JP2003034735A - Fine powder composition and thermoplastic powder blended with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic powder which gives a powder compact excellent in melt cohesion and in mold releasability when it is taken out from the forming surface of a mold. SOLUTION: The fine powder composition consists of 10-50 wt.% of (A) a fine powder having a primary diameter of 5-300 nm of which the surface is not treated with a silicone oil and 90-50 wt.% of (B) a fine powder having a primary diameter of 5-300 nm of which the surface is treated with a silicone oil.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fine powder composition and a thermoplastic powder containing the fine powder composition. More specifically, the present invention provides a specific
The present invention relates to a fine powder composition composed of various types of fine powder, and a thermoplastic powder obtained by blending the fine powder composition with a granular thermoplastic resin or thermoplastic elastomer.

[0002]

2. Description of the Related Art Conventionally, a sheet-shaped molded article having a complicated uneven pattern such as leather grain and stitches on its surface has been used as a skin material for automobile interior parts and the like. As such a molded body, a molded body obtained by powder molding a powder of an olefinic thermoplastic elastomer has been proposed (for example, JP-A-5-1183 and JP-A-5-505).
No. 0, JP-A-10-30036, etc.).

However, when the powder is stored for a long period of time or repeatedly subjected to powder slush molding, the powders gradually agglomerate and the powder fluidity decreases, and as a result, the obtained molded body has a lack of wall or pinholes. There is a problem that such a problem occurs.

In order to solve such a problem, a fine powder is blended on the surface of a powder made of an olefinic thermoplastic elastomer to improve long-term storability and powder fluidity, so that a complicated shape can be obtained. A method for producing a powder slush compact is known (for example, JP-A-5-7060).
No. 1, JP-A No. 11-286578, etc.).

In Japanese Patent Laid-Open No. 11-286578, 1 is added to a pulverized product of a specific thermoplastic elastomer composition.
A thermoplastic elastomer composition powder is described in which a fine powder having a secondary particle size of 300 nm or less is blended.
However, although the powder flow characteristics can be improved and a compact having a complicated shape can be produced by blending such a fine powder having a specific primary particle diameter, the obtained powder slush compact is obtained. When it is taken out from the molding surface of the mold, because the fine powder physically bites into a fine decorative portion such as a complicated grain pattern or stitch pattern on the molding surface of the mold,
Poor releasability (easiness of peeling when a sheet formed on the molding surface of the mold is peeled from the mold), creases are generated in the obtained powder slush molded product, and in some cases, the molding There was a problem that the problem of the body breaking occurred.

Further, in JP-A No. 11-286578, a fine powder having a primary particle size of 300 nm or less and having a surface treated with silicone oil is blended with the above-mentioned granular thermoplastic elastomer composition. Accordingly, a thermoplastic elastomer composition powder having excellent long-term storage stability and powder flowability is described. A powder compact molded by using the powder has excellent releasability. However, since the melt cohesiveness between the powders is remarkably hindered by the silicone oil, there is a problem that a molded product excellent in strength and appearance cannot be obtained. For this reason, there has been a demand for a thermoplastic powder capable of giving a powder compact having excellent productivity and practicality.

[0007]

Under these circumstances, the problem to be solved by the present invention is to provide a fine powder composition comprising two specific types of fine powder and a granular thermoplastic resin or thermoplastic elastomer. The present invention relates to a thermoplastic powder containing the fine powder composition, which is excellent in melt cohesiveness and in mold release property when taken out from the molding surface of a mold.

[0008]

That is, the first invention in the present invention relates to a fine powder composition comprising the following (A) and (B) (A): not surface-treated 1 Secondary particle size is 5-300n
10 to 50% by weight of fine powder having m (B): Fine powder having a primary particle diameter of 5 to 300 nm, the surface of which is surface-treated with silicone oil 90 to 90
50% by weight Further, the second invention of the present invention relates to a thermoplastic powder comprising a granular thermoplastic resin or a thermoplastic elastomer in which a specific amount of the fine powder composition of the first invention is blended. Is. The third invention of the present invention relates to the thermoplastic powder of the second invention, further comprising a specific amount of powder having a primary particle size of more than 300 nm and 10 μm or less.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The fine powder composition of the present invention comprises the following (A) and (B). (A): Fine powder whose surface is not treated with silicone oil, and whose primary particle size is 5 to 300 nm (B): Fine powder whose surface is treated with silicone oil And fine powder having a primary particle size of 5 to 300 nm

(A) is a fine powder whose surface is not treated with silicone oil and has a primary particle size of 5
It is a fine powder having a particle size of 300 nm. (A)
Examples thereof include inorganic oxides, pigments, vinyl chloride resins for pastes, and fatty acid metal salts. Also, Japanese Patent Laid-Open No. 2000-3362
It is also possible to use an acrylate-based polymer having a glass transition temperature of 60 ° C. or higher and a non-halogen-based resin having a specific sphericity, which are described in Japanese Patent Laid-Open No. 19 and Japanese Patent Laid-Open No. 2001-123019.

The primary particle size of (A) is required to be 300 nm or less, 200 nm or less, and further 5 nm to 1
It is preferably 50 nm. Primary particle size is 300 nm
If it exceeds the above range, the powder flowability of the thermoplastic powder obtained is not sufficiently improved, and defects such as lack of thickness and pinholes occur in the obtained powder compact. Here, the primary particle size means that a photograph of (A) is taken by a transmission electron microscope (TEM),
This is a value obtained by measuring the diameter of particles by arbitrarily selecting about 1000 particles and dividing the diameter of these particles by the number of particles.

As the inorganic oxide, alumina, silica,
Alumina silica and the like can be mentioned.

Almost all of alumina has the chemical formula Al ₂
It is a fine powder composed of O ₃ units. Alumina has various crystal forms, but any crystal form can be used. These are called α-alumina, β-alumina, γ-alumina, etc. depending on the crystal form. Alumina C (γ-alumina) manufactured by Degussa, AKP-G008 (α-alumina) manufactured by Sumitomo Chemical Co., Ltd.
And so on.

Most of silica has a chemical formula of SiO ₂
It is a fine powder composed of units. Crushing natural diatomaceous earth,
It is produced by a method such as decomposition of sodium silicate. Examples include OX50 manufactured by Degussa. Alumina silica is an inorganic oxide containing the above-mentioned alumina and silica as main components.

It is also possible to use an inorganic oxide whose surface is treated with a fatty acid ester organic lubricant such as erucic acid amide.

As the pigment, azo type, phthalocyanine type,
Organic pigments such as selenium and dye lake, oxides such as titanium oxide, chromolybdenum molybdate, selenium sulfide compounds,
Inorganic pigments such as ferrocyan compounds and carbon black are used. When a pigment is used, it may be supported on a carrier such as calcium carbonate, metal soap, or magnesium oxide.

(A) is used alone or has a primary particle size of 30.
A plurality of those having a thickness of 0 nm or less are used in combination.
For example, the inorganic oxide can be used alone, or the pigment and the inorganic oxide can be used in combination.

(B) is a fine powder whose surface is treated with silicone oil and has a primary particle size of 5 to 5.
It is a fine powder of 300 nm.

(B) is produced by treating the surface of the aforementioned fine powder with silicone oil.

The primary particle size of (B) is required to be 300 nm or less, 200 nm or less, and further 5 nm to 1
It is preferably 50 nm. Primary particle size is 300 nm
If it exceeds the above range, the powder flowability of the thermoplastic powder obtained is not sufficiently improved, and defects such as lack of thickness and pinholes occur in the obtained powder compact. Here, the primary particle size is measured by the method described above.

The silicone oil is usually added in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the fine powder before surface treatment. When the silicone oil used for the surface treatment is less than 0.1 part by weight, there is a problem that the mold releasability of the powder compact formed by powder molding the thermoplastic powder is poor. On the other hand, if it exceeds 10 parts by weight, the melt cohesiveness of the thermoplastic powder at the time of powder molding is deteriorated, so that a powder compact excellent in strength and appearance cannot be obtained.

Examples of the method for producing (B) include a method in which a fine powder to be surface-treated and silicone oil are put into a high-speed rotary mixer such as a Henschel mixer and stirred. Stirring is usually performed at room temperature,
You may heat if necessary.

The viscosity of the silicone oil at 25 ° C. is preferably 0.5 to 50,000 centistokes, more preferably 10,000 to 10,000 centistokes. When the viscosity exceeds 50,000 centistokes, the silicone oil does not uniformly adhere to the fine powder to be surface-treated, so that the obtained (B) may have tackiness.

As (B), for example, R2 manufactured by Degussa
02 (silica whose surface is treated with silicone oil) and the like.

(B) is used alone or has a primary particle size of 30
A plurality of those having a thickness of 0 nm or less are used in combination.
For example, an inorganic oxide whose surface is treated with silicone oil can be used alone, or can be used in combination with a pigment whose surface is treated with silicone oil.

The fine powder composition in the present invention comprises (A) 10 to 50% by weight and (B) 90 to 50% by weight. Here, the blending amount of (A) with respect to the total amount of (A) and (B) is preferably 15 to 45% by weight, and more preferably 20 to 40% by weight. Here, if the content of (A) is less than 10% by weight, the melt cohesiveness of the thermoplastic powder is inferior, and a powder compact excellent in strength and appearance cannot be obtained. Further, when (A) exceeds 50% by weight, the releasability of the powder compact is insufficient.

In the present invention, by incorporating the fine powder composition into the granular thermoplastic resin or thermoplastic elastomer described later, the melt cohesiveness is excellent and the releasability at the time of taking it out from the molding surface of the mold. It is possible to produce a thermoplastic powder that gives a powder compact excellent in heat resistance.

The fine powder composition is based on 100 parts by weight of a granular thermoplastic resin or thermoplastic elastomer described below.
The total amount is 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight.
If the blending amount is less than 0.1 parts by weight, the flow characteristics of the thermoplastic powder obtained will be inferior, and defects such as lack of wall and pinholes will occur in the obtained powder compact. Also, 10
If the amount is more than parts by weight, the melt cohesiveness of the thermoplastic powder is inferior, which causes a problem that the strength of the obtained powder compact decreases.

The fine powder composition may be blended with the granular thermoplastic resin or thermoplastic elastomer described below by uniformly adhering the fine powder composition onto the granular thermoplastic resin or thermoplastic elastomer. If there is, it is not particularly limited. For example, a blending method using a blender with a jacket, a high-speed rotary mixer, a Nauta mixer, or the like can be used. Among them, a method such as Henschel mixer or super mixer, in which mutual adhesion is prevented and uniform dispersion is performed by applying a shearing force is preferable. Further, the compounding is usually performed at room temperature.

At this time, the fine powder composition comprising (A) and (B) may be previously prepared by a blender or the like and then blended into a granular thermoplastic resin or thermoplastic elastomer, or (A), (B) and the granular thermoplastic resin or thermoplastic elastomer may be blended at once. Further, for example, after blending the granular thermoplastic resin or thermoplastic elastomer and (A), the rest (B) may be blended, or the order may be reversed.

The thermoplastic powder used in the present invention is
It is made of a thermoplastic resin or a thermoplastic elastomer.

The thermoplastic resin is at least one selected from polyolefin resins, ABS (acrylonitrile-butadiene-styrene copolymer) resins, polystyrene and the like, which will be described later.

As the thermoplastic elastomer, a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer or a blend thereof. And the like (see, for example, “Thermoplastic Elastomer Composition” published by Shoji Matsuzaki, Chemical Industry Daily, 1991).

The styrene thermoplastic elastomer is a copolymer of a conjugated diene and a vinyl aromatic compound or a hydrogenated product thereof.

Examples of the conjugated diene include conjugated dienes having 4 to 8 carbon atoms such as butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene.

The vinyl aromatic compound has one of its vinyl groups.
The 2-position or 2-position may be substituted with an alkyl group such as a methyl group. Examples of the vinyl aromatic compound include vinyl aromatic compounds having 8 to 12 carbon atoms such as styrene, p-methylstyrene and α-methylstyrene.

Examples of the styrene-based thermoplastic elastomer include butadiene-styrene copolymer rubber, isoprene-styrene copolymer rubber, butadiene / isoprene-styrene copolymer rubber, butadiene-p-methylstyrene copolymer rubber or these. The hydrogenated products are listed.

These styrenic thermoplastic elastomers are composed of at least one structural unit. As the structural unit, a vinyl aromatic compound polymer block, a random copolymer block of a vinyl aromatic compound and a conjugated diene, a block formed by hydrogenating a conjugated diene polymer block, or these conjugated diene units are hydrogenated. Blocks and the like are included.

Examples of the styrene thermoplastic elastomer include a styrene / butadiene copolymer, a styrene / isoprene copolymer, a styrene / butadiene copolymer, a styrene / isoprene copolymer, a styrene / butadiene / styrene copolymer, and a styrene. Examples thereof include an isoprene-styrene copolymer, a styrene-butadiene / isoprene-styrene copolymer, a styrene-styrene / butadiene-styrene copolymer, a styrene-styrene / isoprene-styrene copolymer or a hydrogenated product thereof. In addition, "-" indicates the boundary of the structural unit, and "." Indicates that two or more compounds are used in combination within the structural unit.

The content of the vinyl aromatic compound unit in the styrene-based thermoplastic elastomer is preferably 50% by weight or less, and more preferably 20% by weight or less, in order to obtain a powder compact having excellent flexibility. . If this content exceeds 50% by weight, the obtained powder compact tends to become brittle.

Such styrene-based thermoplastic elastomers are disclosed, for example, in JP-A-2-36244 and JP-A-3.
-72512, JP-A-7-118335,
JP-A-56-38338, JP-A-61-6073
It can be easily manufactured by the method described in Japanese Patent No. 9 or the like.

Examples of the olefin thermoplastic elastomer include a composition comprising a polyolefin resin and a rubber polymer, and an olefin rubber polymer.
The olefin-based thermoplastic elastomer is disclosed in, for example, JP-A-5-5050, JP-A-10-30036,
It can be produced by the method described in JP-A-10-231392.

The polyolefin resin is at least one kind selected from olefin homopolymers or copolymers having high crystallinity. As the olefin, ethylene, propylene, 1-butene, 1-hexene, 1-
Examples thereof include olefins having 2 to 8 carbon atoms such as octene. Examples of the polyolefin resin include polyethylene, polypropylene, poly (1-butene), a copolymer of propylene and ethylene, and propylene and other α-.
Examples thereof include copolymers with olefins (such as 1-butene). When the polyolefin resin is a propylene-ethylene copolymer resin or a propylene-1-butene copolymer resin, the thermoplastic elastomer of the present invention can give a powder molded product having excellent heat resistance and flexibility. It is preferable in terms.

The crystallinity of the polyolefin resin is 50.
% Or more, and 60% or more is preferable from the viewpoint of heat resistance and strength of the obtained powder compact. Here, the crystallinity is obtained by an X-ray diffraction method.

It is also possible to use a copolymer obtained by copolymerizing two or more kinds of monomers selected from ethylene and α-olefins having 3 to 8 carbon atoms in two or more steps. For example, a copolymer obtained by homopolymerizing propylene in the first step and copolymerizing propylene with ethylene or an α-olefin other than propylene in the second step can be used. From the viewpoint of the strength of the molded product obtained by the powder molding method, the melt flow rate (MF) of the polyolefin resin measured at 230 ° C. under a load of 2.16 kgf according to JIS K-7210.
R) is usually 20 to 500 g / 10 minutes, preferably 5
0 to 300 g / 10 minutes, particularly preferably 100 to 30
It is within the range of 0 g / 10 minutes. As the polyolefin-based resin, it is also possible to use a resin obtained by decomposing it with an organic peroxide or the like and highly fluidized.

The rubbery polymer is an olefinic rubbery polymer such as an ethylene-α-olefin copolymer, a propylene-α-olefinic copolymer or a conjugated diene polymer, or the above-mentioned styrene-based polymer. It is at least one type selected from plastic elastomers and the like.

The ethylene-α-olefin-based copolymer is a copolymer of ethylene and α-olefin, a copolymer of ethylene, α-olefin and non-conjugated diene, and the like, which has almost no crystallinity. Polymers having a coalescence or crystallinity of less than 50%. Here, the crystallinity is obtained by the X-ray diffraction method described above.

Here, the α-olefin used in the ethylene-α-olefin copolymer is an α-olefin having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, 1-octene. Is preferably used. The ethylene-α-olefin-based copolymer is
Non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, cyclopentadiene, 2-methyl-2,5-norbornadiene and 5-ethylidene-2-norbornene, styrene, α-methylstyrene, 2,4- Monomers such as vinyl aromatic compounds such as dimethylstyrene and p-methylstyrene may be copolymerized.

Examples of such ethylene-α-olefin copolymers include ethylene-propylene copolymers,
Examples thereof include ethylene-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers and ethylene-propylene-5-ethylidene-2-norbornene copolymers. The ethylene-α-olefin-based copolymer may be crosslinked.

The α-olefin unit content is usually 5 to.
It is in the range of 40% by weight, more preferably 10 to 35% by weight, and the ethylene unit content is usually 60 to 95% by weight, preferably 65 to 90% by weight. α-olefin unit content and ethylene unit content are ¹³ C-NMR
Method or infrared absorption spectroscopy.

From the viewpoint of the strength of the molded product obtained by molding the thermoplastic elastomer composition of the present invention, the ethylene-α-olefin-based copolymer of ASTM D-
The Mooney viscosity {ML _{1 + 4} (100 ° C.)} measured at 100 ° C. according to 927-57T is usually 10 to 350, more preferably 15 to 300.

The propylene-α-olefin copolymer is a copolymer of propylene and α-olefin, a copolymer of propylene, ethylene and α-olefin, and the like, which has almost no crystallinity or It is a polymer having a crystallinity of less than 50%. Here, the crystallinity is
It is a value obtained by an X-ray diffraction method. Such a propylene-α-olefin-based copolymer is disclosed, for example, in Japanese Patent Laid-Open No.
It is described in Japanese Patent Publication No. 1-323034.

The conjugated diene polymer is a conjugated diene polymer or a hydrogenated product of a conjugated diene polymer.

The conjugated diene polymer is a polymer obtained by polymerizing or copolymerizing at least one conjugated diene. Examples of the conjugated diene include conjugated dienes having 4 to 8 carbon atoms such as butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene. Examples of the conjugated diene polymer include polybutadiene, polyisoprene, polypentadiene, butadiene-isoprene copolymer and the like.

The hydrogenated product of the conjugated diene polymer is a hydrogenated conjugated diene polymer obtained by hydrogenating the conjugated diene polymer. Examples of the hydrogenated conjugated diene polymer include hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated polypentadiene, and hydrogenated butadiene-isoprene copolymer.

Such conjugated diene-based polymers are disclosed, for example, in JP-A-2-36244 and JP-A-3-72512.
JP-A No. 7-118335, JP-A No. 56-
It can be easily produced by the methods described in JP-A-38338, JP-A-61-60739 and the like.

When a hydrogenated product of a copolymer of a conjugated diene, which is one of the above-mentioned styrene-based thermoplastic elastomers, and a vinyl aromatic compound is used as the rubber-like polymer, all of the hydrogenated conjugated diene units are used. The ratio of the number of hydrogenated conjugated diene units having a side chain of 2 or more carbon atoms to the number is
Although it depends on the type of the conjugated diene monomer used in the polymerization, it is usually 50% or more, preferably 60 to
95%, and further 70 to 90% is excellent in flexibility of the powder molded product made of the thermoplastic elastomer obtained, and when it is taken out from the mold in the fourth step, the powder molded product is folded. It is preferable in that it is difficult for my whitening. Such a ratio can be determined by ¹ H-NMR measurement. Further, in this case, the hydrogenation rate of the styrene-based thermoplastic elastomer must be 80% or more, preferably 90%.
% Or more, particularly 95% or more is preferable from the viewpoint of heat resistance and light resistance of the obtained powder compact.

MFR of these rubbery polymers (JIS K
The melt flow rate is preferably 2 to 200 g / 10 minutes, more preferably 5 to 100 g / 10 minutes, and particularly preferably 10 to 100 g / 10 minutes according to -7210 and measured at 230 ° C. under a load of 2.16 kgf. It is preferable that the powder molding method can provide a molded article having excellent appearance and strength.

As the rubbery polymer, other rubbery polymers such as natural rubber, butyl rubber, chloroprene rubber, epichlorohydrin rubber and acrylic rubber, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer And a saponified product thereof, an ethylene-methyl methacrylate copolymer, an ethylene-glycidyl acrylate-vinyl acetate copolymer, an ethylene-glycidyl methacrylate-vinyl acetate copolymer and the like.

Among these rubbery polymers, tan δ-temperature dependence curve obtained by solid viscoelasticity measurement of a composition obtained by kneading with a polyolefin resin,
In the temperature range of 70 to 30 ° C, ta of polyolefin resin is
A rubber polymer that gives a new single tan δ peak at a temperature different from both the n δ peak temperature and the tan δ peak temperature of the rubber polymer is excellent in flexibility of the obtained powder molded product and is bent when bent. It is preferably used because it has the property that the part does not whiten. Further, even a rubbery polymer having no such property has an advantage that the cold impact resistance of the powder compact obtained by blending is improved.

These olefin-based thermoplastic elastomers can be obtained by melt-kneading a polyolefin-based resin, a rubbery polymer and various components to be blended if necessary. Further, by mixing the organic peroxide and the crosslinking aid during the melt-kneading, a partially crosslinked composition in which the rubbery polymer part is mainly crosslinked can be obtained.

For kneading, a known single-screw extruder, twin-screw extruder, kneader, roll or the like is used. The above-mentioned various component additives and various polymers are compounded, for example, by a method using a polyolefin resin or a rubbery polymer in which these additives are preliminarily compounded, or when kneading or dynamically crosslinking the above components. To be done.

When an olefinic thermoplastic elastomer comprising a polyolefin resin and a rubbery polymer is used, the weight ratio thereof is usually 5:95 to 95: 5, preferably 20:80 to 50:50, more preferably 30: 7
0 to 45:55. When the content of the polyolefin-based resin is less than 5% by weight, the obtained powder molded article may have tackiness, resulting in insufficient heat resistance and cold resistance. On the other hand, when the content of the polyolefin resin exceeds 95% by weight, the flexibility of the obtained powder compact is insufficient, and a powder compact excellent in touch and scratch resistance cannot be obtained.

Of the above-mentioned rubbery polymers, olefinic rubbery polymers such as ethylene-α-olefin copolymers, propylene-α-olefinic copolymers and conjugated diene polymers are It can also be used as the olefinic thermoplastic elastomer of the invention. However, if the powder of the olefinic rubbery polymer used in this case has tackiness at room temperature, it is difficult to manufacture a powder molded product, and therefore it is necessary not to have tackiness.

When the olefin rubber polymer is used as the olefin thermoplastic elastomer of the present invention,
As the olefin rubbery polymer, ethylene-α-olefin copolymers such as ethylene-1-butene copolymer, ethylene-1-hexene copolymer and ethylene-1-octene copolymer are usually used. It The crystallinity determined by these X-ray diffraction methods is preferably 20 to 45%.

Normal and preferred α-olefin unit content and ethylene unit content of the ethylene-α-olefin copolymer, Mooney viscosity {ML _{1 + 4} (100 ° C.)}
Is as described above.

In this case, although the flexibility and scratch resistance of the obtained powder compact are excellent, the melting point of the copolymer is usually as low as 100 ° C. or lower, so that it is applied to applications requiring heat resistance. Is restricted.

The vinyl chloride thermoplastic elastomer is
It is a thermoplastic elastomer in which a polyvinyl chloride resin, a plasticizer and, if necessary, a stabilizer and a pigment are mixed. Examples of the vinyl chloride-based thermoplastic elastomer include Summit FLX manufactured by Sumitomo Chemical Co., Ltd. In addition, the vinyl chloride thermoplastic elastomer is NB
R (acrylonitrile-butadiene copolymer rubber),
A rubbery polymer such as EVA (ethylene-vinyl acetate copolymer rubber) may be blended. In this case, a powder compact excellent in cold shock resistance can be obtained.

The thermoplastic polyester elastomer is, for example, a hard segment made of an aromatic polyester (for example, a condensation product of 1,4-butanediol and terephthalic acid) and an aliphatic polyether (for example, condensation of polytetramethylene glycol and terephthalic acid). Or a soft segment composed of an aliphatic polyester, and optionally a pigment or a stabilizer is added to the thermoplastic elastomer. Further, the polyester-based thermoplastic elastomer may further contain a rubber polymer such as NBR (acrylonitrile-butadiene copolymer rubber) or EVA (ethylene-vinyl acetate copolymer rubber). A powder compact having excellent cold shock resistance can be obtained.

The thermoplastic polyamide elastomer is
It is a block copolymer having a crystalline polyamide having a high melting temperature as a hard segment and an amorphous polyether or polyester having a low glass transition temperature as a soft segment. A pigment and a stabilizer are added as needed. The thermoplastic polyamide-based elastomer is roughly classified into two types, a polyether ester amide type and a polyester amide type. Further, the thermoplastic polyamide-based elastomer further includes NBR (acrylonitrile-butadiene copolymer rubber) and EVA (ethylene-
A rubbery polymer such as a vinyl acetate copolymer rubber) may be blended, and in this case, a powder molded product having excellent cold shock resistance can be obtained.

The thermoplastic polyurethane elastomer is a thermoplastic elastomer having polyurethane in the hard segment and polyol or polyester in the soft segment. A pigment and a stabilizer are added as needed. Examples of the powder composed of the thermoplastic polyurethane elastomer include Meltex LA manufactured by Sanyo Kasei Co., Ltd.

These thermoplastic resins or thermoplastic elastomers include mineral oil type softeners, phenol type, sulfite type, phenylalkane type, phosphite type,
It may contain various additives such as amine-based and amide-based heat stabilizers, weather stabilizers, antistatic agents, pigments, metallic soaps, waxes, fungicides, antibacterial agents, fillers and the like.

In addition to the fine powder composition, the thermoplastic powder of the present invention further comprises (C) a primary particle size based on 100 parts by weight of a pulverized product of a granular thermoplastic resin or thermoplastic elastomer. 0.1 to 5 parts by weight of powder having a particle size of more than 300 nm and 10 μm or less may be blended. In this case, as compared with the case where the fine powder composition is used alone,
Further, a thermoplastic powder having excellent bulk specific gravity (packing property) and aggregation resistance can be obtained.

The method of blending the above-mentioned fine powder and (C) into the granular thermoplastic resin or thermoplastic elastomer is not particularly limited. For example, a blending method using a blender with a jacket, a high-speed rotary mixer, a Nauta mixer, or the like can be used. Above all, like Henschel mixer and super mixer,
A method of preventing mutual adhesion by applying a shearing force and uniformly dispersing is preferable. Further, the compounding is usually performed at room temperature.

At this time, the granular thermoplastic resin or thermoplastic elastomer, the above-mentioned fine powder composition and (C) may be blended all at once, or the granular thermoplastic resin or thermoplastic elastomer and After blending the fine powder composition, (C) may be blended, or after blending the granular thermoplastic resin or thermoplastic elastomer and (C), the fine powder composition is blended. You may. Further, the granular thermoplastic resin or thermoplastic elastomer may be blended after the fine powder composition and (C) are mixed in advance.

Examples of the component constituting (C) include the above-mentioned inorganic oxides, pigments, vinyl chloride resin for paste, fatty acid metal salts and the like. In addition, JP 2000-3
It is also possible to use an acrylate-based polymer having a glass transition temperature of 60 ° C. or higher and a non-halogen-based resin having a specific sphericity described in Japanese Patent No. 36219 or JP 2001-123019 A.

When powder-molding the above-mentioned thermoplastic powder, the complex dynamic viscosity η at 250 ° C. of the thermoplastic resin or thermoplastic elastomer constituting the thermoplastic powder
^* (1) is preferably 1 × 10 ^{2 to} 5 × 10 ⁴ poise, and more preferably 3 × 10 ² to 8 × 10 ³ poise. Here, the complex dynamic viscosity η ^* (ω) is the following calculation formula (1) using the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ (ω) at a temperature of 250 ° C. and a vibration frequency ω. The complex dynamic viscosity η ^* (1) is the complex dynamic viscosity at ω = 1 rad / sec. η ^* (ω) = {[G ′ (ω)] ² + [G ″ (ω)] ² } ^1/2 / ω (1) If η ^* (1) exceeds the above upper limit, the thermoplastic powder The melt flowability is poor, and it tends to be difficult to produce a powder compact by a compacting method such as a powder compacting method, which has a low shearing rate at the time of 1 sec ^-1 or less.

When the thermoplastic powder of the present invention is powder-molded, it should be 0.28 or less, preferably 0.01 to 0.20, and more preferably 0.0 to 0.20.
It is preferably in the range of 3 to 0.15. Here, the Newtonian viscosity index n is the following using the complex dynamic viscosity η ^* (1) and the complex dynamic viscosity η ^* (100) measured at a temperature of 250 ° C. and a vibration frequency ω = 100 rad / sec. It is a value calculated by the calculation formula (2). When ^{n = {logη * (1)} -logη * (100)} / 2 (2) Newtonian viscosity index n exceeds the upper limit of the foregoing, the mechanical strength of the resulting powder compact tends to be low.

When the thermoplastic powder of the present invention is a powder made of a thermoplastic elastomer, the above-mentioned kneading and dynamic crosslinking are carried out so as to satisfy the above-mentioned physical properties indicated by the complex dynamic viscosity and Newtonian viscosity index. Degree, the type and amount of each component constituting the thermoplastic elastomer, the type and amount of the cross-linking agent or cross-linking aid in the dynamic cross-linking, the type of additive and the amount thereof are appropriately selected. . Among them the shear rate in the kneading and dynamic crosslinking greatly impact the physical properties of the shear rate 1 × 10 ³ seconds ^{- 1} or more it is preferred that kneading and dynamic crosslinking at.

The thermoplastic powder can be produced by a method of mechanically crushing the above-mentioned thermoplastic resin or thermoplastic elastomer, a strand cut method, a die face cut method, a solvent treatment method and the like.

As a method of mechanically pulverizing a thermoplastic resin or a thermoplastic elastomer, there are a freeze pulverization method and a room temperature pulverization method. The freeze pulverization method is a method in which the thermoplastic resin or thermoplastic elastomer is cooled to a glass transition temperature or lower, preferably −70 ° C. or lower, more preferably −90 ° C. or lower, and pulverized while keeping the cooled state.

In order to grind the thermoplastic resin or the thermoplastic elastomer while keeping it in a cooled state, it is preferable to grind by a method having good grinding efficiency and less heat generation. For example, an impact type grinder such as a ball mill is used. The mechanical crushing method used is used. The powder made of the thermoplastic resin or thermoplastic elastomer in this method is usually Tyler standard sieve 24 mesh (opening 700 μm ×
700 μm), preferably 28
The size is such that it passes through a mesh (opening 590 μm × 590 μm), and more preferably 32 mesh (opening 5
00 μm × 500 μm), particularly preferably 42 mesh (mesh opening 355 μm × 355 μm).

The method of blending the fine powder with the powder of the thermoplastic resin or the thermoplastic elastomer is not particularly limited as long as the fine powder is uniformly attached to the pulverized product of the thermoplastic elastomer. Absent. For example, a blending method using a blender with a jacket or a high-speed rotary mixer can be used. Above all, like Henschel mixer and super mixer,
A method of preventing mutual adhesion of the powders by applying a shearing force and uniformly dispersing the powders is preferable. Further, the compounding is usually performed at room temperature.

The powder made of a thermoplastic resin or a thermoplastic elastomer can also be produced by the following method. In this case, a powder having excellent powder fluidity can be obtained without blending the above-mentioned fine powder, but the blending of the fine powder can further improve the powder fluidity.

Solvent treatment method: A thermoplastic resin or a thermoplastic elastomer is treated at a temperature not higher than its glass transition temperature (usually -70 ° C.).
Thereafter, the mixture is cooled to preferably −90 ° C. or lower) and pulverized.
Then, the powder produced by the above-mentioned freeze pulverization method, in a solvent having poor compatibility with a thermoplastic resin or a thermoplastic elastomer, in the presence of a dispersant and an emulsifier, the melting temperature of the powder or more, preferably the melting 30 ~ 5 than temperature
After stirring at a temperature higher by 0 ° C., the mixture is cooled (see, for example, JP-A-62-280226). In the solvent treatment method, as the solvent, for example, ethylene glycol, polyethylene glycol, polypropylene glycol or the like is usually 300 to 10 per 100 parts by weight of the powder.
It is used in an amount of 00 parts by weight, preferably 400 to 800 parts by weight. As the dispersant, for example, ethylene-acrylic acid copolymer, silicic acid anhydride, titanium oxide and the like are used usually in the range of 5 to 20 parts by weight, preferably 10 to 15 parts by weight, per 100 parts by weight of the powder. . As the emulsifier, for example, polyoxyethylene sorbitan monolaurate, polyethylene glycol monolaurate, sorbitan tristearate, etc. are usually 3 to 15 parts by weight, preferably 5 to 10 parts by weight per 100 parts by weight of the powder.
Used in the range of parts by weight.

Strand cut method: A molten thermoplastic resin or thermoplastic elastomer is extruded from a die into the air to form a strand, which is cooled and cut (see, for example, JP-A-50-149747).
In the above-mentioned strand cut method, the die outlet diameter is usually 0.1 to 3 mm, preferably 0.2 to 2 m.
It is in the range of m. The discharge rate of the thermoplastic elastomer per discharge port of the die is usually 0.1 to 5 kg / hour,
It is preferably in the range of 0.5 to 3 kg / hour. The take-up speed of the strand is usually in the range of 1 to 100 m / min, preferably 5 to 50 m / min. The cooled strand is usually 1.4 mm or less, preferably 0.3 to
It is cut to 1.2 mm.

Die face cutting method: A molten thermoplastic resin or a molten thermoplastic elastomer is cut while being extruded from a die into water. In the die face cutting method, the discharge port diameter of the die is usually 0.1.
-3 mm, preferably 0.2-2 mm. The discharge speed of the thermoplastic elastomer per discharge port of the die is usually 0.1 to 5 kg / hour, preferably 0.5.
In the range of up to 3 kg / hour. The temperature of water is usually 30-
It is in the range of 70 ° C, preferably 40 to 60 ° C.

When the thermoplastic elastomer is a vinyl chloride thermoplastic elastomer or a polyurethane thermoplastic elastomer, it is also possible to obtain the spherical thermoplastic elastomer powder in one step during the polymerization.

The above-mentioned thermoplastic powder can be applied to various powder molding methods such as a powder slush molding method, a fluidized dipping method, an electrostatic coating method, a powder spraying method and a powder rotational molding method. For example, the powder slush molding method is performed as follows.

First step: a step of applying a fluorine-based and / or silicone-based release agent on the molding surface of the mold. When powder molding is performed with the thermoplastic powder of the present invention, it may be difficult to remove the obtained powder compact (sixth step) depending on the shape. Therefore, the molding surface of the mold should be preliminarily silicone-based or fluorine-based spray. It may be coated with a spray such as. Examples of the silicone-based spray include KF96SP manufactured by Shin-Etsu Silicone Co., Ltd. (diluted with organic solvent) and the like, and examples of the fluorine-based spray include Daifree GA-6010 (diluted with organic solvent) and ME- manufactured by Daikin.
413 (water diluted product) and the like.

Second step: a step of supplying the thermoplastic powder to the molding surface of the mold heated above the melting temperature of the thermoplastic powder. It is supplied onto the molding surface of a mold heated to 320 ° C., preferably 210 to 300 ° C. In this way,
The mold is, for example, a gas heating furnace system, a heat medium oil circulation system,
It is heated by a method of immersion in heat medium oil or heat fluidized sand, a high frequency induction heating method, or the like. The heating time for heat-sealing the thermoplastic powder is appropriately selected according to the size and thickness of the target molded body.

Third step: the step of heating the thermoplastic powder on the molding surface of the second step for a predetermined time, and fusing the powders whose surfaces have been melted to each other for a predetermined time on the molding surface. During the heating, the powders whose surfaces are at least melted are fused with each other.

Fourth step: a step of collecting the powder which has not been fused after the lapse of the predetermined time in the third step. The powder which has not been fused is recovered after the lapse of the predetermined time.

Fifth step: If necessary, a step of further heating the mold on which the molten thermoplastic powder is placed. If necessary, the mold on which the molten thermoplastic powder is placed is further heated. .

Sixth step: After the fifth step, the mold is cooled and the molded body formed thereon is removed from the mold. The mold is cooled and the molded body formed thereon is removed. Remove from mold.

A foamed molded article can be produced by powder-molding the thermoplastic powder of the present invention containing a foaming agent and further foaming it. The foaming agent may be contained in the powder in advance, or may be coated on the surface of the powder by a rotary mixer such as the above-mentioned Henschel mixer.

As the foaming agent, a thermal decomposition type foaming agent is usually used. Examples of the thermal decomposition type foaming agent include azodicarbonamide, 2,2′-azobisisobutyronitrile, azo compounds such as diazodiaminobenzene, benzenesulfonyl hydrazide, benzene-1,3-sulfonylhydrazide, p- Sulfonylhydrazide compounds such as toluenesulfonylhydrazide, N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-
Nitroso compounds such as N, N′-dimethyl terephthalamide, azide compounds such as terephthal azide, carbonates such as sodium bicarbonate, ammonium bicarbonate, and ammonium carbonate are included. Among them, azodicarbonamide is preferably used. The foaming agent is usually compounded at a temperature equal to or lower than the decomposition temperature of the foaming agent. The foaming agent can be blended at the same time as the above-mentioned fine powder composition or individually.

Further, the thermoplastic powder of the present invention may contain a foaming aid and a cell regulator together with the foaming agent.

A powder compact obtained by molding the thermoplastic powder of the present invention is useful as a skin material, but a two-layer compact having a foam layer laminated on one surface side thereof is used as a skin material. Good. Such a two-layer molded body can be integrally manufactured by a powder molding method (see Japanese Patent Laid-Open No. 5-473, etc.), or a separately manufactured foamed body can be attached to the powder molded body obtained above by an adhesive or the like. It can also be manufactured by a method of adhering.

Furthermore, it is also possible to obtain a composite molded article composed of a non-foamed layer-foamed layer-non-foamed layer by a powder molding method. In this case, the non-foamed layers may be the same or different.

A polyurethane foam may be used as the foam layer of the two-layer molded product or the composite molded product. In this case, when the adhesiveness between the non-foamed layer and the polyurethane foam is poor, the adhesiveness can be improved by pretreating the adhesive surface of the molded body with a primer such as chlorinated polyethylene. The polyurethane foam is fixed at a predetermined position with a certain gap between the molded body and a core material described later.
It is molded by injecting a mixed liquid of polyol and polyisocyanate into the gap and foaming under pressure.

Such a molded product, a two-layer molded product or a composite molded product is suitable as a skin material laminated on a thermoplastic resin core material. For example, the molded product has a thermoplastic resin core material laminated on one surface side thereof. The two-layer molded product or the composite molded product can be used for a multilayer molded product in which a thermoplastic resin core material is laminated on the foam layer side.

As the thermoplastic resin in the thermoplastic resin core material, for example, polyolefins such as polypropylene and polyethylene, and thermoplastic resins such as ABS (acrylonitrile-butadiene-styrene copolymer) resin are used. Among them, polyolefin such as polypropylene is preferably used. Such a multilayer molded body can be easily prepared by, for example, a method of supplying a thermoplastic resin melt to one surface side of the molded body and pressurizing it, or a method of supplying a thermoplastic resin melt to the foam layer side of a two-layer molded body and pressurizing it. Can be manufactured.

Further, in a two-layer molded product, a composite molded product or a multi-layer molded product, the powder molded product obtained by powder molding the thermoplastic powder of the present invention is coated with a paint to obtain scratch resistance of the powder molded product. It is also possible to improve wear resistance. As the paint, known urethane-based,
A one-component type or two-component type paint such as an acrylic type can be used.

[0105]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. [1] Complex dynamic viscosity η ^* (1) and Newtonian viscosity index n of olefinic thermoplastic elastomer used in Examples Dynamic analyzer (RD manufactured by Rheometrics Co., Ltd.)
S-7700 type) was used to measure the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ (ω) at a vibration frequency ω = 1 radian / sec or 100 radian / sec, and the above calculation formula (1 ) Was used to calculate the complex dynamic viscosities η ^* (1) and η ^* (100). The measurement was performed in the parallel plate mode, applied strain of 5%, and sample temperature of 250 ° C. Also, η ^* (1) and η
^* (100) was used to determine the Newtonian viscosity index n by the above calculation formula (2). [2] Evaluation of releasability of powder slush molded product obtained by powder slush molding of thermoplastic powder made of olefinic thermoplastic elastomer, into a mold of a powder slush molded product obtained by powder slush molding by the method described below. The width of the contacting part is 10 cm
The end portion of the powder slush molded body was peeled off so that
Then, the powder slush molding was taken out of the mold while keeping the direction of force horizontal (180 °) to the mold surface. The force required for the removal per 10 cm width was measured using a spring balance. [3] Evaluation of Meltability of Powder Slush Molded Product Formed by Powder Slush Molding of Thermoplastic Powder Made of Olefinic Thermoplastic Elastomer The meltability of the powder slush molded product obtained by powder slush molding by the method described below is shown below. It was evaluated according to the standard. ◯: The back surface of the powder slush molded product was uniformly melted, and no unevenness was observed. X: The back surface of the powder slush molded product was not melted uniformly and unevenness was observed.

Example 1 [Production of olefinic thermoplastic elastomer powder] Propylene-ethylene copolymer resin [Sumitomo Chemical Co., Ltd., ethylene unit content 5% by weight, MFR = 220 g]
/ 10 minutes] 100 parts by weight, hydrogenated product of styrene-butadiene-styrene copolymer [total styrene unit content 15% by weight, MFR = 30 g / 10 minutes, hydrogenation rate 98%] 100 parts by weight and ethylene / propylene Rubber [Sumitomo Chemical Co., Ltd., propylene unit content 27% by weight, MFR = 1
g / 10 minutes] 50 parts by weight were kneaded at a temperature of 170 ° C. using a single-screw kneader [VS 40 mm extruder manufactured by Tanabe Plastic Machinery Co., Ltd.] to obtain a composition [η
^* (1) = 1.2 × 10 ³ poise, n = 0.07],
This was cut with a cutting machine to obtain pellets. The pellets were cooled to −120 ° C. using liquid nitrogen, and then pulverized while maintaining the cooled state, and a pulverized product of an olefinic thermoplastic elastomer [Tyler standard sieve 42 mesh (opening 355
μm × 355 μm). Then, per 100 parts by weight of this pulverized material, 70% by weight of fine powder (silica manufactured by Degussa, OX-50) having a surface with a primary particle size of 50 nm and not treated with silicone oil, and a primary particle size of 14 nm 1 part by weight of a fine powder composition consisting of 30% by weight of fine powder whose surface is treated with silicone oil (fine powder R202 manufactured by Degussa, silica treated with silicone oil) and the primary particle size is 3 μn 2 parts by weight of fine powder (alumina silica, JC-30 manufactured by Mizusawa Chemical Co., Ltd.) were blended with a Henschel mixer to obtain a thermoplastic powder composed of an olefin-based thermoplastic elastomer.

[Manufacture of Powder Compact and Evaluation of Releasability] (1) Nickel mold (15c) having an uneven pattern on the surface
m × 15 cm × 3 mm thickness) was subjected to a honing treatment (washing treatment) using a mixture of sand and glass beads. (2) The mold was placed on an iron plate (hot plate) heated to 290 ° C. and heated. The surface temperature of the mold is 260
When it reaches ℃, sprinkle the above-mentioned thermoplastic powder,
The thermoplastic powders were melted and fused together. 1
After 0 seconds, the thermoplastic powder that had not been fused was recovered by being blown off. The mold was placed on the above-mentioned iron plate for 60 seconds, and then the mold was water-cooled, and the releasability of the obtained powder slush molding was evaluated. The results are shown in Table 1. The thickness of the powder slush molding was about 1 mm.

Comparative Example 1 Fine powder (Silica OX-50 manufactured by Degussa Co., Ltd.) 1 whose surface having a primary particle size of 50 nm is not treated with silicone oil per 100 parts by weight of the pulverized product in Comparative Example 1
The releasability was evaluated according to Example 1 except that the parts by weight were blended. The results are shown in Table 1.

Comparative Example 2 In Example 1, fine powder having a primary particle diameter of 14 nm per 100 parts by weight of the pulverized material, the surface of which was treated with silicone oil (Degussa's fine powder R202, treated with silicone oil). The releasability was evaluated according to Example 1 except that 1 part by weight of silica) was blended. The results are shown in Table 1.

Comparative Example 3 In Example 1, a fine powder whose primary particle diameter was 50 nm and whose surface was not treated with silicone oil per 100 parts by weight of the pulverized product (silica manufactured by Degussa, OX-50)
0.3 parts by weight and 0.7 parts by weight of fine powder having a primary particle size of 14 nm whose surface is treated with silicone oil (fine powder R202 manufactured by Degussa Co., silica treated with silicone oil) Was evaluated for releasability according to Example 1. The results are shown in Table 1.

[0111]

[Table 1]

[0112]

As described above, according to the present invention, a fine powder composition comprising two specific types of fine powder and a granular thermoplastic resin or thermoplastic elastomer are blended with the fine powder composition. It was possible to provide a thermoplastic powder which provides a powder compact having excellent melt cohesiveness and excellent releasability when taken out from the molding surface of the mold.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 12, 2002 (2002.7.1)
2)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

The thermoplastic powder used in the present invention is
The granular thermoplastic resin or thermoplastic elastomer described above
A fine powder composition is blended.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

The thermoplastic powder of the present invention is granular.
When it is composed of a thermoplastic elastomer, the degree of kneading and dynamic crosslinking described above, the type of each component constituting the thermoplastic elastomer, and the type of each component constituting the thermoplastic elastomer so as to satisfy the physical property values shown by the complex dynamic viscosity and the Newtonian viscosity index described above. The amount to be used, the type and amount of the crosslinking agent or crosslinking aid in the dynamic crosslinking, the type and amount of the additive, and the like are appropriately selected. Above all, the shear rate in kneading or dynamic crosslinking has a great influence on the above-mentioned physical property values, and it is preferable to perform kneading or dynamic crosslinking at a shear rate of 1 × 10 ³ sec ⁻¹ or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0080

[Correction method] Change

[Correction content]

Granular thermoplastic resin or thermoplastic elastomer
The mer can be produced by a method of mechanically pulverizing the above-mentioned thermoplastic resin or thermoplastic elastomer, a strand cut method, a die face cut method, a solvent treatment method, or the like.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

In order to grind the thermoplastic resin or the thermoplastic elastomer while keeping it in a cooled state, it is preferable to grind by a method having good grinding efficiency and less heat generation. For example, an impact type grinder such as a ball mill is used. The mechanical crushing method used is used. Granular heat in this way
The plastic resin or thermoplastic elastomer has a size that normally passes through a Tyler standard sieve 24 mesh (opening 700 μm × 700 μm), preferably a size that passes through 28 mesh (opening 590 μm × 590 μm),
More preferably 32 mesh (opening 500 μm × 50
0 μm), particularly preferably 42 mesh (opening 355)
(μm × 355 μm).

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0083

[Correction method] Change

[Correction content]

Granular thermoplastic resin or thermoplastic elastomer
The method of blending the fine powder with the polymer is not particularly limited as long as the fine powder is uniformly attached to the pulverized product of the thermoplastic elastomer. For example, a blending method using a blender with a jacket or a high-speed rotary mixer can be used. Among them, a method such as a Henschel mixer or a super mixer, in which mutual adhesion of the powders is prevented by applying a shearing force and the powders are uniformly dispersed is preferable. Further, the compounding is usually performed at room temperature.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

Granular thermoplastic resin or thermoplastic elastomer
The mer can also be produced by the following method.
In this case, a powder having excellent powder fluidity can be obtained without blending the above-mentioned fine powder, but the blending of the fine powder can further improve the powder fluidity.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AC011 AC021 AC031 AC061                       AC091 AC141 BB001 BB021                       BB031 BB041 BB111 BB121                       BB141 BB151 BB161 BB171                       BC031 BC041 BC051 BD031                       BG041 BL011 BN151 BP011                       CK021 CL081 DE046 DE146                       DJ006 FB096 FD016 FD32                       GF00 GH00 GH01

Claims (3)

[Claims] 1. The following (A) 10 to 50% by weight and (B)
A fine powder composition comprising 90 to 50% by weight. (A): Fine powder whose surface is not treated with silicone oil, and whose primary particle size is 5 to 300 nm (B): Fine powder whose surface is treated with silicone oil And fine powder having a primary particle size of 5 to 300 nm 2. A thermoplastic powder comprising 100 parts by weight of a granular thermoplastic resin or thermoplastic elastomer and 0.1-10 parts by weight of the fine powder composition according to claim 1 in total. 3. The thermoplastic powder (C) according to claim 2, further comprising 0.1 to 10 parts by weight of the following (C): a powder having a primary particle size of more than 300 nm and 10 μm or less.