JP2002088210A - Thermoplastic elastomer resin composition and molded article therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer resin composition that has specific viscoelastic properties suitable for powder rotational molding without gasification of the composition during the molding and without occurrence of blocking and generation of pin holes, and that has breaking performance desirable for an instrument panel skin part having an air bag section consolidated thereto. SOLUTION: This thermoplastic elastomer resin composition comprises (a) 100 pts.wt. of a thermoplastic polyurethane resin in which the difference (T2-T1) is <=15 deg.C, (T1) being a temperature of the resin at which the dynamic viscosity indicates 5×103 Pa.s at a frequency of 1 Hz and (T2) being a temperature of the resin at which the dynamic viscosity indicates 1×103 Pa.s at a frequency of 1 Hz, and the dynamic viscosity of the resin is 10-6×102 Pa.s at 220 deg.C and at a frequency of 1 Hz, as well as (b) 1-200 pts.wt. of an aromatic vinyl compound polymer and/or a copolymer thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic elastomer resin composition and a molded article from the composition.
More specifically, the present invention relates to a thermoplastic elastomer resin composition exhibiting fluidity suitable for rotary powder molding, and a molded article from the composition.

[0002]

2. Description of the Related Art For molding interior parts of automobiles, in particular instrument panels and the like that require a soft feeling on the surface, rotary powder molding that has excellent grain transferability and can form a high-quality skin material is used. And a resin composition for powder molding has been proposed (for example, JP-A-7-82433 and JP-A-2000-102939). One of the materials used as a raw material resin is a polyolefin-based elastomer, but there is a problem that the obtained molded product is easily damaged. Although a composition in which this problem is improved by decoration of the composition or surface decoration such as painting has been studied, the cost is high and it is not practical. By using an acrylonitrile-styrene-acrylate copolymer resin, the above problem is solved, but the melt viscosity is extremely high, and a skin material having excellent appearance and the like cannot be formed by powder rotational molding.

[0003] JP-A-8-325348 discloses a thermoplastic polyurethane elastomer composition having excellent scratch resistance and moldability. However,
When powder rotational molding is performed using the composition, some components generate gasification or decomposition gas, thereby forming a gas layer on the surface (between the mold and the skin) of the molded product, There are problems such as the occurrence of patterns on the surface and the inability to reproduce details. This phenomenon becomes remarkable especially when molding is performed at a high temperature. It is possible to cover the pattern by painting or the like in a later step, but this is costly. In addition, a part of the surface of the resin that is collected and reused without being attached to the mold is melted by heating at the time of the previous molding, thereby causing agglomeration of powders (hereinafter, referred to as blocking), Blocking particles are produced. When this is reused,
Problems such as pinholes are caused in the obtained molded product.

[0004] A desired property of the skin material used for the instrument panel is the tearability of the skin when the airbag is mounted. In recent years, a closing member (referred to as an airbag cover) of a passenger side airbag has been integrally formed with an instrument panel, whereby a skin material is also formed on the airbag portion and other instrument panels. The parts are made of the same material and the same molding. When deploying the airbag, in order to deploy and inflate the airbag from an intended position, a square-shaped thin portion is provided in advance at a predetermined position of the skin material (generally, the back surface of the skin), and this portion is selectively formed. It is designed to be split. Therefore, as the skin material, a material that is more easily split is preferable, and a material having relatively low strength and elongation is desired. However, the thermoplastic urethane-based elastomer composition described above is used for other material systems,
For example, it is not suitable as a skin material of an instrument panel integrally having the airbag portion because it has higher strength and elongation than, for example, a vinyl chloride resin, an olefin-based elastomer, and an acrylonitrile-styrene-acrylate copolymer resin.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems. Specifically, the present invention has a specific viscoelastic property suitable for rotary powder molding, gasification during molding,
It is an object of the present invention to provide a thermoplastic elastomer composition which is free from blocking and pinhole generation and has a tearing property desired for the skin of an instrument panel integrally having an airbag portion.

[0006]

As a result of various studies, the present inventors have found that a thermoplastic polyurethane-based resin (hereinafter abbreviated as "TPU") having a specific viscoelastic property has a specific aromatic vinyl resin. It has been found that the above problem can be avoided by using a polymer and / or copolymer of a compound, and the present invention has been accomplished. That is, the present invention has the following components: (a) Temperature _{(T 1)} to a resin that exhibit dynamic viscosity 5 × ¹⁰ 3 Pa · s at a frequency 1Hz Temperature _{(T 1)} and the temperature _(T 2) A difference between the temperature (T ₂ ) at which the resin exhibits a dynamic viscosity of 1 × 10 ³ Pa · s at the frequency, (T ₂ −T ₁ ) is 15 ° C. or less,
And 100 parts by weight of a thermoplastic polyurethane resin wherein the resin exhibits a dynamic viscosity of 10 Pa · s to 6 × 10 ² Pa · s at the frequency at 220 ° C., and (b)
Aromatic vinyl compound polymer and / or copolymer
A thermoplastic elastomer resin composition containing 1 to 200 parts by weight. Further, the present invention relates to a temperature (T ₁ ) at which the composition comprising the above (a) and (b) exhibits a dynamic viscosity of 5 × 10 ³ Pa · s at a frequency of 1 Hz at a temperature (T ₁ ). , The difference from the temperature (T ₂ ) at which the composition at the temperature (T ₂ ) exhibits a dynamic viscosity of 1 × 10 ³ Pa · s at the frequency, where (T ₂ −T ₁ ) is 20 ° C. or less. Yes,
The thermoplastic elastomer resin composition described above, wherein the composition exhibits a dynamic viscosity of 10 Pa · s to 6 × 10 ² Pa · s at the frequency at 220 ° C. It is preferable that the composition further contains (c) 0.01 to 15 parts by weight of an unsaturated carboxylic acid or a derivative thereof and / or an unsaturated glycidyl compound or a derivative thereof based on 100 parts by weight of the component (b). It is preferable that the composition further contains 0.01 to 4.0 parts by weight of the organic peroxide (d) based on 100 parts by weight of the component (b) and is subjected to dynamic crosslinking. Further, the present invention comprises any one of the thermoplastic elastomer resin compositions described above, has a major axis of 400 μm or less, and has a ratio of major axis to minor axis of 3: 1.
１ ： 1: 3. Furthermore, the present invention also relates to a molded product having a thickness of 0.2 to 3 mm obtained by subjecting the above resin granules to rotary powder molding. In addition, the present invention also relates to a molded article having the molded body having a thickness of 0.2 to 3 mm as a skin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component of the resin composition of the present invention will be described in detail.

Component (a): thermoplastic polyurethane resin
(TPU) The resin of the component (a) in the present invention has a dynamic viscosity of 5 × 10 ³ P at a frequency of 1 Hz at a temperature (T ₁ ).
The resin at the temperature (T ₁ ) indicating a · s and the temperature (T ₂ ) has a dynamic viscosity of 1 × 10 ³ Pa at the frequency.
The difference from the temperature (T ₂ ) indicating s, (T ₂ −
T ₁ ) is 15 ° C. or less, and the resin has a dynamic viscosity of 10 Pa · s to 6 × 1 at 220 ° C. at the frequency.
It is a thermoplastic polyurethane resin showing 0 ² Pa · s.

The dynamic viscosity decreases gradually with temperature,
At around 5 × 10 ³ Pa · s, it starts to drop sharply and 1 × 1
0 ³ Pa · s. In the present invention, the behavior of such a viscosity, the temperature indicating the 5 × ¹⁰ 3 Pa · s and _{T 1,} the temperature indicating the 1 × ¹⁰ 3 Pa · s and _{T 2,} the _difference, T 1 -T ₂ was 15 ° C. or less. In other words, temperature _{T 2} and _{T 1} are both due to the melting of TPU, lies temperature range at which the viscosity is decreasing, the temperature difference _(T 2 -T ₁₎ is 15 ℃ or less, the resin temperature It means that the viscosity of the TPU decreases rapidly with the increase.

[0010] Since the TPU exhibiting such a viscosity behavior is rapidly melted near the surface of the mold, a sufficient amount of the TPU adheres to the mold, while softening or melting away from the vicinity of the surface. Will be recovered. Therefore, it is possible to form a skin material having a uniform thickness and excellent appearance and feel.

The upper limit of the temperature difference (T ₂ −T ₁ ) is 15 ° C.
It is. When the temperature difference is 12 ° C. or less, a skin material having particularly excellent appearance and the like can be obtained, which is preferable. When the temperature difference exceeds 15 ° C., there is a problem that the time required for molding tends to be long, air is easily entrapped, and this air remains as it is on the skin material formed. Further, the TPU is melted away from the vicinity of the surface of the mold, and a part of the melted TPU forms an agglomerate. The agglomerates do not melt quickly when reused, and thus have the problem of causing defects such as pinholes. The lower limit of the temperature difference (T ₂ −T ₁ ) is actually about 5 ° C.

The upper limit of the dynamic viscosity of the TPU at a temperature of 220 ° C. is 6 × 10 ² Pa · s, preferably 3 × 1 ² Pa · s.
0 ² Pa · s, more preferably 15 × 10 Pa · s, and the lower limit is 10 Pa · s, preferably 50 Pa · s
It is. The TPU having a viscosity exceeding the upper limit value has low fluidity in a molten state at the time of molding the rotary powder, and it is difficult to obtain a skin material having a uniform thickness. Further, there are problems such as generation of pinholes, and it is difficult to obtain a skin material having excellent appearance and feel. On the other hand, a TPU having a viscosity less than the lower limit described above causes problems such as easy occurrence of a bloom phenomenon and poor chemical resistance.

[0013] Generally, the TPU comprises a polyol, a diisocyanate, and a chain extender. In particular, the TPU of the present invention having the above-mentioned viscosity behavior has a linear structure in which molecules are easily arranged, and has a large number of urethane bonds per molecule and a large bonding force due to hydrogen bonds. It has high reactivity and the degree of crosslinking is relatively small.

The TPU having the above structure is a polyisocyanate and a polyol, and the total amount of the polyisocyanate and the polyol is 100 to 5
It can be prepared using 00 ppm of a urethane polymerization catalyst and 1 to 5 moles of a chain extender in a molar ratio to a polyol. Further, the polyol and the polyisocyanate may be not only difunctional but also trifunctional or more. For example, TPU generated by a polyaddition reaction between an adipate-type polyester polyol having hydroxyl groups at both ends of a condensate of adipic acid and 1,4-butanediol and 1,6-hexamethylene diisocyanate (HDI) is obtained. No.

As the polyol, there may be mentioned polyester polyol, polyester ether polyol, polycarbonate polyol and polyether polyol. Polyester polyols include aliphatic dicarboxylic acids, such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids, such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; Acids, such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or acid esters thereof,
Or acid anhydride and ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,
1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-
Nonanediol and the like, or a polyester polyol obtained by a dehydration condensation reaction with a mixture thereof; polylactone diol and the like obtained by ring-opening polymerization of a lactone monomer such as ε-caprolactone.

As the polycarbonate polyol, ethylene glycol, 1,3-propylene glycol,
1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, neopentyl glycol, 1,8-
Examples thereof include products obtained by reacting at least one polyhydric alcohol such as octanediol, 1,9-nonanediol, and diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, and the like.

Examples of the polyester ether polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. Alicyclic dicarboxylic acids, such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or acid esters or acid anhydrides thereof, and glycols such as diethylene glycol or propylene oxide adducts; or Products obtained by a dehydration condensation reaction with these mixtures are mentioned.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran, and copolyethers thereof.

Although the number average molecular weight of the polyol is not particularly limited, it is usually from 500 to 10,000, and particularly preferably from 1,0.
It is preferably from 00 to 4,000. If the number average molecular weight is too large, the number of soft segments increases and the number of hard segments decreases at the same molar ratio. For this reason, a TPU having excellent moldability may not be obtained because the crystallinity is lowered and the change in viscosity during melting is small. On the other hand, if the number average molecular weight is too small, the number of hard segments increases, and the elastomer becomes hard, so that a skin material excellent in appearance, feel and the like may not be obtained.

Examples of the isocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalenediisocyanate, tolylene diisocyanate,
6-hexamethylene diisocyanate (HDI), isophorone diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, tetramethyl xylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanatomethyloctane, lysine Ester triisocyanate, 1,
Examples include 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, and the like. Among them, HDI, MDI, hydrogenated MDI, and the like are preferable because the molecular structure has symmetry. When an isocyanate-terminated prepolymer having isocyanates at both ends is used, the hydrogen bonding strength of the hard segment can be increased, and a crystal phase can be grown.

The chain extender can partially grow a hard segment in the TPU molecular chain and increase the crystallinity. However, if the amount of the chain extender is too large, it is necessary to pay attention to the fact that the elastomer becomes too hard due to excessive progress of the crystal or an increase in the number of hard segments. As the chain extender, a low molecular weight polyol is used, for example, ethylene glycol, 1,3-propylene glycol, 1,
2-propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
Fats such as 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, glycerin Aromatic polyol, 1,4-dimethylolbenzene, bisphenol A, bisphenol A
And aromatic glycols such as ethylene oxide or propylene oxide adducts.

The TPU is produced in a one-shot process or a two-stage process by adding a catalyst to the polyol, the chain extender, and the isocyanate. After completion of the polymerization, the TPU is cured in an electric furnace or the like. After cooling, the mixture is coarsely pulverized, kneaded with an extruder after adding an additive, and pelletized. The ratio (NCO / OH ratio) of the equivalent of the isocyanate group (NCO group) to the equivalent of the hydroxyl group (OH group) derived from the polyol component and the chain extender in the polymerization is in the range of 0.98 to 1.02. Is preferable. If the NCO / OH ratio is less than 0.98, the moldability during rotary powder molding is improved, but the chemical resistance and the like of the obtained skin material are reduced. On the other hand, when this ratio exceeds 1.02, the degree of crosslinking of the TPU due to allophanate bonds, burette bonds and the like becomes too high, and the moldability decreases. Even if the NCO / OH ratio is higher than the above value, if the amount of the polymerization catalyst is large, N
Since the CO group is consumed and the NCO group contributing to urethanization is substantially reduced, the molecular weight does not increase, and the decrease in moldability may be suppressed.

There are many other factors that affect the crystallinity and viscosity of TPU. For example, when a polyester polyol is hydrogen-bonded to a urethane bond, the soft segment becomes longer and the hard segment becomes relatively shorter, so that the crystallinity may decrease. In addition, the use of a tri- or higher functional polyisocyanate and / or polyol lowers the crystallinity. In order to achieve the intended object of the present invention, it is preferable that the amount of these components is suppressed to 5 mol% or less.

Component (b): an aromatic vinyl compound polymer and
And / or copolymer The component (b) in the present invention includes polystyrene, poly-α-methylstyrene, acrylonitrile-styrene copolymer (AS resin), styrene-methylmethacrylate resin (MS resin), and styrene-maleic anhydride. Copolymer, rubber-modified polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin),
In addition to acrylonitrile-ethylene-propylene-styrene copolymer (AES resin), acrylonitrile-acrylate-styrene copolymer (AAS resin), etc., styrene-isoprene-styrene block copolymer (SI
S), SIS hydrogenated styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-butadiene-styrene block copolymer (SBS), SB
A block copolymer of an aromatic vinyl compound such as a styrene-ethylene-butene-styrene block copolymer (SEBS), which is a hydrogenated product of S, and a conjugated diene;
Copolymers generally called styrene-based polymers such as butadiene random copolymer (SBR) and hydrogenated product of SBR (H-SBR) are exemplified. These can be used alone or in combination of two or more. Particularly preferred is a block copolymer of an aromatic vinyl compound and a conjugated diene compound.

Here, the aromatic vinyl compound-conjugated diene compound block copolymer comprises at least one polymer block A mainly composed of an aromatic vinyl compound and a polymer block B mainly composed of a conjugated diene compound. Or a mixture obtained by hydrogenating the block copolymer, or a mixture thereof, for example, AB, ABA, BABA, A -B-
Examples thereof include an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, or a hydrogenated product thereof. The above-mentioned (hydrogenated) block copolymer (hereinafter, the (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) is obtained by converting an aromatic vinyl compound into 5 to 60 parts. % By weight, preferably 20 to 50% by weight. The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of only an aromatic vinyl compound, or one having an aromatic vinyl compound exceeding 50% by weight, preferably 70% by weight or more. Conjugated diene compound (hereinafter, (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound). The polymer block B based on a (hydrogenated) conjugated diene compound preferably consists solely of the (hydrogenated) conjugated diene compound or contains 50% by weight of the (hydrogenated) conjugated diene compound. And more preferably 70% by weight or more and a copolymer block of an aromatic vinyl compound. In each of the polymer block A mainly composed of the aromatic vinyl compound and the polymer block B mainly composed of the (hydrogenated) conjugated diene compound, the aromatic vinyl compound in the molecular chain or the (hydrogenated) ) The distribution of the conjugated diene compound may be random, tapered (the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks A mainly composed of an aromatic vinyl compound or two or more polymer blocks B mainly composed of a (hydrogenated) conjugated diene compound, they have different structures even if they have the same structure. There may be.

As the aromatic vinyl compound constituting the (hydrogenated) 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 (hydrogenated) block copolymer of the present invention having the above structure has a weight average molecular weight in terms of polystyrene of preferably 5,000 to 100,000,
More preferably, it is in the range of 10,000 to 100,000, and still more preferably 30,000 to 80,000.
The molecular weight distribution (ratio (Mw / Mn) between weight average molecular weight (Mw) and 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 linear,
It may be branched, radial, or any combination thereof. In addition, the molecular weight in this invention was measured by GPC under the following conditions, and calculated | required by converting from the polystyrene sample whose molecular weight is known. Eluent: THF Flow rate: 1.0 ml / min Detector: RI Column: Tosoh polystyrene gel TSK-GEL GMH _XL × 2 Column temperature: 40 ° C. Sample concentration: 10 mg / 10 ml of THF

Numerous methods have been proposed as methods for producing these block copolymers. Typical methods include, for example, a lithium catalyst or a method described in Japanese Patent Publication No. 23798/1972. A method obtained by performing block polymerization in an inert solvent using a Ziegler-type catalyst is exemplified. 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.

The amount of component (b) is 100 parts (a)
The lower limit is 1 part by weight, preferably 2 parts by weight, and the upper limit is 200 parts by weight, preferably 150 parts by weight, more preferably 100 parts by weight with respect to parts by weight. If it exceeds 200 parts by weight, good slush moldability (article) cannot be obtained, and the oil resistance and wear resistance of the molded article decrease. on the other hand,
If the amount is less than 1 part by weight, stringing may occur at the time of molding, and good airbag cleavability cannot be obtained.

Preferably, a temperature (T ₁ ) at which the composition comprising the above (a) and (b) exhibits a dynamic viscosity of 5 × 10 ³ Pa · s at a frequency of 1 Hz, Dynamic viscosity at frequency 1 × 10 ³ Pa · s
The difference between the showing at a temperature _{(T 2), (T 2} -T 1) is 20 ° C. or less, more preferably 15 ℃ or less,
The composition has a dynamic viscosity at 220 ° C. at the frequency of 10 Pa · s to 6 × 10 ² Pa · s, more preferably 1 Pa · s to 6 × 10 ² Pa · s.
It indicates 00 Pa · s to 6 × 10 ² Pa · s.

Component (c): unsaturated carboxylic acid or its component
Derivatives and / or unsaturated glycidyl compounds or
By mixing the component (c) with the derivative resin composition, the compatibility between the component (a) and the components other than the component (a) is improved. Further, by adding the component (d) and subjecting it to dynamic crosslinking, the oil resistance and wear resistance of the molded product can be remarkably improved. If an elastomer containing a polyurethane polymer and a copolymer is used as a skin of an automobile interior part composed of an olefin core material and an intermediate foamed layer of urethane foam, the elastomer can be crushed and recycled at once.

Examples of the unsaturated carboxylic acids or derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid and derivatives thereof, such as acid anhydrides, acid halides, amides, imides and esters. Preferably, maleic anhydride (MAH) is used.

As the unsaturated glycidyl compound or a derivative thereof, a glycidyl compound having an unsaturated group capable of copolymerizing with an olefin and a glycidyl group in a molecule is preferable, and glycidyl methacrylate (GMA) is particularly preferably used.

The amount of component (c) is 100 parts (b).
The lower limit is 0.01 part by weight, preferably 0.1 part by weight, and the upper limit is 15 parts by weight, preferably 10 parts by weight, more preferably 5 parts by weight with respect to parts by weight. Exceeding the above upper limit not only causes severe yellowing of the composition and deteriorates the heat distortion resistance and mechanical properties, but also reduces the phase of the component in the resin composition when the component (a) is blended. The effect of improving the solubility is no longer recognized, and the component volatilizes after molding, causing a fogging phenomenon and the generation of pinholes on the surface of the molded product.

Component (d): Organic peroxide In the dynamic crosslinking of the present invention, it is preferable to use an organic peroxide as a crosslinking agent. As the organic peroxide, for example, dicumyl peroxide, di-t
tert-butyl peroxide, 2,5-dimethyl-
2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (ter
t-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, te
rt-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-
Butyl cumyl peroxide and the like can be mentioned.

Among them, 2,5-dimethyl-2,5-di- (te) is preferable 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 component (d) added is 100 parts (b).
The lower limit is 0.01 part by weight, preferably 0.05 part by weight, more preferably 0.10 part by weight, and the upper limit is 4.00 parts by weight, preferably 3.50 parts by weight, based on parts by weight. Preferably it is 3.00 parts by weight. If it is less than the lower limit, the required crosslinking cannot be obtained. On the other hand, when the ratio exceeds the upper limit, the crosslinking is excessively advanced, and the dispersion of the crosslinked product is deteriorated.

In addition to the above components, the resin composition of the present invention contains a peroxide decomposable olefin resin and / or
Or a copolymer containing the same; liquid polybutadiene; release agents such as stearic acid and silicone oil; lubricants such as polyethylene wax; inorganic fillers such as pigments and alumina; antioxidants; foaming agents (organic and inorganic) A flame retardant (a hydrated metal compound, red phosphorus, ammonium polyphosphate, antimony, silicone) and the like can be added as required.

The peroxide-decomposable olefin-based resin and / or a copolymer containing the same have an effect of improving the dispersion of the component (b) in the obtained composition and improving the appearance of a molded article. The lower limit is 10 parts by weight, preferably 25 parts by weight, and the upper limit is 150 parts by weight, based on 100 parts by weight of the component (b). Preferably 1
00 parts by weight. 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-based resin suitable as the peroxide-decomposable olefin-based resin and / or a copolymer containing the same is rrrr / l- in pentad fraction by ¹³ C-nuclear magnetic resonance absorption method.
mmmm is 20% or more, and a melting peak temperature (Tm) determined by a differential scanning calorimetry is 150 ° C. or more and a melting enthalpy (ΔHm) is 100 J / g or less. Preferably, Tm is 150 ° C to 167 ° C,
ΔHm 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.

Examples of the peroxide-decomposable olefin-based resin include high-molecular-weight homo-type polypropylenes such as isotactic polypropylene and propylene and other small amounts of α-olefins such as ethylene, 1-butene, 1-hexene and 4-methyl. Copolymers with -1-pentene and the like are 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. MFR of peroxide decomposable olefin resin is 0.1 g / 10
In less than minutes, the moldability of the obtained elastomer is reduced,
When the MFR exceeds 10 g / 10 minutes, the rubber elasticity of the obtained elastomer composition deteriorates, which is not preferable.

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 boiling heptane having a melt index of 0.1 to 4 g / 10 min. A peroxide-decomposable olefin resin composed of insoluble polypropylene, or a boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more and an intrinsic viscosity [η] of 0.1.
A peroxide decomposable olefin-based resin composed of 5-9.0 dl / g of boiling heptane-insoluble polypropylene can also be used.

Liquid polybutadiene is a liquid polymer which is transparent at room temperature and has a main chain fine structure of vinyl 1,2-bonded, trans 1,4-bonded, and cis 1,4-bonded. Here, the vinyl 1,2-bond is 30% by weight.
The content is preferably not more than 30% by weight, and if it exceeds 30% by weight, the low-temperature properties of the obtained composition are deteriorated.

The number average molecular weight of the liquid polybutadiene is:
It is preferably from 1,000 to 5,000, more preferably from 3,000 to 4,000. If the amount is less than the lower limit, the heat-resistant deformation resistance of the obtained composition decreases, and if it exceeds the upper limit, the compatibility of the obtained composition with component (a) decreases.

The liquid polybutadiene is preferably a copolymerizable compound having one or more groups selected from an epoxy group, a hydroxyl group, an isocyanate group and a carboxyl group. Among them, those having a hydroxyl group and a copolymerization-reactive unsaturated double bond are particularly preferable. Commercially available products include, for example, R-45H manufactured by Idemitsu Petrochemical Co., Ltd.
T (trademark).

The lower limit of the liquid polybutadiene is 1 part by weight, preferably 3 parts by weight, and the upper limit is 30 parts by weight, preferably 1 part by weight, per 100 parts by weight of the component (b).
0 parts by weight. If the amount is less than the lower limit, the effect of addition is not recognized, and if the amount exceeds the upper limit, the mechanical properties of the composition deteriorate.

In the dynamic crosslinking in the present invention, it is preferable to further use a crosslinking aid. Examples of the crosslinking assistant include polyvinyl monomers such as divinylbenzene and triallyl cyanurate, or ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl. Examples include polyfunctional methacrylate monomers such as methacrylate. By using such a compound, a uniform and efficient crosslinking reaction can be expected. Among them, triethylene glycol dimethacrylate is effective because it is easy to handle and works as a dispersing aid.

The lower limit of the addition amount of the crosslinking assistant is 0.01 part by weight, preferably 0.05 part by weight, more preferably 0.1 part by weight, based on 100 parts by weight of the component (b) at the time of addition.
1 part by weight, and the upper limit is 10.0 parts by weight, preferably 8.0 parts by weight, more preferably 6.0 parts by weight.
If the amount is less than 0.01 parts by weight, required crosslinking cannot be obtained. If the amount exceeds 10 parts by weight, the crosslinking efficiency decreases. Also,
The addition amount of the crosslinking aid is about 1.10 of the addition amount of the organic peroxide.
A ratio of 0 to 3.0 times is preferred.

The resin composition of the present invention can be produced by kneading component (a) and component (b). 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.

When component (c) and optional components are used, first, a crosslinking agent for component (d) is added to components other than component (a) and kneaded under heating. Preferably, a crosslinking aid is also added. By this step, a composition in which each component is uniformly dispersed can be obtained.

Next, the component (a) is added to the composition obtained in the above step and kneaded. The kneading method 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 cross-linking reaction is completed at the same time as the dispersion of each component further proceeds. Conveniently, the step of side-feeding component (a) and subjecting it to dynamic crosslinking is carried out continuously.

As a kneading method, a method using a single-screw extruder or a twin-screw extruder having an L / D of 20 or more, or a method using a Banbury mixer is preferable. For example, when kneading with a twin-screw extruder, the number of rotations of the screw is 20 to 350.
When the reaction is performed under the conditions of rpm, preferably 40 to 250 rpm, dispersion of each component is good and a material having good physical properties can be obtained.

The resin composition of the present invention is also provided as a granular material having a predetermined form. In the powder rotational molding method, it is necessary that the powder itself has excellent fluidity so that the powder is uniformly attached to a mold having a complicated shape and a surplus portion is easily removed. The present inventors, a thermoplastic elastomer resin,
It was previously discovered that the fluidity could be drastically improved by forming a granular material having a predetermined shape and size in place of the conventional powder, and a patent application was filed (Japanese Patent Application No. 11-1).
No. 39056). By providing the resin composition of the present invention in the form of the granular material, the fluidity during powder molding is further improved.

FIGS. 1 and 2 are photographs of the granules of the present invention (resin granules of Example 5 described later). Although the granules are slightly elongated particles, they are substantially spherical, so that good fluidity can be obtained. The major axis of the grain is obtained by measuring the longest axis (hereinafter, referred to as “major axis”) in a photographic image at about 20 to 30 times. The range of the major axis can be appropriately determined according to the shape of the mold, the resin component, and the like. It suffices that voids are not formed when flowing into a mold and small enough to flow into details. In powder slush molding of automotive interior parts, the thickness is preferably 400 μm or less, more preferably 360 μm or less. On the other hand, if it is too small, it is considered that there is no advantage in terms of fluidity or handling as compared with conventional powders. In the photographic image, the ratio of the major axis to the shortest one in the direction perpendicular to the major axis (hereinafter referred to as “minor axis”) is in the range of 3: 1 or less, preferably 2: 1 or less, more preferably 1.5: 1 or less. is there.

The above-mentioned granular material can be produced by an underwater cutting method. With the underwater cutting method, a thermoplastic elastomer resin composition is extruded into water from an extruder die hole,
This is a method in which the extruded resin is cut by a blade provided very close to the die to obtain a granular material. In the present invention, for example, underwater pelletizing systems (Und) manufactured by Gala
erwater Pelletizing System
ms), and the resin is cooled and cut immediately after extrusion. In order to obtain a granular material having the size of the present invention, the discharge opening diameter of the die is 3 mm or less, preferably 1.0 mm or less, more preferably 0.5 mm or less. The discharge rate of the thermoplastic elastomer composition per discharge port of the die is usually 10 to 250 g / hour, preferably 20 to 250 g / hour.
１００100 g / hour. To prevent blocking,
The temperature of the water is usually from 5 to 80 ° C, preferably from 30 to 80 ° C.
７０70 ° C. Further, an anti-blocking agent may be added to water. As a method other than the underwater cutting method, there is a method of spraying or cooling a molten resin by a spray or an atomizer to form granules.

A molded product obtained by subjecting the above resin granular material to rotary powder molding will be described below with reference to FIG. The resin granular material 1 is stored in the basket 2. Next, the heating oil is circulated in the heat circulating pipe 31 and is usually heated for about 90 seconds to set the powder rotary molding die 3 at a predetermined temperature. Then, the basket 2 is moved to the molding die 3 as shown in FIG. Combine. At this time, the circulating oil is 230-2
Adjust to 40 ° C. In a state where the powder rotary mold 3 and the basket 2 are combined, it is rotated several times in the direction of arrow a. By this rotation, the resin granular material 1 in the basket 2 adheres to the mold surface of the mold 3 and is melted by the heat of the mold surface to form a molded body 4 having a thickness of 0.2 to 3 mm.
After the powder rotary mold 3 and the basket 2 have been rotated a predetermined number of times, they are stopped, and the basket 2 is removed from the mold 3. Next, the circulating oil is switched to cooling oil, and the circulating oil is cooled for about 60 seconds while circulating the cooling oil, and when the mold is removed, a molded body 4 having a thickness of 0.2 to 3 mm is obtained.

From the molded article 4, a molded article containing the molded article as a skin, for example, an automobile instrument panel,
Can be made. FIG. 4 shows a molded article including the skin.
This will be described with reference to FIG. FIG. 4 shows upper and lower open dies 5 and 6 for forming an instrument panel.
The upper mold 5 has a shape for mounting a core material 7 which is a core material of an instrument panel. The core member 7 is made in advance by injection molding of polypropylene or the like. First,
The molded body 4 is mounted according to the design shape of the lower mold 6 and the upper mold 5 is mounted.
The core member 7 is mounted using a jig or the like as appropriate. Thereafter, with the mold released, a liquid reaction mixture 8 made of a foamed resin material is injected into the lower mold 6 through the injector nozzle 9 into the lower mold 6, and after injecting a predetermined amount, the upper and lower molds are immediately closed. The reaction mixture in the mold foams and hardens to form a synthetic resin foam layer. The synthetic resin foam layer forms an intermediate layer joined to the core material 7 and the skin body 4, thus obtaining an instrument panel which is a molded article integrally having the molded body 4 as a skin.

The resin composition of the present invention can be in the form of pellets or powders in addition to the above-mentioned granules, and is subjected to various moldings such as injection molding, extrusion molding, hollow molding and stretch blow molding. be able to. Injection molding is performed using, for example, FS-120 manufactured by Nissei Resin Industry Co., Ltd., and has a length of 150 m.
m, width 25mm, thickness 4mm when molding a resin plate,
It can be performed under the following conditions. Molding temperature: 180 ° C. Injection speed: 55 mm / sec Injection pressure: 1400 kg / cm ² Holding pressure: 400 kg / cm ² Injection time: 6 seconds Mold temperature: 35 ° C. Cooling time: 45 seconds Extrusion molding is performed by, for example, Yamaguchi Corporation. When molding a resin plate with a width of 40 mm and a thickness of 5 mm using a 40 mm extruder manufactured by Seisakusho,
It can be performed under the following conditions. Extrusion temperature: 180 ° C. Screw rotation speed: 40 rpm The hollow molding can be performed under the following conditions, for example, when forming a hollow container having a diameter of 150 mm using a 40 mm hollow molding machine manufactured by Japan Steel Works, Ltd. Extrusion temperature: 180 ° C. Screw rotation speed: 40 rpm Stretch blow molding is performed, for example, when stretch blow molding is performed using a 150 mm stretch blow molding machine (die diameter: 400 mm).
It can be performed under the following conditions. Extrusion temperature: 180 ° C Screw rotation speed: 40 rpm Blow ratio: 3 times

[0059]

EXAMPLES The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. The amounts in the table mean parts by weight unless otherwise specified.

[0060] material components used in Examples (a): thermoplastic polyurethane resin Nippon Miractran Co. E785PBAF (trade _{name) T 1: 138 ℃, T} 2: 149 ℃, T 2 -T 1: 11 ℃ 220 ℃, Dynamic viscosity at a frequency of 1 Hz: 130 Pa
Component s (b): Aromatic vinyl compound copolymer Septon 2002 (SEPS) manufactured by Kuraray Styrene content: 30% by weight Isoprene content: 70% by weight Number average molecular weight: 55,000 Weight average molecular weight: 60 000 Molecular weight distribution: 1.09 Hydrogenation rate: 90% or more Component (c): unsaturated carboxylic acid, etc. Maleic anhydride manufactured by Kanto Chemical Co., Ltd. Component (d): organic peroxide Perhexa 25B (2, manufactured by NOF Corporation) 5-dimethyl-
2,5-di (t-butylperoxy) hexane) Crosslinking aid: NK ester IND (2, manufactured by Shin-Nakamura Chemical Co., Ltd.)
- methyl-1,8-octanediol dimethacrylate (85%), 1,9-mixture) Comparative Example thermoplastic polyurethane resin used in (1-nonanediol dimethacrylate (15%)) Nippon Miractran Co. E785PK601 T ₁ 188 ° C., T ₂ : 216 ° C., T ₂ -T ₁ : 28 ° C. 220 ° C., dynamic viscosity at a frequency of 1 Hz: 730 Pa
· S (2) Nippon Miractran Co. _{E180 T 1: 127 ℃, T} 2: 145 ℃, T 2 -T 1: 18 ℃ 220 ℃, dynamic viscosity at a frequency of 1 Hz: 100 Pa
・ S

Preparation of Compositions Compositions were prepared at the component ratios shown in Tables 1 and 2, respectively. First, components other than the component (a) are kneaded with a twin-screw extruder, an organic peroxide and a crosslinking aid are added, and dynamic crosslinking is performed at a kneading temperature of 200 ° C., a screw rotation of 150 rpm, and an extruder discharge rate of 20 kg / hour. Processed. Next, the component (a) was kneaded by side feeding.

Preparation of Granules The preparation of granules was carried out at the outlet of the extruder with Gala Indus.
tries, Inc. Underwater Pel
The test was performed at a die temperature of about 250 ° C., a discharge rate of 30 g / die, and a water temperature of 60 ° C., with the aid of letizing systems.

Evaluation method (1) Hardness: Measured by the JIS type A method described in JIS K6253. (2) Tensile strength: Measured by the method described in JIS K6251. The sample used was a 2 mm-thick injection molded sheet, and the test piece was a No. 3 dumbbell. (3) 100% elongation modulus: Measured by the method described in JIS K6251. The sample used was a 2 mm-thick injection molded sheet, and the test piece was a No. 3 dumbbell. (4) Tensile elongation: Measured by the method described in JIS K6251. The sample used was a 2 mm-thick injection molded sheet, and the test piece was a No. 3 dumbbell. (5) Amount of generated gas Powder rotation molding was performed at a mold surface temperature of 225 ° C. using a molding die of an oil circulation heating system, and the amount of white smoke gas generated before cooling the mold was visually observed. ：: Almost no gas was generated. Δ: Gas was generated to the extent that a problem occurred during mass production. X: Gas was remarkably generated. (6) Transferability The transferability of the grain of the molded product obtained by the powder rotary molding was visually observed. ：: very excellent transferability was exhibited. Δ: The transfer of the grain was blurred in some places. X: The transfer of the grain was blurred as a whole. (7) Scratch resistance The Taber abrasion test was performed on the surface of the powder rotary molded product under the following conditions. After rubbing the worn wheel CS-10 with a load of 250 g for 100 cycles, the surface of the molded product was visually inspected for scratches. ：: Almost no scratch was observed. Δ: Slight scratch was observed. X: The scratch was remarkable. (8) Pinhole of molded article The surface of the molded article obtained by the powder rotary molding was observed with a 5-fold loupe. ：: There was no pinhole. Δ: There was a pinhole in a part. X: There was a pinhole as a whole. (9) Blocking At the time of powder rotational molding, it was observed whether or not the material collected in the powder box was blocked by heat history. ：: None at all. Δ: Slight blocking was observed. ×: Remarkably blocked. (10) Measuring method of dynamic viscoelastic properties Measuring device: Model RDA-70 manufactured by Rheometrics
0 Frequency 1 Hz Strain load 1% 25 to 240 ° C. was performed at a heating rate of 3 ° C./min. The sample was a TPU between two 20 mm diameter disc plates.
Alternatively, the composition was prepared by pressurizing and heating the composition at 230 ° C. The sample thickness was adjusted within ± 0.2 mm, and the thickness was corrected in the measurement. T ₂ −T ₁ and the viscosity at 220 ° C. shown in Tables 1 and 2 are values for each composition. (11) Airbag Cleavage Test Using each composition as a skin layer, an instrument panel is formed by a powder rotational molding method according to the configuration shown in FIGS. 3 and 4 of Japanese Patent Application No. 2000-105254, and the back surface of the instrument panel is formed. A groove was provided at a predetermined position so as to be cleaved when the airbag was deployed. A module case in which an airbag and a gas generator, etc., which are folded and stored, is mounted on the test instrument panel, and the ambient temperature is normal temperature (20 ± 10 ° C.), high temperature (90 ° C.), low temperature (90 ° C.). -3
(0 ° C.) for 4 hours, then taken out in a natural environment, and the airbag was opened within 3 minutes. ：: Normal cleavage. Δ: Cleavage takes time.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

As described above, since the thermoplastic elastomer resin composition of the present invention does not contain a volatile softening agent, no gas is generated at the time of molding and the transferability is excellent. Also,
Since a polyurethane resin having a specific melt viscosity is used, there are no pinholes in the rotomolded product and there is no blocking problem. The composition of the present invention is suitable for forming an instrument panel having excellent airbag tearability.

[0067]

[Brief description of the drawings]

FIG. 1 is an optical micrograph (×) of a resin granule of Example 5.
30).

FIG. 2 is an optical micrograph (×) of a resin granule of Example 5.
70).

FIG. 3 is a cross-sectional view of a powder rotary molding die, showing a method for molding a molded body having a thickness of 0.2 to 3 mm.

FIG. 4 is a cross-sectional view of a case where a liquid reaction mixture is injected into the back surface of a molded body to be a skin when producing a molded article having a molded body having a thickness of 0.2 to 3 mm as a skin according to the present invention.

[0068]

[Explanation of symbols]

 Reference Signs List 2 basket 3 powder rotary mold 4 molded body having thickness of 0.2 to 3 mm 5 upper mold for instrument panel molding 6 lower mold for instrument panel molding 7 core material 8 liquid reaction mixture

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 3/24 CFF C08J 3/24 CFFZ 4J026 5/00 5/00 C08K 5/09 C08K 5/09 5 / 101 5/101 5/14 5/14 C08L 75/04 C08L 75/04 // B29K 21:00 B29K 21:00 75:00 75:00 B29L 31:58 B29L 31:58 (72) Inventor Kentaro Iwanaga Aichi 3-72 Imaike-cho, Anjo-shi, Japan Inside INOAC Corporation (72) Inventor Michihisa Tasaka 3-11-5 Nihonbashi Honcho, Chuo-ku, Tokyo Inside Riken Vinyl Industry Co., Ltd. (72) Inventor Yamanaka Minami Minami 3-11-5 Nihonbashi-Honcho, Chuo-ku, Tokyo F-term (reference) 4F070 AA18 AA53 AB08 AC35 AC44 AE08 DA05 DA55 DC01 DC05 FC05 GA05 4F071 AA12X AA22 AA22X AA34X AA53 AA75 BB01 BB05 BB06 BC12 4F205 AA31 AA45 AB03 AC04 AH25 GA01 GB01 GC04 GE16 GE21 GN01 4J002 BC03X BC06X BC07X BH01X BN06X BN15X BP01X CK02W EF046 E077 EF046 E076 EF046 EH076 EK046 A7 AB02 AC16 AC18 BA25 BA27 DB13

Claims (7)

[Claims] 1. The following components: (a) a temperature (T ₁ ) at which a resin at a temperature (T ₁ ) shows a dynamic viscosity of 5 × 10 ³ Pa · s at a frequency of 1 Hz; and a temperature (T ₂ ) The difference between the temperature (T ₂ ) at which the certain resin exhibits a dynamic viscosity of 1 × 10 ³ Pa · s at the frequency, (T ₂ −T ₁ ) is 15 ° C. or less,
And 100 parts by weight of a thermoplastic polyurethane resin wherein the resin exhibits a dynamic viscosity of 10 Pa · s to 6 × 10 ² Pa · s at the frequency at 220 ° C., and (b)
Aromatic vinyl compound polymer and / or copolymer
A thermoplastic elastomer resin composition containing 1 to 200 parts by weight. 2. A temperature (T ₁ ) at which the composition comprising (a) and (b) exhibits a dynamic viscosity of 5 × 10 ³ Pa · s at a frequency of 1 Hz, at a temperature (T ₁ ); A difference from the temperature (T ₂ ) at which the composition at the temperature (T ₂ ) exhibits a dynamic viscosity of 1 × 10 ³ Pa · s at the frequency, wherein (T ₂ −T ₁ ) is 20 ° C. or less. And the composition has a dynamic viscosity of 10 P at 220 ° C. at the frequency.
^2. A method according to claim 1, wherein the value of a · s is about 6 × 10 ² Pa · s.
The thermoplastic elastomer resin composition as described in the above. 3. Component (b): 100 parts by weight,
(C) unsaturated carboxylic acid or its derivative and / or unsaturated glycidyl compound or its derivative
Characterized by further comprising 0.01 to 15 parts by weight,
The thermoplastic elastomer resin composition according to claim 1. 4. Component (b): 100 parts by weight,
(D) Organic peroxide 0.01 to 4.0
The thermoplastic elastomer resin composition according to any one of claims 1 to 3, further comprising parts by weight and being subjected to dynamic crosslinking. 5. The thermoplastic elastomer resin composition according to claim 1, wherein the major axis is 400 μm.
m or less, and the ratio of the major axis to the minor axis is 3: 1 to 1: 3.
Resin granules. 6. A molded product having a thickness of 0.2 to 3 mm obtained by subjecting the resin granular material according to claim 5 to rotary powder molding. 7. A molded article having the molded article according to claim 6 as a skin.