JP2000344962A - Thermoplastic elastomer composition for powder molding and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer composition whose molding temperature can be lowered and which can give molded articles having excellent flexibility and is useful for powder molding. SOLUTION: This thermoplastic elastomer composition for powder molding comprises (I) 100 pts.wt. of a component, (II) 5 to 300 pts.wt. of a component and (III) 1 to 200 pts.wt. of a component, and has a complex dynamic viscosity η*of 1.5×105 poises at 250 deg.C and a Newtonian viscosity index n of <=0.67. The component I: a polyolefin-based resin. The component II: (II-1) a hydrogenated aromatic vinyl compound-conjugated dienic compound copolymer and/or (II-2) an ethylene-α-olefinic copolymer. The component III: one or more materials selected from (III-1): a petroleum resin, (III-2): a wax, and (III-3): a terpenic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition for powder molding, a powder of the thermoplastic elastomer composition, a powder molding method, a molded article, and a method for producing a molded article. More specifically, the present invention relates to a thermoplastic elastomer composition for powder molding which can be molded at a low molding temperature and can obtain a molded article having excellent flexibility, and a molding method using the powder. Things.

[0002]

2. Description of the Related Art Conventionally, a sheet-like molded article having a complicated uneven pattern such as a leather grain or a stitch on its surface has been used as a skin material for automobile interior parts and the like. As such a molded article, as an alternative to a conventional molded article of vinyl chloride resin,
A molded product obtained by powder-molding a powder obtained by pulverizing an olefin-based thermoplastic elastomer has been proposed (for example, JP-A-5-5050 and JP-A-7-500).
See No. 82433. ). In a powder molding technique using such a thermoplastic elastomer, a lower molding temperature is required from the viewpoint of shortening the molding cycle and the like. In addition, many molded articles such as automobile interior parts are required to have improved flexibility. As a method of improving flexibility, a method of compounding a large amount of a rubber component is known.
However, when a large amount of the rubber component is blended, there is a problem that the molding temperature becomes high.

[0003]

Under these circumstances, the problem to be solved by the present invention is to reduce the molding temperature and to obtain a molded article having excellent flexibility. The object is to provide a thermoplastic elastomer composition, a thermoplastic elastomer composition powder using the composition, and a molded article.

[0004]

That is, the first invention of the present invention comprises the following (A) 100 parts by weight, (B) 5 to 5
300 parts by weight and (c) 1 to 200 parts by weight,
Complex dynamic viscosity η ^* (1) at 50 ° C. is 1.5 × 10 ⁵
Not more than poise and the Newtonian viscosity index n is 0.6
The present invention relates to a thermoplastic elastomer composition for powder molding which is 7 or less. (A): Polyolefin resin (B): The following (B-1) and / or (B-2) (B-1): Hydrogenated aromatic vinyl compound-conjugated diene compound copolymer (B-2) : Ethylene-α-olefin-based copolymer rubber (c): at least one of the following (c-1), (c-2) and (c-3) (c-1): petroleum resin (c) 2): Waxes (c-3): Terpene-based resin The second invention of the present invention relates to a thermoplastic elastomer composition powder comprising the thermoplastic elastomer composition of the first invention. The third invention of the present invention relates to a method for molding the thermoplastic elastomer composition powder of the second invention and a molded product obtained by powder molding.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention is a polyolefin resin. The polyolefin-based resin is at least one selected from crystalline polymers or copolymers obtained by polymerizing or copolymerizing one or more olefins. Examples of the olefin include olefins having 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene. Examples of (a) include polypropylene, α-olefin copolymers containing propylene as a main component other than propylene, poly (1-butene), high-pressure polyethylene, low-pressure polyethylene, linear low-density polyethylene, and ethylene. -Α olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer and the like.

The hydrogenated aromatic vinyl compound-conjugated diene compound copolymer of the component (b-1) of the present invention is obtained by hydrogenating an aromatic vinyl compound-conjugated diene compound copolymer, A hydrogenated product of a vinyl group-conjugated diene compound block copolymer rubber is preferable, and a known product can be used.

Specific examples of the aromatic vinyl compound (b-1) include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene,
Examples thereof include dichlorostyrene, monobromostyrene, ethylstyrene, and vinylnaphthalene. Among them, styrene is preferred from the viewpoint of industrialization.

Specific examples of the conjugated diene compound (b-1) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and 2-neopentyl-1,3-
Examples thereof include butadiene, 2-chloro-1,3-butadiene, and 2-cyano-1,3-butadiene. Among them, butadiene and isoprene are preferable from the viewpoint of industrialization.

The component (b-2) of the present invention comprises ethylene-α
-Olefin copolymer rubber. As the ethylene-α-olefin copolymer rubber, a known ethylene-α
-Olefin copolymer rubber and ethylene-α-olefin-non-conjugated diene copolymer rubber.

The α-olefin in the ethylene-α-olefin copolymer rubber includes, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-pentene, 1-octene, 1-decene and the like. Α-olefins having 3 to 10 carbon atoms are exemplified, with propylene being preferred. Examples of the non-conjugated diene include 1,4-hexadiene, dicyclopentadiene,
Non-conjugated dienes such as 5-ethylidene-2-norbornene can be mentioned.

The component (b-2) is preferably an ethylene-propylene copolymer rubber from the viewpoint of low-temperature impact properties.

The component (b) used in the present invention is the above (b-1) and / or (b-2). When (b-1) and (b-2) are used in combination, the ratio of (b-1) / (b-2) is not particularly limited.

The component (c) of the present invention is at least one selected from the group consisting of petroleum resins, waxes, and terpene resins.

Petroleum resins are low molecular weight thermoplastic hydrocarbon resins derived from cracked petroleum fractions and differ from higher molecular weight polymers made from nearly pure starting materials such as polyethylene, polypropylene, polystyrene and the like. There is no problem even if the petroleum resin has been subjected to a treatment such as hydrogenation for improving the odor and color tone.

As the waxes, either natural waxes or synthetic waxes can be used. What are natural waxes?
Paraffin wax which is a solid wax at normal temperature separated and purified from vacuum distilled distillate oil, and microcrystalline wax (microcrystalline wax) which is a solid wax at normal temperature separated and purified from vacuum distillation residual oil or heavy distillate oil is can give. In addition, animal waxes, vegetable waxes, and mineral waxes are also included. These natural waxes may be modified by an addition reaction or a substitution reaction. Synthetic waxes include Fischer-Tropsch wax synthesized from natural gas by the Fischer-Tropsch method, polyethylene wax and the like.

The terpene resin is a resin obtained by polymerizing terpenes such as hemiterpene, monoterpene, sesquiterpene and diterpene, and having a molecular weight of about several hundreds to several thousands. In addition, those to which hydrogenation and other compounds are added for improving heat resistance and the like are also included.
As (c), those which are solid at ordinary temperature are preferable from the viewpoint of handling properties.

The thermoplastic elastomer composition of the present invention comprises:
It contains 100 parts by weight of (A), 5 to 300 parts by weight of (B) and 1 to 200 parts by weight of (C), and preferably 100 parts by weight of (A) and 10 to 200 parts by weight of (B). And (c) containing 5 to 100 parts by weight, if (b) is too small, the obtained molded article is inferior in flexibility,
On the other hand, if it is excessive, the meltability of the thermoplastic elastomer composition is inferior. If (c) is too small, the meltability of the thermoplastic elastomer composition is not sufficient, while if it is too large, the mechanical strength of the obtained molded article is poor.

The thermoplastic elastomer composition of the present invention comprises:
In addition to the essential components (a) to (c), if necessary, other rubber components such as butadiene-based copolymers, isoprene-based copolymers and hydrogenated products thereof, and styrene-based thermoplastic elastomers Etc. may be added. It is also possible to carry out a crosslinking reaction by adding a peroxide as required. Further, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a pigment, a filler, a flame retardant, a mineral oil-based softener, a foaming agent, and a foaming aid may be added. Good.

As a method for obtaining the thermoplastic elastomer of the present invention, a method of melt-kneading with a single-screw extruder, a twin-screw extruder or the like can be mentioned.

The thermoplastic elastomer composition of the present invention comprises:
Complex dynamic viscosity η ^* (1) at 250 ° C. is 1.5 × 1
0 is ⁵ poises, preferably not more than 5 × 10 ³ poise, more preferably not more than 3 × 10 ³ poise.
The lower limit of η * (1) is usually 1 × 10 poise, preferably 3 × 10 poise, and more preferably 1 × 10 ² poise. Here, the complex dynamic viscosity η * (ω) measured at 250 ° C. at the vibration frequency ω is:
It is a value calculated based on the formula (1) using the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ (ω) measured at the vibration frequency ω at 250 ° C. η * (ω) = (1 / ω) ｛[G ′ (ω)] ² + [G ″ (ω)] ² ｝ ^1/2 (1)

When η * (1) exceeds 1.5 × 10 ⁵ poise, the melt fluidity of the thermoplastic elastomer composition becomes insufficient, and the processability in the powder molding method tends to decrease.

The thermoplastic elastomer composition of the present invention comprises:
The Newtonian viscosity index n calculated from the following equation (2) is 0.
67 or less, preferably 0.01 to 0.3,
Especially preferably, it is a thing of 0.03-0.25. n = {logη * (1) −logη * (100)} / 2 (2)

The thermoplastic elastomer composition of the present invention comprises:
It is used for powder molding as a thermoplastic elastomer composition powder. Examples of a method for obtaining the powder include a known pulverizing method, a strand cutting method, a die face cutting method, and a solvent treatment method.

The powder of the present invention has an average particle size of 1.2 m.
m and a bulk specific gravity of 0.30 g / cc or more are preferable. If the average particle size is too large or the bulk specific gravity is too small, pinholes may be easily generated in the molded product obtained by the powder molding method.

The thermoplastic elastomer composition powder of the present invention contains (d) 0.1 to 10 parts by weight of a fine powder having an average particle size of 10 μm or less per 100 parts by weight of the thermoplastic elastomer composition powder. It may be used as a blended composition. This has the effect of increasing the bulk specific gravity of the thermoplastic elastomer composition powder. The bulk specific gravity is a value measured according to JIS K6721.

The thermoplastic elastomer composition powder comprises:
For example, a method of pulverizing a thermoplastic elastomer composition at a temperature equal to or lower than its glass transition point (hereinafter, referred to as a freeze-pulverization method), and a method of subjecting the powder to a solvent treatment to form a spheroid (hereinafter, referred to as a solvent treatment method). For example, JP-A-62-280
See No. 226. ), A method of hot-melting a thermoplastic elastomer composition, extruding it from a die to form a strand, and then taking or stretching the strand, cutting the strand after cooling (hereinafter referred to as a strand cutting method; 149747), a method of hot-melting a thermoplastic elastomer composition, and extruding the same into water from a die and cutting it immediately after a discharge port of the die (hereinafter, referred to as a die face cut method). Can be manufactured.

When the thermoplastic elastomer composition is produced by a freeze pulverization method, it is usually produced by pulverizing a thermoplastic elastomer composition at a low temperature not higher than the glass transition temperature. For example, a freeze grinding method using liquid nitrogen is suitably used. -70 ° C or less,
Preferably, the thermoplastic elastomer composition pellets cooled to −90 ° C. or lower can be obtained by a mechanical pulverization method using an impact pulverizer such as a ball mill. Pulverization at a temperature higher than -70 ° C is not preferred because the particle size of the pulverized thermoplastic elastomer composition becomes coarse and the powder moldability decreases. In order to prevent the polymer temperature from exceeding the glass transition temperature during the pulverization operation, a method that generates less heat and has a high pulverization efficiency is preferable. Further, it is preferable that the crushing device itself is cooled by external cooling.

When produced by a solvent treatment method, the thermoplastic elastomer composition has a temperature below its glass transition point,
Usually, it is pulverized at a temperature of -70 ° C or less, preferably -90 ° C or less, and then treated with a solvent. Here, the solvent treatment means that the pulverized thermoplastic elastomer composition is stirred in the presence of a dispersant and an emulsifier in a medium having a low compatibility with the pulverized thermoplastic elastomer composition, at or above the melting temperature of the thermoplastic elastomer composition, preferably This is a method of heating to a temperature 30 to 50 ° C. higher than the melting temperature to form a spheroid, then cooling and taking out.

As the medium in the solvent treatment, for example, ethylene glycol, polyethylene glycol,
Examples thereof include polypropylene glycol, and the amount of use is not particularly limited, but is in the range of 300 to 1,000 parts by weight, preferably 400 to 800 parts by weight, per 100 parts by weight of the thermoplastic elastomer used.

Examples of the dispersant include ethylene-acrylic acid copolymer, silicic anhydride, titanium oxide and the like. The amount of the dispersant is usually 5 to 20 parts by weight, preferably 100 to 100 parts by weight of the thermoplastic elastomer used. Is 10-1
The range is 5 parts by weight.

Examples of the emulsifier include, but are not limited to, polyoxyethylene sorbitan monolaurate, polyethylene glycol monolaurate, and sorbitan tristearate. It is usually in the range of 3 to 15 parts by weight, preferably 5 to 10 parts by weight based on parts by weight.

When manufactured by the strand cutting method, the discharge diameter of the die is usually in the range of 0.1 to 3 mm, preferably 0.2 to 2 mm, and the discharge speed from the die is usually 0.1 to 5 kg / hour / hole. , Preferably 0.5 to 3 kg
/ Hour / hole range, strand take-up speed is usually 1-10
0 m / min, preferably in the range of 5 to 50 m / min. The cut length after cooling is usually 1.4 mm or less, preferably 1.2 mm or less.

In the case of manufacturing by a die face cut method, the discharge opening diameter of the die is usually in the range of 0.1 to 3 mm, preferably 0.2 to 2 mm, and the discharge speed from the die is usually 0.1 to 5 kg / hour / hour. Hole, preferably 0.5-3kg
/ Hour / hole range.

The fine powder having an average particle size of 10 μm or less is contained in 100 parts by weight of the thermoplastic elastomer powder produced by the freeze pulverization method, the solvent treatment method, the strand cut method, and the die face cut method. By mixing 10 to 10 parts by weight, the bulk specific gravity (packing property),
A thermoplastic elastomer composition powder having excellent blocking resistance can be obtained.

It should be noted that powders produced by the freeze pulverization method, the solvent treatment method, the strand cut method, and the die face cut method are sometimes referred to as pellets.

The thermoplastic elastomer composition powder of the present invention is used in a powder molding method.

In order to produce a molded article by a powder molding method, the thermoplastic elastomer composition powder of the present invention may be powder-molded. Examples of the powder molding method include a fluid immersion method, an electrostatic coating method, a powder spraying method, a powder rotating method, and a powder slush molding method.

As a preferable powder molding method, a method including all the following steps can be mentioned. First step: a step of supplying the thermoplastic elastomer composition powder of the present invention onto a molding surface of a mold heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition. Heating the thermoplastic elastomer composition powder obtained in one step for a predetermined time, and fusing the thermoplastic elastomer composition powder having at least its surface fused to each other third step: after a lapse of a predetermined time in the second step ,
Step of recovering the non-fused thermoplastic elastomer composition powder Fourth step: If necessary, further heating the mold on which the molten thermoplastic elastomer composition powder is placed Fifth step: Fourth step After the step, the step of cooling the mold and removing the molded body from the mold

Examples of the method for heating the mold include a gas heating furnace method, a heating medium oil circulation method, a dipping method in heating medium oil or hot fluidized sand, and a high-frequency induction heating method.

The temperature of the mold when the thermoplastic composition powder is heat-sealed to the mold is usually 150 to 300 ° C., preferably 190 to 270 ° C. The time from supply of the thermoplastic elastomer composition powder onto the molding surface to removal thereof is not particularly limited, and is appropriately selected depending on the size and thickness of the target molded product.

By molding a thermoplastic elastomer composition powder containing a foaming agent, a foam having excellent flexibility can be produced.

For example, in order to produce a foam by a powder molding method, the thermoplastic elastomer composition powder of the present invention containing a foaming agent may be foamed after powder molding.

As the blowing agent, a thermal decomposition type blowing agent is usually used. Examples of the thermal decomposition type blowing agent include azo compounds such as azodicarbonamide, 2,2'-azobisisobutyronitrile and diazodiaminobenzene. , Sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, benzene-1,3-sulfonyl hydrazide, p-toluenesulfonyl hydrazide, N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-N, N
Nitroso compounds such as' -dimethylterephthalamide, azide compounds such as terephthalazide, sodium bicarbonate,
Carbonates such as ammonium bicarbonate and ammonium carbonate. Among them, azodicarbonamide is preferably used.

As a method for producing a thermoplastic elastomer composition powder containing a foaming agent, a method of mixing the foaming agent with the thermoplastic elastomer composition powder, a method of preparing the thermoplastic elastomer composition in advance at a decomposition temperature or lower. After kneading the foaming agent, it can be obtained by powdering. In addition, a foaming assistant, a cell adjuster, and the like may be mixed together with the foaming agent.

The molded product obtained by molding the thermoplastic elastomer composition powder of the present invention is useful as a skin material, and a two-layer molded product having a foam layer laminated on one surface side is used as the skin material. May be used. Such a two-layer molded body is formed by a powder molding method (see Japanese Patent Application Laid-Open No. 5-473 and the like).
Can be integrally manufactured, or can be manufactured by a method of bonding a separately manufactured foam to the molded article obtained above with an adhesive or the like.

In order to produce a two-layer molded body by the powder molding method, for example, a mold which may have a complicated pattern on its molding surface is heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition. The above-mentioned thermoplastic elastomer composition powder is supplied on the molding surface of the mold, and the thermoplastic composition powders are thermally fused to each other to obtain a sheet-like molten material on the molding surface, and then the thermal fusion is not performed. The excess thermoplastic elastomer composition powder is removed, and then a thermoplastic elastomer composition powder containing a foaming agent is supplied onto the sheet-like melt, and the powders are thermally fused to each other to form a sheet on the molding surface. After obtaining a sheet-like melt, excess thermoplastic elastomer composition powder that has not been heat-sealed may be removed, and then further heated and foamed to form a foamed layer.

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

Examples of the foaming agent include the same pyrolytic foaming agents as described above. Examples of the thermoplastic polymer composition containing such a foaming agent include vinyl chloride resins, polyolefins, and olefinic thermoplastic elastomers. Etc. containing a foaming agent.
The polyethylene-based foamable composition used in Japanese Patent Publication No. 0 can also be used.

Further, a polyurethane foam can be used as the foam layer. In this case, since the adhesiveness between the thermoplastic elastomer composition and the polyurethane tends to be inferior, usually, the adhesiveness can be improved by pretreating the adhesive surface of the molded article with a primer such as chlorinated polyethylene.

The polyurethane foam is fixed at a predetermined position with a predetermined gap between the above-mentioned molded article and a core material described later, and a mixture of polyol and polyisocyanate is injected into the gap, and the polyurethane foam is pressurized. It is molded by foaming.

The thermoplastic elastomer composition powder of the present invention is formed into a molded product by powder molding.

The following can be mentioned as examples of the composite molded body. First, there can be mentioned a two-layer molded article in which a foam layer is laminated on one surface side of the molded article.
Second, a two-layer molded article in which a thermoplastic resin core material is laminated on one surface side of the molded article can be given. Third, a three-layer molded article in which a thermoplastic resin core material is laminated on the foam layer side of the two-layer molded article can be given. As a specific example of such a molded article, there can be mentioned a method for producing a two-layer molded article in which a thermoplastic resin melt is supplied to one surface side of the molded article and then cooled under pressure.

Further, there can be mentioned a method for producing a three-molded body in which a thermoplastic resin melt is supplied to the foam layer side of the two-layered molded body and the mixture is pressurized and cooled.

The molded article or the two-layer molded article obtained by powder molding the above-mentioned thermoplastic elastomer composition powder of the present invention is suitable as a skin material laminated on a thermoplastic resin core material. Can be used for a multilayer molded body in which a thermoplastic resin core material is laminated on one surface side, and a two-layer molded body is a multilayer molded body in which a thermoplastic resin core material is laminated on the foamed layer side. Can be used.

As the thermoplastic resin in the thermoplastic resin core material, for example, a polyolefin such as polypropylene or polyethylene, or a thermoplastic resin such as an ABS (acrylonitrile-butadiene-styrene copolymer) resin is used. Among them, a polyolefin such as polypropylene is preferably used.

In such a multilayer molded article, for example, a thermoplastic resin melt is supplied to one surface side of the molded article and pressurized, or the thermoplastic resin melt is supplied to the foam layer side of the two-layer molded article, and heat treatment is performed. It can be easily manufactured by a pressing method.

The thermoplastic resin melt is a thermoplastic resin which is heated to a temperature higher than its melting temperature and is in a molten state. The supply of the thermoplastic resin melt may be before the pressurization or may be simultaneous with the pressurization. The pressurization may be performed by using a mold or the like, or may be performed by the supply pressure of the thermoplastic resin melt. Examples of such a molding method include an injection molding method, a low-pressure injection molding method, and a low-pressure compression molding method.

Specifically, for example, when the above-described molded body is used as a skin material, the molded body is supplied between a pair of opened molds, and then, one side of the molded body and the other side are formed. After supplying or supplying the thermoplastic resin melt between one of the opposing molds, both molds may be clamped, and in the case of using a two-layer molded body as the skin material, an open pair is used. After supplying the two-layer molded body between the molds, and then supplying or while supplying the thermoplastic resin melt between the foamed layer of the molded body and one of the molds opposed thereto, the two molds are supplied. You only have to clamp the mold. Here, the opening / closing direction of the two dies is not particularly limited, and may be a vertical direction or a horizontal direction.

When a molded article or a two-layer molded article produced by using the above-described powder molding die is used as the skin material,
The powder molding die can be used as one of the dies in the production of the multilayer molded body while holding the molded body or the two-layer molded body on the molding surface. According to this method,
Since the molded article or the two-layer molded article on which the pattern of the mold has been transferred is supplied between the molds without being separated from the mold, the pattern formed on the surface of the molded article is hardly destroyed, and the desired multilayer molding is performed. You can get the body.

The thermoplastic resin melt may be supplied after the clamping of both the molds is completed. However, a multilayer molded article in which a molded article or a two-layer molded article as a skin material has a small displacement and a pattern transfer degree is improved. It is preferable that both dies be clamped during or after supply while both dies are not closed.
The method of supplying the thermoplastic resin melt is not particularly limited. For example, the thermoplastic resin melt can be supplied from a resin passage provided in one of the molds facing the molded product or the two-layer molded product.
Alternatively, the supply nose of the molten resin may be inserted between the two dies to supply the molten resin, and thereafter, the supply nose may be retracted outside the system to close both the dies.

As the pair of dies, a pair of male and female dies in which the outer peripheral surface of one die and the inner peripheral surface of the other die can slide can be used. In this case, by keeping the clearance between the sliding surfaces of the two dies approximately equal to the thickness of the molded article or the two-layer molded article, a multilayer molded article having an extra skin material at its end can be obtained. By folding this extra skin material on the back surface of the multilayer molded body, a multilayer molded body whose end is covered with the skin material layer can be obtained.

The olefinic thermoplastic elastomer composition of the present invention can be optimally used for automobile parts, industrial equipment parts, electric / electronic parts, building materials, miscellaneous goods, etc. by utilizing its excellent characteristics. In automobile parts, it can be used for interior skins of instrument panels, doors, pillars and the like.

[0063]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The evaluation of the thermoplastic elastomer composition was performed by the following method. [1] Complex dynamic viscosity η ^* (1) and Newton viscosity index n Dynamic analyzer (RD) manufactured by Rheometrics
S-7700), the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ (ω) were measured at a vibration frequency of 1 radian / sec and 100 radian / sec, and the above-mentioned equation (1) was used. The complex dynamic viscosities η ^* (1) and η ^* (100) were calculated according to the following formula: The measurement was performed in a parallel plate mode, at an applied strain of 5% and at a temperature of 250 ° C. Further, η ^* (1) and η ^* (100)
Was used to determine the Newtonian viscosity index n according to the above equation (2). [2] Evaluation of flexibility Evaluation of the touch of the slush molded body was performed. After preparing a press sheet at 200 ° C. and at 200 ° C., the flexural modulus was also measured in accordance with JIS K7203. [3] Manufacture of molded body by slush molding method Nickel electroforming mold (30 cm
× 30 cm, thickness 3 mm), and about 1 kg of a thermoplastic elastomer powder was sprinkled on the molding surface. After a certain period of time, the unfused powder is removed, and the above-mentioned mold on which the fused thermoplastic elastomer is placed is placed in the mold for 25 minutes.
It was left for 1 minute in a heating furnace heated to 0 ° C. One minute later, it was taken out of the heating furnace and cooled, and the formed body was removed from the mold. The time from sprinkling the powder on the heated mold until removing the unfused powder is
The thickness of the molded body formed after cooling was adjusted to about 1 mm. The heating temperature of the mold was changed, and the occurrence of pinholes was visually evaluated. Table 1 shows the results.・ ・ ・: Almost no pinhole △: Slight pinhole occurred ×: Pinhole was noticeably generated

Example 1 [Production of thermoplastic elastomer composition powder] As (a) a propylene-ethylene copolymer resin (ethylene unit content: 5% by weight, MFR = 228 g / 10 min (JIS K7210 (load: 2.16 kg) , Temperature 230
C)) 100 parts by weight, hydrogenated butadiene-styrene copolymer as (b) (styrene unit content 12% by weight,
Ratio of conjugated diene unit having a side chain having 2 or more carbon atoms to all hydrogenated conjugated diene units: 77%, hydrogenation rate: 98
%, MFR = 10 g / 10 min (JIS K7210 (load 2.16 kg, temperature 230 ° C.)) 100 parts by weight, and ethylene-propylene copolymer rubber (manufactured by Sumitomo Chemical Co., Ltd., S
POV0141, propylene unit content 27% by weight, M
FR = 1g / 10min (JISK7210 (load 2.16
kg, temperature 190 ° C.)) 25 parts by weight, as (c) aromatic hydrogenated petroleum resin (Arukawa Chemical Co., Inc., Alcon P-14)
0) 25 parts by weight, 0.24 parts by weight of antioxidant (IRGANOX-1076 manufactured by Ciba Specialty Chemicals)
Was kneaded at 180 ° C. using a twin-screw extruder to obtain pellets of a thermoplastic elastomer composition. The pellets were cooled to −120 ° C. using liquid nitrogen, and then pulverized while maintaining the cooling state to obtain a thermoplastic elastomer composition powder (passing through a 32 mesh Tyler standard sieve). 100 parts by weight of the thermoplastic elastomer composition powder thus obtained and 1 part by weight of silica (manufactured by Degussa, grade OX-50),
And alumina silica (Grade JC-3 manufactured by Mizusawa Chemical Co., Ltd.)
0) 2 parts by weight of super mixer (Kawada Seisakusho, 5
L super mixer) at room temperature, 1500 rpm
For 2 minutes to obtain a thermoplastic elastomer powder containing fine powder. Powder slush molding was performed using the thermoplastic elastomer powder. Further, a sheet having a thickness of 2 mm was prepared from the obtained powder with a press set at 200 ° C., and the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ (ω) were measured at a vibration frequency of 1 radian / sec. The complex dynamic viscosities η ^* (1) and η ^* (100) were calculated by the above formula (1) using the parallel plate mode, applied strain of 5%, and temperature of 250. Η ^* (1) and η ^* (100)
Was used to determine the Newtonian viscosity index n according to the above equation (2). Table 1 shows the results.

Comparative Example 1 A propylene-ethylene copolymer resin (ethylene unit content 5% by weight, MFR = 228 g / 10 min,
Load: 2.16 kg, temperature: 230 ° C) 100 parts by weight,
(B) Hydrogenated butadiene-styrene copolymer (content of hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms with respect to all hydrogenated conjugated diene units; styrene unit content: 12% by weight; 77%, hydrogenation rate 98%, MFR
= 10g / 10min, load 2.16kg, temperature 230 ° C)
100 parts by weight, and ethylene-propylene copolymer rubber (manufactured by Sumitomo Chemical Co., Ltd., SPO V0141, propylene unit content 27% by weight, MFR = 1 g / 10 minutes, load 2.1)
6 kg, temperature 190 ° C.) 50 parts by weight, antioxidant 0.2
4 parts by weight (IRGA manufactured by Ciba Specialty Chemicals)
NOX-1076) was kneaded at 180 ° C. using a twin-screw extruder to obtain pellets of a thermoplastic elastomer composition. The pellets were cooled to −120 ° C. using liquid nitrogen, and then pulverized while maintaining the cooling state to obtain a thermoplastic elastomer composition powder (passed through a 32 mesh Tyler standard sieve). Subsequent mixing of the fine powder and production of a molded body by the slush molding method were performed in the same procedure as in Example 1. η ^* (1) and Newton's viscosity index n were determined in the same procedure as in Example 1. Table 1 shows the results.

Example 2 As (a), a propylene-ethylene copolymer resin (ethylene unit content: 5% by weight, MFR = 228 g / 10 min,
(Weight 2.16 kg, temperature 230 ° C) 40 parts by weight, (b)
Hydrogenated butadiene-styrene copolymer (content of styrene unit: 16% by weight, ratio of hydrogenated conjugated diene having a side chain having 2 or more carbon atoms to all hydrogenated conjugated diene units: 75%, water Attachment rate 98%, MFR = 10g / 1
0 minutes, load 2.16 kg, temperature 230 ° C.) 45 parts by weight,
And 5 parts by weight of ethylene-propylene copolymer rubber (manufactured by Sumitomo Chemical Co., Ltd., SPO V0141, propylene unit content 27% by weight, MFR = 1 g / 10 minutes, load 2.16 kg, temperature 190), and microcrystalline as (c) Wax (LUUVAX-2191, manufactured by Nippon Seiro) 10
Parts by weight and 0.1 parts by weight of an antioxidant (IRGANOX-1076 manufactured by Ciba Specialty Chemicals Co., Ltd.) were mixed with a Labo Plastomill kneader (Toyo Seiki Seisakusho Co., Ltd., Model 65C-1).
50), and the mixture was kneaded at 180 ° C. to obtain a thermoplastic elastomer composition. After forming into a pressed sheet at 200 ° C., η ^* (1), Newton's viscosity index, and flexural modulus were determined. Table 2 shows the results.

Example 3 As (a), a propylene-ethylene copolymer resin (ethylene unit content: 5% by weight, MFR = 228 g / 10 min,
(Weight 2.16 kg, temperature 230 ° C) 40 parts by weight, (b)
As a hydrogenated butadiene-styrene copolymer (styrene unit content: 16% by weight, a ratio of hydrogenated conjugated diene units having side chains having 2 or more carbon atoms to hydrogenated conjugated diene units: 75%, Hydrogenation rate 98%, MFR = 10g
/ 10 minutes, load 2.16 kg, temperature 230 ° C.) 45 parts by weight, and ethylene-propylene copolymer rubber (manufactured by Sumitomo Chemical Co., Ltd., SPO V0141, propylene unit content 27)
% By weight, MFR = 1 g / 10 min, load 2.16 kg, temperature 190) 5 parts by weight, (c) 10 parts by weight of a terpene resin (manufactured by Yasuhara Chemical Co., Clearon M-115), 0.1 parts by weight of antioxidant Part (IRGANOX1076 manufactured by Ciba Specialty Chemicals) and a lab plast mill kneader (Model 65C-150 manufactured by Toyo Seiki Seisaku-sho, Ltd.)
And kneaded at 180 ° C. to obtain a thermoplastic elastomer composition. After forming a press sheet at 200 ° C,
η ^* (1), Newton's viscosity index, and flexural modulus were determined. Table 2 shows the results.

Comparative Example 2 A propylene-ethylene copolymer resin (ethylene unit content 5% by weight, MFR = 228 g / 10 min,
(Weight 2.16 kg, temperature 230 ° C) 40 parts by weight, (b)
As a hydrogenated butadiene-styrene copolymer (styrene unit content: 16% by weight, a ratio of hydrogenated conjugated diene units having side chains having 2 or more carbon atoms to hydrogenated conjugated diene units: 75%, Hydrogenation rate 98%, MFR = 10g
/ 10 min, load 2.16 kg, temperature 230 ° C.) 40 parts by weight, and ethylene-propylene copolymer rubber (Sumitomo Chemical Co., Ltd., SPO V0141, propylene unit content 27)
% By weight, MFR = 1 g / 10 min, load 2.16 kg, temperature 190) 20 parts by weight and 0.1 part by weight of an antioxidant were added to a Labo Plastomill kneader (Toyo Seiki Seisakusho, Model 65C)
-150) to obtain a thermoplastic elastomer composition. After forming into a pressed sheet at 200 ° C., η ^* (1), Newton's viscosity index, and flexural modulus were determined. Table 2 shows the results.

[0069]

Table 1 Powder slush moldability, flexibility, and η
^* (1) and n evaluation results

[0070]

[Table 2] η ^* (1), n, and flexibility evaluation results

[0071]

As described above, according to the present invention, a thermoplastic elastomer composition for powder molding and a composition capable of lowering the molding temperature and obtaining a molded article having excellent flexibility are provided. The thermoplastic elastomer composition powder to be used, the powder molding method, the molded article, and the method for producing the molded article could be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 45/00 C08L 45/00 53/02 53/02 57/02 57/02 65/00 65/00 91 / 06 91/06 // B29K 21:00 B29L 31:58 F-term (reference) 4F071 AA12X AA13X AA15X AA20X AA22X AA39X AA69 AA71 AA75X AF21 BA01 BB13 BC07 4F205 AA03K AA04E AA12K AA45 GB07 A04 GC07A04 AE03Y BA01Y BB03W BB05W BB06W BB08W BB12W BB14W BB15W BB15X BB17W BK00Y BP01X CE00Y FA086 FD016

Claims (6)

[Claims] 1. The following (A) 100 parts by weight, (B) 5 to 5
300 parts by weight and (c) 1 to 200 parts by weight,
Complex dynamic viscosity η ^* (1) at 50 ° C. is 1.5 × 10 ⁵
Not more than poise and the Newtonian viscosity index n is 0.6
A thermoplastic elastomer composition for powder molding, which is 7 or less. (A): Polyolefin resin (B): The following (B-1) and / or (B-2) (B-1): Hydrogenated aromatic vinyl compound-conjugated diene compound copolymer (B-2) : Ethylene-α-olefin-based copolymer rubber (c): at least one of the following (c-1), (c-2) and (c-3) (c-1): petroleum resin (c) 2): Waxes (c-3): Terpene resin 2. The thermoplastic elastomer composition according to claim 1, wherein (c) is a solid at room temperature. 3. A thermoplastic elastomer composition powder comprising the thermoplastic elastomer composition according to claim 1. 4. A thermoplastic elastomer composition powder 1
The thermoplastic elastomer composition powder according to claim 3, wherein 0.1 to 10 parts by weight of the following (d) is blended per 00 parts by weight. (D): Fine powder having an average particle size of 10 μm or less 5. A method for producing a molded article, comprising the following steps. The first step: a step of supplying the thermoplastic elastomer composition powder according to claim 3 or 4 onto a molding surface of a mold heated to a melting temperature of the thermoplastic elastomer composition or higher. Heating the thermoplastic elastomer composition powder obtained in the first step on the molding surface of the first step for a predetermined time, and fusing the thermoplastic elastomer composition powder having at least its surface fused to each other third step: After a lapse of a predetermined time in the two steps,
Step of recovering the non-fused thermoplastic elastomer composition powder Fourth step: If necessary, further heating the mold on which the molten thermoplastic elastomer composition powder is placed Fifth step: Fourth step After the step, the step of cooling the mold and removing the shaped body from the mold 6. A molded product obtained by the production method according to claim 5.