. The amount of the hydrogenated petroleum resin is 0% based on 100 parts by weight of the component (a).
１００100 parts by weight. When the amount exceeds 100 parts by weight, not only the obtained composition is hardly softened, but also the characteristics of the petroleum resin as a tackifier become remarkable, and the mechanical properties of the composition deteriorate. Further, when a non-hydrogenated petroleum resin is used, the thermal stability of the obtained composition is poor and the object of the present invention cannot be achieved.

(G) Component Inorganic Filler An inorganic filler can be blended as required. This filler has the effect of improving some physical properties such as compression set of the molded article, and has the economical advantage of increasing the amount. Conventional inorganic fillers can be used satisfactorily, for example, calcium carbonate, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, carbon black, etc. There is. Of these, calcium carbonate or talc is particularly preferred. The amount of the inorganic filler is 0 to 100 parts by weight, preferably 0 to 60 parts by weight, based on 100 parts by weight of the component (a). If the amount exceeds 100 parts by weight, the mechanical strength of the obtained elastomer composition is remarkably reduced, and the hardness is increased, so that flexibility is lost, and a rubbery product cannot be obtained.

Organic peroxide Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di- (te
rt-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis ( tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-
Examples thereof include chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

Of these, 2,5-dimethyl-2,5-di- (te) is preferred in terms of odor, coloring and scorch stability.
Most preferred are rt-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene.

The amount of peroxide added is preferably in the range of 0.1 to 3.0 parts by weight, more preferably 100 parts by weight of the composition comprising components (a) to (g) at the time of peroxide addition. Is 0.5 to 2.5 parts by weight, more preferably 0.8 to 2.5 parts by weight. 0.
If the amount is less than 1 part by weight, the required crosslinking cannot be obtained. 3.
If the amount exceeds 0 parts by weight, the crosslinking proceeds excessively, and the dispersion of the crosslinked product becomes poor.

In the process for producing the thermoplastic elastomer composition of the present invention, a polyfunctional vinyl monomer such as divinylbenzene or triallyl cyanurate, or ethylene glycol dimethacrylate or diethylene glycol Mixing a polyfunctional methacrylate monomer such as methacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, or diallyl ester of orthophthalic acid, isophthalic acid, or terephthalic acid as a crosslinking aid. Can be. With such a compound, a uniform and efficient crosslinking reaction can be expected.

In particular, in the present invention, when triethylene glycol dimethacrylate and diallyl phthalate are used in combination, it is easy to handle and the peroxide-crosslinked modified olefin polymer rubber of component (c) which is the main component of the article to be treated Has good compatibility with the polyester copolymer of component (e) and has a peroxide solubilizing effect, and acts as a peroxide dispersing agent, so that the crosslinking effect by heat treatment is uniform and effective. It is most preferable because a crosslinked thermoplastic elastomer having a good balance between hardness and rubber elasticity can be obtained.

Crosslinking agent The amount of the crosslinking aid used in the present invention ranges from 0.1 to 10 parts by weight based on 100 parts by weight of the composition comprising components (a) to (f) at the time of addition. It is more preferably 1.0 to 8 parts by weight, and more preferably 2 to 8 parts by weight.
6 parts by weight. The addition amount of the crosslinking assistant is preferably about 2 to 2.5 times the addition amount of the peroxide. If the amount is less than 0.1 part by weight, required crosslinking cannot be obtained. If the amount exceeds 10 parts by weight, the crosslinking efficiency decreases.

Antioxidants The optional antioxidants include 2,6.
-Di-tert-p-butyl-p-cresol, 2,6
Phenolic antioxidants such as di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4-dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Agents, phosphite antioxidants and thioether antioxidants. Among them, phenolic antioxidants and phosphite antioxidants are preferred.

The amount of the antioxidant added is based on 100 parts by weight of the composition comprising components (a) to (f) at the time of addition.
The range is preferably 3 parts by weight or less, more preferably 1 part by weight or less. The antioxidant is preferably added to the first step of the production method described below in order to prevent hydrolysis resistance such as TPEE.

The mixing ratio of the components (a) to (g) is arbitrarily determined in consideration of the degree of crosslinking which particularly affects the quality of the obtained thermoplastic elastomer composition.

[Production Method] As a means for heat treatment and compounding in the method for producing the resin composition of the present invention, a conventional method can be used satisfactorily. For example, the following 3
It can be manufactured by a process, but is not limited to this.

In the first step, component (a), component (b), at least part of component (c), at least part of component (d) and at least part of component (e), and optionally, Component (f), antioxidant, light stabilizer, colorant,
Various additives such as a flame retardant and a component (g) are melt-kneaded in advance. As the kneading method, a method usually used for rubber, plastics and the like can be used satisfactorily. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, various kneaders and the like are used. By this step, a composition in which each component is uniformly dispersed can be obtained.

In the second step, a peroxide and, if desired, a crosslinking aid are added to the composition obtained in the first step, and the mixture is further kneaded under heating to cause crosslinking. As described above, it is particularly preferable that the components (a) to (g) are melt-kneaded in advance to cause micro-dispersion, and then the organic peroxide is added to cause cross-linking.
This step can be generally performed by kneading using a twin-screw extruder, a Banbury mixer, or the like. The first and second steps may be a single step, and the components may be mixed and melt-kneaded.

In the third step, the remaining component (c), the remaining component (d) and the remaining component (e), if any, are added to the crosslinked composition obtained in the second step. In addition, knead. The kneading can be generally performed using a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, various kneaders, or the like. In this step, the reaction is completed at the same time as the dispersion of each component further proceeds.

As a kneading method, it is preferable to use a twin-screw extruder or a Banbury mixer having an L / D of 47 or more, since all the steps can be performed continuously. Further, for example, when kneading with a twin-screw extruder, the rotation speed of the screw is 80 to 250 rpm, preferably 80 to 100 rpm.
When the reaction is performed under the condition of m, each component has good dispersion and good physical properties can be obtained.

The kneading temperature is desirably set in the first step so that each component is completely melted and easily mixed. In the second step, an organic peroxide,
It is desirable to set the temperature so that a shear force is applied to each component and the reaction proceeds uniformly. In the third step, it is desirable to set the temperature so that the reaction is completed at the same time as the mixing of the components proceeds.

The component (a) must be blended in the first step or at the latest in the second step. Thereby, a part of the component (a) causes a crosslinking reaction, and as a result, an effect is obtained that the dispersibility of each component is improved. Component (b) and component (f) are preferably blended in the first step.
If the components (b) and (f) are blended in the third step, they cause bleed-out, stickiness and deterioration of physical properties, which is not preferable. Component (c) can be compounded in its entirety in the first step, but in order to adjust processing characteristics, flowability, mechanical strength, etc., an appropriate amount is mixed in the first step and the remaining amount is adjusted in the second or third step. It can be blended in the process. In the latter case, when the component (e) is blended in the third step, the composition partially crosslinked in the presence of the peroxide and a part of the component (c) blended in the second or third step are compatible with each other. Microdispersed in the composition,
It is preferable because it has the effect of improving the physical properties such as mechanical strength of the obtained elastomer composition. When component (e) is not blended in the third step, it is preferable to blend an appropriate amount of component (c) in the first step. As described above, the component (d) is preferably blended in an appropriate amount in the first step and the remaining amount in the third step. As a result, the composition partially crosslinked in the presence of the peroxide and a part of the component (d) blended in the third step are compatible with each other and microdispersed in the composition. This has the effect of improving physical properties such as properties and mechanical strength. The inorganic filler can be blended in one or both of the first step and the third step.

The degree of crosslinking of the thermoplastic elastomer composition obtained by crosslinking as described above can be represented by the gel fraction and the dynamic elastic modulus. The gel fraction was 100 g for 1 g of the sample.
After wrapped in a mesh wire mesh and extracted in boiling xylene using a Soxhlet extractor for 10 hours, it can be expressed by the ratio of the weight of the residual solid content to 1 g of the sample. The dynamic elastic modulus can be represented by a storage elastic modulus of melt viscoelasticity using a parallel plate. In the present invention, the preferred degree of cross-linking, 30-45% by weight gel fraction, in particular 35 to 45% by weight, in the storage elastic modulus 10 ⁵ ~10 ⁷ Pa. Below this range, the resulting thermoplastic elastomer composition has poor high-temperature compression set and oil resistance. If the ratio exceeds this range, the flexibility is lost, and the moldability deteriorates, and at the same time, the tensile properties decrease.

Since the thermoplastic elastomer composition thus obtained has a more uniform micro-dispersion of each component than the composition obtained by the prior art, physical properties such as compression set, tensile strength and the like are lower. It is a stable and good composition.

[0063]

The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The amounts in the table mean parts by weight unless otherwise specified. The evaluation method used in Examples and Comparative Examples was as follows. 1) Hardness: JIS K6301, JIS S6050
6.3 mm pressure press sheet was used for the test piece. 2) Tensile strength: According to JIS K 6301, a test piece was prepared by punching a 1 mm thick pressed sheet into a No. 3 die using a dumbbell. The tensile speed was 500 mm / min. 3) Tensile elongation: According to JIS K 6301, a test piece was prepared by punching a 1 mm thick pressed sheet into a No. 3 die using a dumbbell. The tensile speed was 500 mm / min. 4) 100% elongation stress: According to JIS K 6301, a test piece was prepared by punching a 1 mm thick pressed sheet into a No. 3 die using a dumbbell. The tensile speed was 500 mm / min. 5) Rebound resilience: A press sheet having a thickness of 4 mm was used as a test piece in accordance with BS903. 6) Compression set: According to JIS K 6262, a 6.3 mm-thick press sheet was used as a test piece. 120
The measurement was performed under the conditions of ° C × 72 hours, 150 ° C × 22 hours, and 25% deformation. 7) Tear strength: According to JIS K 6301, a test piece was prepared by stamping a 2.5 mm-thick press sheet into a B-shape with a dumbbell. The tensile speed was 500 mm / min. 8) Oil resistance: According to JIS K 6301, a test piece was prepared by punching a 1 mm thick press sheet into a No. 3 die using a dumbbell. Using ASTM No. 2 oil, 120 ° C x 72
The change in weight after soaking for 30 hours and the change in weight after soaking in 30 ° C. × 168 hours were measured. 9) Stain resistance: A 1 mm thick press sheet was used as a test piece in accordance with JIS K6902. The contaminated material was shoe ink, washed with water after 23 ° C. × 24 hours, and the discolored state was visually checked. 10) Formability: 8.5 mm x 5 with an 80 ton injection molding machine
A sheet having a thickness of 3 mm × 3 mm was molded under predetermined conditions, and when there was no delamination or deformation and no flow mark that significantly deteriorated the appearance, the moldability was determined to be good. 11) Stickiness: When no bleeding or bloom of a low molecular weight substance was observed in the above molded product and there was no stickiness even when touched by hand, it was determined that stickiness was good.

The following were used as each component. Component (a): hydrogenated block copolymer Septon 4077 manufactured by Kuraray Co., Ltd. Styrene content: 30% by weight Isoprene content: 70% by weight Number average molecular weight: 260,000 Weight average molecular weight: 320,000 Molecular weight distribution: 1 .23 Hydrogenation rate: 90% or more Component (b): non-aromatic rubber softener Diana Process Oil PW-90 manufactured by Idemitsu Kosan Co., Ltd. Type: paraffinic oil Weight average molecular weight: 540 Content of aromatic component: 0. 1% or less Component (c): Peroxide crosslinked type modified olefin resin PE-1 BondFast BF-E manufactured by Sumitomo Chemical Co., Ltd. Type: Epoxy copolymer containing epoxy group MFR: 3 g / 10 minutes PE-2 BondFast manufactured by Sumitomo Chemical Co., Ltd. 7L Type: Epoxy group-containing ethylene copolymer MFR: 3 g / 10 minutes Component (d): Peroxide Decomposable olefinic resin PP-1 Mitsui Petrochemical Co. CJ700 Type: PP MFR: 7 g / 10 min used in the first step of Example 5 and Comparative Examples 1 and 2. PP-2 TPO E2640 manufactured by Idemitsu Petrochemical Co., Ltd. Type: low crystalline polypropylene MRF: 2.5 g / 10 min Used in the first step of Examples 6 to 10 and Comparative Examples 3 to 12. PP-3: BC03B manufactured by Mitsubishi Yuka Co., Ltd. Type: PP MFR: 30 g / 10 min Used in the third step of Examples 1 to 10, Comparative Examples 1 to 7 and 9 to 12. Component (e): Polyester-based elastomer, polyamide-based elastomer or polyurethane-based elastomer TPEE-1 4047 manufactured by Toray DuPont Type: polyester-based elastomer TPAE-1 2533SA01 manufactured by ATOCHEM Company: polyamide-based elastomer TPUE-1 Nippon Milactran company Ltd. E190 type: polyurethane elastomer - component (f): hydrogenated petroleum resin Idemitsu Petrochemical Aimabu P-140 type: hydrogenated petroleum resin C ₅ - aromatic copolymer hydrogenated resin component (g): inorganic filler RS400 manufactured by Sankyo Seiko Co., Ltd. Type: calcium carbonate Peroxide: 14 manufactured by Nippon Yushi Co., Ltd. Type: 1,3-bis (t-butylperoxyisopropyl) benzene Crosslinking assistant: NK ester 3G manufactured by Shin-Nakamura Chemical Co., Ltd. : Trietile Diglycol dimethacrylate Daiso Co., Ltd. Daiso-Dap Monomer Type: diallyl phthalate monomer Antioxidant: Asahi Denka Co., Ltd. PEP-36 Chiba Geigi Ir-1010

Production Method In the first step, components (a) to (c), part of component (d), component (e), component (f), inorganic filler and antioxidant were kneaded. In the second step, the peroxide and the crosslinking aid were kneaded with the above kneaded product. In the third step, the kneaded product and the remainder of component (d) were kneaded. In each of the first, second, and third strokes, the twin-screw kneader was operated at the following temperature at a screw rotation speed of 100 rpm. First step: 230-240 ° C Second step: 180-220 ° C Third step: 200-220 ° C

Example 1 A resin composition was prepared by blending the components in the amounts shown in Table 1. Table 1 shows the results. The resin composition of the present invention has excellent mechanical properties, oil resistance, stain resistance, and stickiness.

(Comparative Examples 1-2) Component (e) according to the present invention
Comparative Example 1 in which no polyester-based polymer, polyamide-based polymer or polyurethane-based polymer was used, and Comparative Example 2 in which the amount of the component (e) exceeded the range of the present invention was performed. Table 1 shows the results. In Comparative Example 1 in which the component (e) was not used, oil resistance and stain resistance were poor. On the other hand, in Comparative Example 2 in which the component (e) exceeds the range of the present invention, the composition becomes hard and the moldability is poor.

(Examples 2 and 3) In Examples 2 and 3,
The amount of component (e) was changed from that of Example 1. Table 2 shows the amounts and results of the components. As in Example 1, good results were obtained.

(Examples 4 and 5) In Examples 4 and 5,
Component (c) was further compounded in addition to the resin used in Example 1. In Example 4, a polyamide-based copolymer was used as the component (e), and in Example 5, a polyurethane-based copolymer was used. Table 2 shows the amounts and results of the components. As in Example 1, good results were obtained.

Example 6 In Example 6, hydrogenated petroleum resin (f), which is an optional component of the present invention, was further used. Table 3 shows the amounts of the components and the results. Excellent mechanical properties, oil resistance, stain resistance and stickiness.

Comparative Example 3 In Comparative Example 3, the amount of the component (f) according to the present invention was larger than the range of the present invention. Table 3 shows the amounts of the components and the results. The mechanical properties, oil resistance and stain resistance were poor, and the molded product became sticky.

(Examples 7 and 8) In Examples 7 and 8,
The amount of the component (f) hydrogenated petroleum resin was changed from that in Example 6. Table 3 shows the amounts of the components and the results. As in Example 6, good results were obtained.

(Comparative Examples 4 and 5) Comparative Example 4 in which no component (c) peroxide-crosslinked modified olefin resin according to the present invention was used, and Comparative Example 5 in which the amount of component (c) exceeded the range of the present invention was carried out. . Table 4 shows the amounts and results of the components. In Comparative Example 4, tensile elongation, oil resistance and stain resistance are poor. On the other hand, in Comparative Example 5, compression set, oil resistance and stain resistance are poor.

Comparative Examples 6 and 7 The amount of the component (b) softener for non-aromatic rubber according to the present invention was made smaller in Comparative Example 6 than in the range of the present invention, while it was increased in Comparative Example 7. Table 4 shows the amounts and results of the components. In Comparative Example 6, a torque abnormality and a resin pressure abnormality occurred during manufacturing, and both press molding and injection molding could not be performed. In Comparative Example 7, the mechanical properties, oil resistance, and stain resistance were poor, and the molded product was sticky.

(Comparative Examples 8 and 9) The amount of the component (d) peroxide decomposable olefin resin according to the present invention was
From the scope of the present invention, the number was reduced in Comparative Example 8 while the number was increased in Comparative Example 9. Further, in Comparative Example 8, the component (d) was not blended in the third step. Table 5 shows the amounts of the components and the results. In Comparative Example 8, torque abnormality and resin pressure abnormality occurred during production, and both press molding and injection molding could not be performed. In Comparative Example 9, the resin composition became hard and the rubber elasticity was lost.

Comparative Example 10 In Comparative Example 10, the amount of the component (g) inorganic filler, which is an optional component of the present invention, was larger than the range of the present invention. Table 5 shows the amounts of the components and the results.
Poor mechanical properties, oil resistance and stain resistance.

(Examples 9 and 10) The amounts of the organic peroxide and the crosslinking aid to be mixed in the second step were changed from those in Example 7. Table 6 shows the amounts of the components and the results. As in Example 7, good results were obtained.

Comparative Examples 11 and 12 In Comparative Example 11, no organic peroxide and no crosslinking aid were used, while in Comparative Example 12, the amounts of the organic peroxide and the crosslinking aid were extremely large. Table 6 shows the amounts of the components and the results. In Comparative Example 11, the rubber elasticity was deteriorated, the oil resistance and the stain resistance were poor, and the obtained molded product was sticky. In Comparative Example 12, torque abnormality and resin pressure abnormality occurred during production, and both press molding and injection molding could not be performed.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

[Table 6]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification symbol FI C08L 75/04 C08L 75/04 77/00 77/00 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 53 / 02 C08K 5/01 C08L 23/00 C08L 57/02 C08L 67/02 C08L 75/04 C08L 77/00

Claims (12)

(57) [Claims] 1. A block copolymer comprising (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, and And / or 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the same (b) 20 to 300 parts by weight of a softening agent for non-aromatic rubber (c) carboxyl group, acid anhydride, epoxy group or oxy group
Peroxide-crosslinked modified olefin resin modified by sazonyl group , and / or copolymer rubber containing the same 1.0 to 150 parts by weight (d) peroxide decomposed olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing the same (e) at least one selected from the group consisting of polyester-based polymers and copolymers, polyamide-based polymers and copolymers, and polyurethane-based polymers and copolymers Elastomer composition containing 1.0 to 1200 parts by weight of two polymers 2. The thermoplastic elastomer resin composition according to claim 1, further comprising (f) 100 parts by weight or less of a hydrogenated petroleum resin. 3. The thermoplastic elastomer resin composition according to claim 1, further comprising (g) 100 parts by weight or less of an inorganic filler. 4. The composition according to claim 1, further comprising 0.1 to 10 parts by weight of a crosslinking aid which is a monomer having an ethylenically unsaturated group.
4. The thermoplastic elastomer resin composition according to any one of items 1 to 3. 5. A block copolymer comprising: (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound; and And / or 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the same (b) 20 to 300 parts by weight of a softening agent for non-aromatic rubber (c) carboxyl group, acid anhydride, epoxy group or oxy group
Peroxide-crosslinked modified olefin resin modified by sazonyl group , and / or copolymer rubber containing the same 1.0 to 150 parts by weight (d) peroxide decomposed olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing the same (e) at least one selected from the group consisting of polyester-based polymers and copolymers, polyamide-based polymers and copolymers, and polyurethane-based polymers and copolymers A thermoplastic elastomer resin composition comprising 1.0 to 1200 parts by weight of one polymer, wherein at least one of component (a), component (b), component (c) and at least one of component (d) And at least part of the component (e) are heat-treated in the presence of an organic peroxide to form a crosslink, and then the crosslinked product and the remaining components (c), (d) and (e), if any, A method for producing a thermoplastic elastomer resin composition, characterized by blending the remainder. 6. The method for producing a thermoplastic elastomer resin composition according to claim 5, further comprising (f) 100 parts by weight or less of a hydrogenated petroleum resin before the heat treatment. 7. The method for producing a thermoplastic elastomer resin composition according to claim 5, wherein (g) 100 parts by weight or less of an inorganic filler is further added at an optional stage. 8. A composition according to claim 5, wherein at least 3 parts by weight of the component (d) are subjected to a heat treatment in the presence of an organic peroxide, and at least 5 parts by weight are added after the heat treatment.
7. The method for producing a thermoplastic elastomer resin composition according to any one of items 7 to 7. 9. The method for producing a thermoplastic elastomer resin composition according to claim 5, wherein at least 1 part by weight of the component (c) is subjected to the heat treatment. 10. The method for producing a thermoplastic elastomer resin composition according to claim 5, wherein at least 10 parts by weight of the component (e) is subjected to the heat treatment. 11. The cross-linking is carried out in the presence of a cross-linking aid which is a monomer having an ethylenically unsaturated group.
10. The method for producing a thermoplastic elastomer resin composition according to any one of 10 above. 12. The method according to claim 1, wherein the organic peroxide is 0.1 to
The method for producing a thermoplastic elastomer according to any one of claims 5 to 11, wherein the amount is 4.0 parts by weight.