JPH09278979A - Thermoplastic elastomer resin composition and method for producing the same - Google Patents

Abstract

(57) [Abstract] (Correction) [PROBLEMS] A thermoplastic elastomer resin composition that is highly flexible and is excellent in heat distortion resistance, mechanical strength, oil resistance, molding processability, and scratch resistance. SOLUTION: (a) a block copolymer mainly composed of a vinyl aromatic compound and a conjugated diene compound, and / or 100 parts by weight of a hydrogenated block copolymer thereof, (b) a softening agent for a non-aromatic rubber 40 to 300 parts by weight, (c) peroxide cross-linking olefin resin, and / or copolymer rubber containing the same 1.0 to 100 parts by weight, (d) peroxide decomposing olefin resin, and / or it 10 to 150 parts by weight, (e) 1 to 30 parts by weight of polyester-based thermoplastic elastomer, (f) silicone having a weight average molecular weight of 70,000 or more
0.5 to 10 parts by weight and / or perfluoroalkyl group-containing compound 0.1 to 3 parts by weight, (g) straight silicone oil having a weight average molecular weight of 50,000 or less 1 to 20 parts by weight

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer resin composition having excellent flexibility, heat deformation resistance, mechanical strength, oil resistance, molding processability and scratch resistance, and a method for producing the same. is there.

[0002]

2. Description of the Related Art In recent years, a thermoplastic elastomer resin, which is a rubber-like material and does not require a vulcanization step and has a moldability similar to that of a thermoplastic resin, has been used in automobile parts, home electric appliance parts, wire coatings, and footwear. , Is attracting attention in fields such as sundries.

As such a thermoplastic elastomer resin, various types of polymers such as polyolefin type, polyurethane type, polyester type, polystyrene type and polyvinyl chloride type have been developed and are now on the market.

Of these, styrene-butadiene-
Polystyrene-based thermoplastic elastomer resins such as block copolymers (SBS) and styrene-isoprene-block polymers (SIS) are highly flexible, have good rubber elasticity at room temperature, and are thermoplastic elastomer resins obtained from them. The composition has excellent processability.

However, since these polymers have a double bond as a conjugated diene block in the molecule, there are problems in heat aging resistance (heat stability) and weather resistance.

In order to solve this, hydrogenation is carried out on the intramolecular double bond of the block copolymer of styrene and a conjugated diene, whereby an elastomer resin composition having improved thermal stability can be obtained.

Several proposals have been made for thermoplastic elastomer resin compositions using these hydrogenated products, for example, JP-A-50-14742 and JP-A-52-1.
No. 26551 can be cited. And
As an improved method thereof, for example, Japanese Patent Laid-Open No. 58-13203.
No. 2, JP-A-58-145751, JP-A-SHO-5
9-53548, JP-A-59-131613, JP-A-62-48757, and the like, hydrocarbons and α-olefin polymer resins are added to hydrogenated styrene / conjugated diene-block copolymers. A blended composition or a method for producing the same is disclosed.

However, the conventional thermoplastic elastomer resin compositions using these hydrogenated block copolymers have problems in heat distortion resistance, such as heat-press deformation ratio (compression set) and rubber elasticity at high temperature. It was

In order to improve this point, a crosslinkable composition obtained by silane-modifying a composition containing a hydrogenated derivative of such a block copolymer, or a hydrogenated derivative of such a block copolymer. A cross-linked product obtained by cross-linking a composition containing the above in the presence of organic peroxide has been proposed. For example, JP-A-59-6236, JP-A-62-57662, and JP-B-3- 49
927, Japanese Patent Publication No. 3-11291, Japanese Patent Publication No. 3-5838
1 and Japanese Patent Publication No. 6-13628.

However, the crosslinked compositions of hydrogenated block copolymers disclosed by these proposals still have insufficient compression set at high temperature, especially at 100 ° C., and have been conventionally required for vulcanized rubber applications. The current level is that the performance level has not been reached. For example, good workability cannot be obtained and mechanical strength is lowered.

The compositions obtained by these proposals are
The current situation is that the use of an organic peroxide causes stickiness on the surface of a molded article of the composition due to decomposition of the peroxide-decomposable polymer during compounding, which is not preferable in practical use.

The compositions obtained by these proposals are
It is clearly inferior to PVC and TPU in that it is easily scratched. Therefore, in most cases, by adding a lubricant,
It reduces the dynamic friction coefficient and improves scratch resistance. It can also be coated with an ultra high molecular weight polyethylene layer, or 2
Some of them are color-molded to improve the scratch resistance of the thermoplastic elastomer (JP-A-5-4522 and JP-A-7-40508). However, the thermoplastic elastomer composition disclosed therein is inferior in versatility because it requires a special molding method.

Further, there is also one which exhibits slidability by blending ultra-high molecular weight polyethylene (JP-A-1-
No. 313548, Japanese Patent Publication No. 7-81042). However, the thermoplastic elastomer composition disclosed therein has a low degree of freedom in hardness, is inferior in compression set and oil resistance at high temperatures.

[0014]

The present invention provides (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component. Block copolymer consisting of and / or hydrogenated block copolymer obtained by hydrogenating the same 100 parts by weight (b) Softener for non-aromatic rubber 20 to 300 parts by weight (c) Peroxide cross-linking type Olefin resin, and /
Or copolymer rubber containing it 1.0 to 100 parts by weight (d) Peroxide decomposition type olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing it (e) 1 to 30 parts by weight of a polyester-based thermoplastic elastomer (f) 0.5 to 10 parts by weight and / or par of silicone having a weight average molecular weight of 70,000 or more Fluoroalkyl group-containing compound 0.1 to 3 parts by weight (g) A thermoplastic elastomer resin composition containing 1 to 20 parts by weight of straight silicone oil having a weight average molecular weight of 50,000 or less.

The present invention also includes (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component,
1. A block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the same.
00 parts by weight (b) 20 to 300 parts by weight of a non-aromatic softening agent for rubber (c) peroxide cross-linking olefin resin, and / or
Or copolymer rubber containing it 1.0 to 100 parts by weight (d) Peroxide decomposition type olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing it (e) 1 to 30 parts by weight of a polyester-based thermoplastic elastomer (f) 0.5 to 10 parts by weight and / or par of silicone having a weight average molecular weight of 70,000 or more Fluoroalkyl group-containing compound 0.1 to 3 parts by weight (g) 1 to 20 parts by weight of straight silicone oil having a weight average molecular weight of 50,000 or less. And (b), at least part of component (c), part of component (d), and component (e), component (f)
And component (g) are heat treated in the presence of organic peroxide to crosslink, and then the crosslinked product and the rest of component (d) and the rest of component (c), if any, are blended. And a method for producing a thermoplastic elastomer resin composition.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Component Block Copolymer The component (a) of the present invention comprises at least two polymer blocks A containing a vinyl aromatic compound as a main component and a polymer block containing a conjugated diene compound as a main component. A block copolymer comprising at least one united block B, a block copolymer 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. The above (hydrogenated) block copolymer (hereinafter, the (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 vinyl aromatic compounds preferably consists of vinyl aromatic compounds only or contains more than 50% by weight of vinyl aromatic compounds, preferably more than 70% by weight (hydrogenated) conjugated diene. 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 the (hydrogenated) conjugated diene compound preferably consists only of the (hydrogenated) conjugated diene compound or is greater than 50% by weight of the (hydrogenated) conjugated diene compound, It is preferably a copolymer block of 70% by weight or more and a vinyl aromatic compound. In each of these polymer block A mainly containing a vinyl aromatic compound and polymer block B mainly containing a (hydrogenated) conjugated diene compound, a vinyl compound in the molecular chain or (hydrogenated)
Random distribution of conjugated diene compounds, tapered (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 composed of vinyl aromatic compounds or polymer blocks B mainly composed of (hydrogenated) conjugated diene compounds, they may have the same structure or different structures. It may be.

As the vinyl aromatic compound constituting the (hydrogenated) block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tertiarybutylstyrene and the like. Of these, styrene is preferred. As the conjugated diene compound, for example, one kind or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, butadiene,
Isoprene and combinations thereof are preferred.

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

The weight average molecular weight of the (hydrogenated) block copolymer used in the present invention having the above structure is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000. More preferably 1
It is in the range of 0,000 to 550,000, particularly preferably 10,000 to 400,000. The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less.

The molecular structure of the (hydrogenated) block copolymer is
It may be linear, branched, radial or any combination thereof.

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

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

Component (b) Non-aromatic Softening Agent for Rubber As the component (b) of the present invention, a non-aromatic mineral oil or a liquid or low molecular weight synthetic softening agent can be used. The mineral oil softening agent used for rubber is a mixture of three aromatic ring, naphthene ring and paraffin chain, and paraffin chain carbon number occupies 50% or more of total carbon number. That is, those having a carbon number of naphthene ring of 30 to 40% are called naphthene type, and those having an aromatic carbon number of 30% or more are called aromatic type.

The mineral oil type rubber softening agents used as the component (b) of the present invention are paraffin type and naphthene type softeners in the above categories. The aromatic softening agent is not preferable because the component (a) becomes soluble due to its use, the crosslinking reaction is inhibited, and the physical properties of the obtained composition cannot be improved.
As the component (b), a paraffinic one is preferable,
Further, among paraffins, those having a small amount of aromatic ring components are particularly preferable.

The properties of these softening agents for non-aromatic rubbers are such that the dynamic viscosity at 37.8 ° C. is 20 to 500 cS.
t, pour point is −10 to −15 ° C., flash point (COC) is 1
Indicates 70 to 300 ° C.

The blending amount of the component (b) is 100 parts of the component (a).
20-300 parts by weight, preferably 4
0 to 150 parts by weight. If the amount exceeds 300 parts by weight, bleeding out of the softening agent is likely to occur, tackiness may be imparted to the final product, and mechanical properties may be deteriorated. If the amount is less than 20 parts by weight, the moldability of the resulting composition will be lost. A part of the component (b) can be blended after the heat treatment in the presence of peroxide, but it is not preferable because it causes bleeding out. The component (b) has a weight average molecular weight of 100.
Those of ˜2,000 are preferable.

(C) Component Peroxide cross-linking type
Fin-based resin and / or copolymer rubber containing the same As the component (c) of the present invention, use should be made of one that causes a crosslinking reaction mainly by heat treatment in the presence of peroxide and reduces its fluidity. You can
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 It is an elastic body of an indeterminate random copolymer containing olefin as a main component, such as a compound rubber and an ethylene / propylene / non-conjugated diene copolymer rubber. Of these, polyethylene or ethylene / propylene copolymer rubber is preferable,
Among them, linear low-density polyethylene is particularly preferable in that an appropriate crosslinked structure can be obtained.

For example, when the component (c) is rubber, the Mooney viscosity, ML1 + 4 (100 ° C.) is preferably 10 to 10.
120, more preferably 40 to 100. When a Mooney viscosity of less than 10 is used, the rubber properties of the resulting elastomer composition are poor. Further, if the number exceeds 120, the molding processability is deteriorated, and particularly the appearance of the molded product is deteriorated.

The ethylene content in the copolymer is suitably 5 to 50% by weight. It is preferably 6 to 20% by weight, more preferably 10 to 15% by weight. When the ethylene content is less than 5% by weight, flexibility of the obtained elastomer composition is insufficient, and when it is more than 50% by weight, mechanical strength is lowered.

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

The amount of component (c) to be added is 100 parts of component (a).
1.0 to 100 parts by weight, preferably 3.
0 to 50 parts by weight. If it is less than 1.0 part by weight, the mechanical properties of the obtained elastomer composition will be deteriorated. 10
If it exceeds 0 parts by weight, the flexibility of the obtained elastomer composition is lowered and the moldability is deteriorated.

Preferably at least half of the amount of component (c), especially 3 parts by weight or more, is blended in before the heat treatment in the presence of peroxide. The balance is blended after the heat treatment, whereby various physical properties can be adjusted as described later.

(D) Component Peroxide-decomposing type
Fin-based resin and / or copolymer containing the same The component (d) of the present invention has the effects of improving the rubber dispersion in the resulting composition and improving the appearance of the molded article. The blending amount of the component (d) is 10 to 150 parts by weight, preferably 25 to 100 parts by weight, based on 100 parts by weight of the component (a). If it is less than 10 parts by weight, the moldability of the obtained elastomer composition will be deteriorated, and if it exceeds 150 parts by weight, the flexibility and rubber elasticity of the obtained elastomer composition will be deteriorated.

The peroxide-decomposable olefinic resin suitable as the component (d) of the present invention has a DS of its homo moiety.
By C measurement, Tm is 150 ° C to 167 ° C, ΔHm is 2
It is in the range of 5 mJ / mg to 83 mJ / mg. The crystallinity can be estimated from Tm and ΔHm. Tm
And, when ΔHm is outside the above range, the rubber elasticity of the obtained elastomer composition at 100 ° C. or higher is not improved.

The peroxide decomposing type olefin resin is preferably used in combination of the following two kinds.

The peroxide-decomposing type olefin resin to be blended before the crosslinking reaction is a high molecular weight homo type polypropylene such as isotactic polypropylene or propylene and a small amount of other α-olefin such as ethylene, 1-.
A copolymer with butene, 1-hexene, 4-methyl-1-pentene and the like is preferable. MFR of the resin (ASTM-D
-1238, L condition, 230 ° C) is preferably 0.1
-10 g / 10 minutes, more preferably 0.1-5 g / 10
Min, more preferably 0.1 to 3 g / 10 min. The peroxide-decomposable olefin resin blended after the crosslinking reaction is one or more of good flowable block, random or homotype PP, such as isotactic polypropylene, or propylene and a small amount of other α-olefin such as ethylene, 1- Butene, 1-hexene, 4-methyl-1
-A copolymer with pentene or the like is preferable. MFR of the resin
Is preferably 5 to 200 g / 10 minutes, more preferably 8 to 150 g / 10 minutes, still more preferably 10 to 100 g.
/ 10 minutes.

When compounded before the crosslinking reaction, if the MFR of the peroxide-decomposable olefin resin is less than 0.1 g / 10 minutes, the moldability of the obtained elastomer will be deteriorated and M
When FR exceeds 10 g / 10 minutes, the rubber elasticity of the obtained elastomer composition deteriorates, which is not preferable.

When compounded after the crosslinking reaction, if the MFR of the peroxide-decomposable olefin resin is less than 5 g / 10 minutes, the moldability of the resulting elastomer will be deteriorated and the MFR will be reduced.
Is more than 200 g / 10 minutes, the rubber elasticity of the obtained elastomer composition deteriorates, which is not preferable.

The amount of component (d) blended is 100 parts of component (a).
10-150 parts by weight, preferably 20-
80 parts by weight. If it is less than 10 parts by weight, the moldability is deteriorated, and if it exceeds 150 parts by weight, the hardness of the obtained elastomer composition becomes too high and the flexibility is lost, so that a product having a rubber-like feel cannot be obtained.

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

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

(E) Component Polyester Thermoplastic E
Rustomer As the component (e) of the present invention, polybutylene terephthalate is a main hard segment, and poly (tetramethylene oxide) glycol is a soft segment, a polyether ester block copolymer, or polybutylene terephthalate is a main hard segment, A polyester ester block copolymer having poly-ε-caprolactone as a soft segment, which does not crosslink even when heat-treated in the presence of peroxide and does not deteriorate in fluidity, can be used. The blending amount of the component (e) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, relative to 100 parts by weight of the component (a). When it exceeds 30 parts by weight, the flexibility of the obtained elastomer composition is lowered and the moldability is deteriorated. The component (e) is, in particular, Tm
Is 160 to 225 ° C., D hardness is 30 or more, and the content of the hard segment is 30 to 80%. The hard segment content is more preferably 50 to 80% or more. By blending the component (e), the oil resistance and heat resistance of the obtained elastomer composition are improved. The heat resistance referred to here is the temperature dependence of compression set and hardness.

(F) Silicone or perfluoroalkyl
The silicone group-containing compound component (f) has a weight average molecular weight of 70,000.
The silicone is 0 or more, preferably 100,000 or more. The upper limit of the molecular weight is not particularly limited, but may be any one of dimethyl-based, methylphenyl-based, methylhydrogen-based or modified silicone, which is preferably 1,000,000, and is not limited thereto. The silicone improves the moldability and molding workability of the composition, and
Improves the surface lubricity and surface gloss of molded products. For ease of handling, thermoplastics such as polyethylene,
High concentration with polypropylene and polystyrene (eg 3
Compounds of 0 to 70% by weight can be used. In particular, a compound with polyethylene is excellent in terms of effect.

The silicone is added in an amount of 0.5 to 10 parts by weight, preferably 1.5 to 5 parts by weight, based on 100 parts by weight of the component (a). Even if blended in an amount of more than 10 parts by weight, further improvement is small and stickiness occurs. Examples of perfluoroalkyl group-containing compounds include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group-containing olefin oligomers,
More preferably, it is an olefin-based oligomer containing a perfluoroalkyl group. In the case of a polymer or oligomer, it preferably has a weight average molecular weight of 2,000 to 20,000, more preferably 5,000 to 10,000. The perfluoroalkyl group-containing compound is 0.1 to 3
It is blended in an amount of parts by weight, preferably 0.1 to 1.5 parts by weight. You may use together the said silicone and a compound containing a perfluoroalkyl group.

(G) Straight silicone oil component (g) Straight silicone oil comprises component (f)
It has a lower molecular weight than silicone and a weight average molecular weight of 5,000 to 50,000, preferably 10,000 to 2
It is 0000. Dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, or modified silicone oil containing other organic groups can be used. If the molecular weight is less than 5,000, bleed-out becomes remarkable. Speaking of viscosity, 1
Those of 00-1,000 cSt are suitable. Straight silicone oil improves the surface lubricity of molded articles.

The straight silicone oil is added in an amount of 1 to 20 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts by weight of the component (a). Even if the amount is more than 20 parts by weight, the further improvement is small and the bleed-out becomes remarkable. Hydrogenated Petroleum Resin In the present invention, a hydrogenated petroleum resin can be added if necessary. Hydrogenated petroleum resin, hydrogenated petroleum resin,
Examples thereof include hydrogenated aliphatic petroleum resin, hydrogenated aromatic petroleum resin, hydrogenated copolymer petroleum resin, hydrogenated alicyclic petroleum resin, and hydrogenated terpene resin. 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 resinous material obtained in various steps of the petroleum refining industry, petrochemical industry, or copolymerization of those steps, particularly unsaturated hydrocarbons obtained in the naphtha decomposition step, as a raw material. Refers to the resin obtained. For example, C
Examples thereof include aromatic petroleum resins containing ₅ fractions as main raw materials, aromatic petroleum resins containing C ₉ fraction as main raw materials, copolymerized petroleum resins thereof, and alicyclic petroleum resins. A preferred water-added petroleum resin is a hydrogenated resin group petroleum resin, and among them, those obtained by copolymerizing a cyclopentadiene compound and a vinyl aromatic compound and hydrogenating are particularly preferable. The hydrogenated petroleum resin used in the present invention is preferably completely hydrogenated. Partially hydrogenated,
It tends to be inferior in terms of thermal stability and weather resistance. The blending amount of the hydrogenated petroleum resin is 100 parts by weight or less, preferably 10 to 80 parts by weight, relative to 100 parts by weight of the component (a). 100
When it exceeds the amount by weight, further softening of the obtained composition becomes difficult to be recognized, the characteristics of the petroleum resin as a tackifier become remarkable, and the mechanical properties of the composition deteriorate. When it is less than 10 parts by weight, softening of the obtained composition is not observed. 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.

Inorganic filler If necessary, an inorganic filler can be added. Inorganic fillers have the effect of improving some physical properties such as compression set of molded articles, and also have the economic advantage of increasing the amount.
Conventional inorganic fillers can be satisfactorily used, 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 preferable.

The amount of the inorganic filler compounded is 100% of the component (a).
0 to 100 parts by weight, preferably 0 to 6 parts by weight
0 parts by weight. When it exceeds 100 parts by weight, the mechanical strength of the obtained elastomer composition is remarkably lowered, and
It is not preferable because the hardness becomes high, the flexibility is lost, and a product having a rubber-like feel cannot be obtained.

Electron Donor An electron donor can be blended if necessary. The electron donor refers to an electron donor having an atom, an ion, or a molecule in its structure that easily gives an electron to a partner. For example, benzene,
Examples thereof include aromatic hydrocarbons such as naphthalene and their substitution products, various amines, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, alcohols, ethers, ketones, aldehydes and alcoholates. Examples of the electron-donating atom and ion include chlorine ion, fluorine ion, and iodine ion. Examples of the electron donating group include an amino group, an imino group, a hydroxyl group, a halogen group, an alkyl group and an allyl group. Examples of the electron-donating monomer include ethyleneimine.

Specific examples of the aromatic hydrocarbon include benzene, toluene, o-xylene, m-xylene, p-xylene, hemimaritin, pseudocumene, prenitene, isodulene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene and propylbenzene. ,
Styrene, cumene, mesitylene, cymene, biphenyl,
Naphthalene, anthracene, indene, phenanthrene, indane, p-terphenyl, diphenylmethane,
Examples include triphenylmethane, bibenzyl, stilbene, and tetralin.

Specific examples of the carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caponic acid, bivalic acid, acrylic acid, methacrylic acid and crotonic acid, and malon. Acid, succinic acid,
Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,
Alicyclic carboxylic acids such as 2-cyclohexanedicarboxylic acid and cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p-tertiary butyl benzoic acid, naphthoic acid, cinnamon bark Aromatic monocarboxylic acids such as acids, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, aromatic polyvalent carboxylic acids such as mellitic acid, etc. .

As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used,
Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl bivalate, isobutyl bivalate, ethyl acrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, dibutyl succinate, Diethyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, dibutyl maleate, diisobutyl maleate, dibutyl sebacate, diethyl sebacate, monomethyl maleate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tertiary butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, cinnamic acid Ethyl, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, dibutyl isophthalate, terephthalate Acid dibutyl, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, butyl trimellitate, tetramethyl pyromellitic acid, tetraethyl pyrolitate,
Examples include tetrabutyl pyromellitic acid and the like.

As the carboxylic acid halide, the acid halides of the above carboxylic acids can be used,
Specific examples thereof include acetate chloride, acetate bromide, acetate iodide, propionyl chloride, butyrate chloride,
Butyric acid bromide, butyric acid iodide, bivalic acid chloride, bivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, Adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, cyclohexanecarboxylic acid chloride, 1-cyclohexenecarboxylic acid chloride, cis-4 -Methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-tolu Acid bromide, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, isophthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid Examples include dichloride and naphthalic acid dichloride. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride and phthalic acid butyl chloride can also be used.

Alcohols are represented by the general formula ROH.
In the formula, R is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl, aralkyl or the like. Specific examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol,
Hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol,
Examples thereof include ethylphenol, isopropylphenol, p-tertiarybutylphenol, n-octylphenol and the like.

The ethers are represented by the general formula ROR '. In the formula, R and R ′ are alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl, aralkyl and the like. R and R'may be the same or different, and may form a ring together. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethylallyl ether, diallyl ether, diphenyl ether, anisole and ethylphenyl ether.
Cyclic ethers such as tetrahydrofuran, pyran and dioxane, chain ethers such as dimethoxyethane, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, 2,3-dihydrofuran,
Cyclic vinyl ethers such as 3,4-dihydro-2H-pyran, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, 2,5-dihydrofuran,
Cyclic allyl ethers such as 5,6-dihydro-2H-pyran, aliphatic amines such as triethylamine and triethylenediamine, aromatic amines such as pyridine and picoline, 2-oxazoline, 6H-1,2,4- Heterocyclic compounds such as oxadiazine may be mentioned.

In the present invention, preferred as the electron donor are toluene and methanol, and particularly preferred is toluene.

In the present invention, the above components (a) to (g) are used.
In addition to the use of an electron donor, the effect of reducing the formation of crosslinked gel in the produced thermoplastic elastomer resin composition is produced. That is, it is considered that the use of the electron donor in the present invention causes the relaxation of the crosslinking rate and produces the above effect. The compounding amount of the electron donor used in the present invention may vary depending on the electron donating ability of the electron donor used, but when compounding before the heat treatment in the presence of peroxide or during the heat treatment, it is generally 15 parts by weight or less, preferably 0.5 to 6.0 parts by weight, and more preferably 2.0 to 100 parts by weight of the component (a).
When the component (g) is heated and mixed (including melt-kneading) with the components (a) to (f) before heat treatment in the presence of peroxide, it is generally 3.0 parts by weight. 100
25 parts by weight or less based on parts by weight, preferably 1.0 to 1
0 parts by weight. Generally, if the amount exceeds the above upper limit, the molded product becomes sticky, which is not preferable. However, those having a low electron donating ability can be added in an amount exceeding 15 parts by weight. The electron donating ability can be generally represented by a chain transfer constant of a polymer radical when an electron donor is used. The chain transfer constant is
The chain transfer constant (Cs) of the styrene polymer radical at 60 ° C. when using an electron donor is 10 ⁻⁴ to 10 ⁻⁶ , though it depends on the type of polymer used, the reaction temperature, and the like.
It is preferred that For example, when toluene is used as the electron donor, the chain transfer constant of the styrene polymer radical is 1.25 × 10 ⁻⁵ .

Organic peroxide The organic peroxide used in the present invention is, for example, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (te.
rt-Butylperoxy) hexane, 2,5-dimethyl-2,5di (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-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy Examples thereof include isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.

Of these, 2,5-dimethyl-2,5-di- (ter) is preferable in terms of odor, coloring and scorch stability.
Most preferred are t-butylperoxy) hexane and 2,5-dimethyl 2,5-di- (tert-butylperoxy) hexyne-3.

The amount of peroxide added is preferably in the range of 0.1 to 3.0 parts by weight based on 100 parts by weight of the components (a) to (e) in total when the peroxide is added,
It is more preferably 0.5 to 2.5 parts by weight, and even more preferably 0.8 to 2.5 parts by weight.

Crosslinking aid In the method for producing the thermoplastic elastomer composition of the present invention, in the partial crosslinking treatment with an organic peroxide,
Divinylbenzene, polyfunctional vinyl monomers such as triallyl cyanurate, or ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,
A polyfunctional methacrylate monomer such as triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate can be added as a crosslinking aid. With such a compound, a uniform and efficient crosslinking reaction can be expected.

In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle and has good compatibility with the peroxide-crosslinking olefin polymer rubber (c) which is the main component of the treated material, In addition, it has a peroxide solubilizing effect and acts as a dispersion aid for peroxide, so the crosslinking effect by heat treatment is uniform and effective, and a crosslinked thermoplastic elastomer having a well-balanced hardness and rubber elasticity can be obtained. preferable. Furthermore, triethylene glycol dimethacrylate has good compatibility with the polyester-based thermoplastic elastomer and can suppress the peeling of the surface layer of the molded product.

The addition amount of the crosslinking aid used in the present invention is
The amount is preferably 0.1 to 10 parts by weight, more preferably 1.0 to 8 parts by weight, and still more preferably 2 to 100 parts by weight with respect to the total of 100 parts by weight of the components (a) to (e) at the time of addition. 6 parts by weight. The amount of the crosslinking aid added is preferably about 2 to 2.5 times the amount of the peroxide added.

Antioxidants Also, as the antioxidants used in some cases, 2,6
-Di-tert-p-butyl-p-cresol, 2,6-
Di-tert-butylphenol, 2,4-dimethyl-
6-tert-butylphenol, 4,4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-
Examples include phenolic antioxidants such as 5-tert-butylphenyl) butane, phosphite antioxidants and thioether antioxidants. Of these, phenol-based antioxidants and phosphite-based antioxidants are preferable.

The amount of the antioxidant added is preferably in the range of 3 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the components (a) to (e) in total. Further, the antioxidant is preferably added to the first step of the production method described later in order to prevent hydrolysis resistance such as TPEE.

The mixing ratios of the components (a) to (g), the electron donor and the crosslinking aid are arbitrarily determined in consideration of the degree of crosslinking which affects the quality of the obtained thermoplastic elastomer composition.

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

In the first step, first, the components (a) and (b), at least a part of the component (c), a part of the component (d), and the component (e), the component (f) and the component (g). ,
Optionally further hydrogenated petroleum resin, electron donor, antioxidant,
Various additives such as a light stabilizer, a colorant, and a flame retardant are melt-kneaded in advance. The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic, and the like.
A single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. By this step, a composition in which each component is uniformly dispersed can be obtained.

In the second step, peroxide and optionally a crosslinking aid are added to the composition obtained in the first step, and the mixture is kneaded with heating to cause crosslinking. In this way, it is particularly preferable that the components (a) to (g) are melt-kneaded in advance to generate a microscopic dispersion and then organic peroxide is added to cause cross-linking.
This step can be generally performed by a kneading method using a twin-screw extruder, a Banbury mixer, or the like.

In the third step, the crosslinked composition obtained in the second step is kneaded with the balance of the component (d) and the balance of the component (c), if any. The kneading can be generally performed using a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders. In this step, the reaction is completed at the same time as the dispersion of each component further progresses.

As a kneading method, it is preferable to use a twin-screw extruder having a L / D of 47 or more or a Banbury mixer because all the steps can be continuously performed. 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 rp.
Under the condition of m, each component is well dispersed and physical properties can be obtained.

In the first step, the kneading temperature is preferably set so that the respective components are completely melted and can be easily mixed. In the second step, it is desirable to apply a shearing force to the organic peroxide and each component, and set the temperature so that 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 respective components proceeds.

The component (a) needs to be blended in the first step or at the second step at the latest. As a result, a part of the component (a) undergoes a crosslinking reaction, and as a result, the dispersibility of each component is improved. JP-A-59-6
Unlike 236, as is apparent from the embodiment of the present invention,
The resin composition obtained by the method of the present invention has the effect of improving heat resistance. The component (b) is preferably blended in the first step. Blending of the component (b) in the third step causes bleed-out. The component (c) can be compounded in its entirety in the first step, but for the purpose of adjusting processing characteristics, fluidity, mechanical strength, etc.,
It is also possible to mix an appropriate amount in the first step and mix the remaining amount in the third step. In the latter case, the composition partially cross-linked in the presence of peroxide and a part of the component (c) compounded in the third step are compatible with each other and micro-dispersed in the composition to obtain a machine of the resulting elastomer composition. It is preferable because it has the effect of improving physical properties such as strength. The component (d) is, as described above,
An appropriate amount is blended in the first step and the remaining amount is blended in the third step. As a result, the composition partially cross-linked in the presence of peroxide and a part of the component (d) compounded in the third step are compatible with each other and micro-dispersed in the composition, resulting in processing characteristics and flow properties of the elastomer composition. And the physical properties such as mechanical strength are improved. Components (e), (f) and (g) are added in the first step or in the second step. The inorganic filler can be blended in either or both of the first step and the third step. The electron donor can be blended in either or both of the first step and the second step. For better function expression and effective use, it is preferable to mix in the second step. When the electron donor is compounded in the first step, the electron donor may be volatilized by melt-kneading, and therefore it is desirable to compound the electron donor in a larger amount than in the second step.

The degree of crosslinking of the thermoplastic elastomer composition obtained by crosslinking in this way can be represented by the gel fraction and the dynamic elastic modulus. The gel fraction is 100 for 1 g of sample.
It can be expressed by the ratio of the weight of the residual solid content to 1 g of the sample, after being wrapped in a mesh wire net and extracted in boiling xylene for 10 hours using a Soxhlet extractor. The dynamic elastic modulus can be expressed by the storage elastic modulus of melt viscoelasticity using a parallel plate.

In the present invention, the degree of crosslinking is a gel fraction, preferably 30 to 45% by weight, more preferably 40 to 45%.
The weight% and storage elastic modulus are preferably 105 to 107 Pa. If it is less than this range, the resulting thermoplastic elastomer composition has poor high-temperature compression set and oil resistance. On the other hand, if it exceeds this range, the moldability deteriorates, and at the same time, the tensile properties deteriorate.

The thermoplastic elastomer composition obtained in this way is better than the composition obtained by the prior art.
Since each component is uniformly micro-dispersed, the composition is stable and has good physical properties such as compression set and tensile strength.

[0078]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. 1) Hardness: JIS K 6301 and JIS S 60
According to 50, a 6.3 mm pressure press sheet was used as the test piece. 2) Tensile strength: According to JIS K 6301, a test piece was a 1 mm thick press sheet punched into a No. 3 mold with a dumbbell and used. The pulling speed was 500 mm / min. 3) Tensile elongation: Based on JIS K 6301, the test piece was a 1 mm thick press sheet punched into a No. 3 mold with a dumbbell and used. The pulling speed was 500 mm / min. 4) 100% elongation stress: Based on JIS K 6301, the test piece used was a 1 mm thick press sheet punched into a No. 3 mold with a dumbbell. The pulling speed was 500 mm / min. 5) 100% permanent elongation: Based on JIS K 6301, the test piece was a 1 mm thick press sheet punched into a No. 3 die with a dumbbell. The pulling speed was 500 mm / min. After holding for 10 minutes at the time of 100% elongation, the chuck was opened, and after leaving for 10 minutes, the length between marked lines was measured. 6) Impact resilience: In conformity with BS903, a 4 mm thick press sheet was used as the test piece. 7) Compression set: According to JIS K 6262, a 6.3 mm thick press sheet was used as a test piece. 70 ° C
It was measured under the conditions of × 22 hours, 100 ° C × 22 hours, 120 ° C × 22 hours, 140 ° C × 22 hours, and 25% deformation. 8) Dynamic friction coefficient and scratch load: A 1 mm thick press sheet was used as a test piece. A surface damage measurement was performed using a HEIDON-type surface profilometer (TYPE 14DR, Shinto Chemical Co., Ltd.), and the load at which damage was confirmed (critical load)
And the dynamic friction coefficient under a load of 200 g was measured. Relative speed: 100 mm / min Counterpart material: Sapphire needle (needle tip 50 μmΦ, 90R) Load: 0-600 g 9) Tear strength: In accordance with JIS K 6301, the test piece is a 2.5 mm thick press sheet, with a dumbbell B It was punched out and used. The tensile strength was 500 mm / min. 10) Oil resistance: Based on JIS K 6301, the test piece was a 1 mm thick press sheet punched into a No. 3 mold with a dumbbell and used. 120 ° C x 24 using ASTM No. 2 oil
Changes in weight and volume over time, residual tensile strength, and 100% elongation stress were measured.

11) Moldability: A flow of forming a 12.5 mm × 13.5 mm × 1 mm thick sheet under a predetermined condition with an injection molding machine of 120 tons without delamination or deformation and significantly deteriorating the appearance. When there was no mark, it was determined that the moldability was good. 12) Stickiness: The molded product in (11) above was considered to have good stickiness when no bleed or bloom of a low molecular weight substance was observed and there was no stickiness when touched with a hand. 13) Bleed-out property 10% with the molded product in (11) compressed 50%.
It was allowed to stand at 0 ° C. for 22 hours, then opened, and when no bleed or bloom of a low molecular weight substance was observed and there was no stickiness when touched with the hand, it was determined that the bleed-out property was good.

The following was used as each component. Component (a): Hydrogenated block copolymer Kuraray Co., Ltd. Septon 4055 Styrene content: 30% by weight Isoprene content: 70% by weight Weight average molecular weight: 130,000 Molecular weight distribution: 1.3 Hydrogenation rate : 90% or more Component (b): Softener for non-aromatic rubber Idemitsu Kosan Co., Ltd. Diana Process Oil PW-9
0 type: paraffin oil Weight average molecular weight: 540 Aromatic component content: 0.1% or less Component (c): Peroxide cross-linking olefin resin PE-1 Idemitsu Petrochemical Co., Ltd. V-0398CN Type: LLDPE Weight average molecular weight: 80,000 EP-1 Sumitomo Chemical Co., Ltd. V-0131 Type: EPR Component (d): Peroxide decomposition type olefin resin Mitsui Petrochemical Co., Ltd. CJ700 Type: PP Example 1 Used in the first and third steps of Comparative Examples 1 to 11 and the third step of Example 6 E2640 manufactured by Idemitsu Petrochemical Co., Ltd. Type: TPO Used in the first step of Example 6 Component (e): Polyester thermoplastic elastomer TPEE-1 B4010AN made by Teijin Ltd. Hard segment: Polybutylene terephthalate 40% Soft segment Component: Polyether ester type TPEE-2 Teijin Ltd. P4128AKN Hard segment: Polybutylene terephthalate 40% Soft segment: Polyester ester type TPEE-3 Teijin Ltd. P4150AKN Hard segment: Polybutylene terephthalate 75% Soft segment : Polyester / ester-based component (f): Silicone Toray Dow Corning Co., Ltd. Silicone BY27
002 (Compound of 50% by weight of dimethylpolysiloxane having a weight average molecular weight of 130,000 and 50% by weight of LDPE) Component (g): Straight silicone oil Toray Dow Corning Silicone SH20
0 (dimethylpolysiloxane having a weight average molecular weight of 17,000, viscosity of 1,000 cSt) Component: Inorganic filler Sankyo Seiko Co., Ltd. RS400 Type: calcium carbonate 10 parts by weight were compounded in all Examples and Comparative Examples. Peroxide: manufactured by NOF CORPORATION Perhexa 25B Type: 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane 2.6 parts by weight were compounded in all Examples and Comparative Examples. Crosslinking auxiliary agent: NK ester 3G manufactured by Shin-Nakamura Chemical Co., Ltd. Type: triethylene glycol dimethacrylate 5.7 parts by weight were compounded in all the examples and comparative examples. Antioxidant: PEP-36 manufactured by Asahi Denka Co., Ltd. 0.2 parts by weight was compounded in all Examples and Comparative Examples. Comparative components: Lubricant Lion Armor Co., Ltd. Armoslip CP Type: Oleylamide, mp 68-74 ° C

Manufacturing Method In the first step, the components (a) to (c), part of the component (d), the components (e) to (g), the inorganic filler, and the 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 rest of the component (d) were kneaded. In each of the first, second and third steps, the biaxial kneader was operated at the screw rotation speed of 100 rpm at the following temperature. First step: 230 to 240 ° C Second step: 180 to 220 ° C Third step: 200 to 220 ° C

Example 1 Components were used in the amounts shown in Table 1. The amount of component (f) indicates the amount of silicone only. The results are shown in Table 1. It has excellent oil resistance and scratch resistance, no stickiness and bleed-out, and good high-temperature compression set.

(Comparative Examples 1 to 4) Component (f) according to the present invention
Comparative Example 1 in which neither silicone nor (g) straight silicone oil was used, and Comparative Examples 2 to 4 in which any one of the component (f), (g) or component (e) polyester elastomer was not used were carried out. The results are shown in Table 1. The scratch resistance is inferior to that of Example 1.

(Comparative Examples 5-8) In Comparative Examples 5-7, the amount of the component (e), (f) or (g) was made larger than the range of the present invention. Table 2 shows the results. All of them are not good in moldability, stickiness or bleed-out property. In Comparative Example 8, the components (e) and (f) were not used, and instead the amount of the component (g) was doubled as compared with Example 1, but the scratch resistance was poor.

(Comparative Examples 9 to 11) In Comparative Example 9, the lubricant conventionally used for obtaining the surface lubricity of the molded product was used. The results are shown in Table 3. Bleed-out property is not good because the lubricant comes out on the surface. Comparative Examples 10 and 1
In No. 1, one or two of the components (e), (f) and (g) according to the present invention were omitted and a lubricant was used, but the bleed-out property is not good.

(Examples 2 to 6) In Examples 2 to 4, the kind of the component (e) or (c) was changed from that in Example 1. The results are shown in Table 4. Both were satisfactory results. Example 5
Then, the amounts of the component (d) in the first and third steps and the amount of the component (b) were changed from those in Example 1. Good results were obtained.

In Example 6, the component (d) added to the first step was changed from that in Example 1, and the amounts of the component (d) in the first and third steps were changed. Although it has a small hardness of 39 A, it has excellent rubber elasticity at high temperatures, oil resistance, and moldability, and has other properties.

(Examples 7 and 8 and Comparative Example 12) As the component (f), the following fluorinated oligomers were used alone or in combination with the above silicone (BY27002). Fluorinated oligomer Megafac F-178RM (Dainippon Ink and Chemicals, Inc.) (perfluoroalkyl group-containing olefin oligomer having a weight average molecular weight of 6,500) The above CJ700 was used as the component (d). Table 5 shows the results.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

[Table 5]

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Claims (8)

[Claims] 1. A block copolymer comprising (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component, and / Or hydrogenated block copolymer obtained by hydrogenating this 100 parts by weight (b) Softening agent for non-aromatic rubber 20 to 300 parts by weight (c) Peroxide cross-linking olefin resin, and /
Or copolymer rubber containing it 1.0 to 100 parts by weight (d) Peroxide decomposition type olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing it (e) 1 to 30 parts by weight of a polyester-based thermoplastic elastomer (f) 0.5 to 10 parts by weight and / or par of silicone having a weight average molecular weight of 70,000 or more Fluoroalkyl group-containing compound 0.1 to 3 parts by weight (g) A thermoplastic elastomer resin composition containing 1 to 20 parts by weight of straight silicone oil having a weight average molecular weight of 50,000 or less. 2. The thermoplastic elastomer resin composition according to claim 1, further comprising 100 parts by weight or less of an inorganic filler. 3. The thermoplastic elastomer resin 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. A block copolymer comprising (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component, and / Or hydrogenated block copolymer obtained by hydrogenating this 100 parts by weight (b) Softening agent for non-aromatic rubber 20 to 300 parts by weight (c) Peroxide cross-linking olefin resin, and /
Or copolymer rubber containing it 1.0 to 100 parts by weight (d) Peroxide decomposition type olefin resin, and / or
Or 10 to 150 parts by weight of a copolymer containing it (e) 1 to 30 parts by weight of a polyester-based thermoplastic elastomer (f) 0.5 to 10 parts by weight and / or par of silicone having a weight average molecular weight of 70,000 or more Fluoroalkyl group-containing compound 0.1 to 3 parts by weight (g) 1 to 20 parts by weight of straight silicone oil having a weight average molecular weight of 50,000 or less. And (b), at least part of component (c), part of component (d), and component (e), component (f)
And component (g) are heat treated in the presence of organic peroxide to crosslink, and then the crosslinked product and the rest of component (d) and the rest of component (c), if any, are blended. A method for producing a thermoplastic elastomer resin composition, comprising: 5. The method according to claim 4, wherein 100 parts by weight or less of the inorganic filler (h) is blended at any stage. 6. The method according to claim 4, wherein at least 3 parts by weight of the component (d) is subjected to a heat treatment in the presence of an organic peroxide, and at least 5 parts by weight is blended after the heat treatment. 7. The method according to claim 4, wherein at least half of the component (c) is subjected to the heat treatment. 8. Crosslinking is carried out in the presence of a crosslinking aid which is a monomer having an ethylenically unsaturated group.
The manufacturing method according to any one of 1.