JP2002161156A - Coated powder molded material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coated powder molded material that has a superior blush ing and wear resistance. SOLUTION: The coated powder molded material consists of a thermoplastic elastomer composition. The elastomer is constituted of a polyolefin resin and the hydrogenated diene copolymer. The rate of the unit number of a hydrogenated conjugated diene having a side chain, whose carbon number is more than 2, with a unit content of a vinyl aromatic compound in the hydrogenated diene copolymer and the unit number of all conjugated diene hydrogenated, and the quantity of the aromatic vinyl in the hydrogenated diene copolymer and all conjugated diene constitution, are shown in a specific formula. More than 80% of a double bond of the conjugated diene unit in the hydrogenated copolymer is hydrogenated, and the numerical average molecular weight of the hydrogenated diene copolymer is 50,000-600,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated powder compact. More specifically, the present invention comprises a thermoplastic elastomer composition containing a polyolefin-based resin and a hydrogenated diene-based copolymer having a specific structure as essential components, is hardly whitened even when bent, and has excellent wear resistance. The present invention relates to a coated powder molded body having a surface coated with a paint, which does not emit luster when heated to a temperature from about 80 ° C. to a temperature lower than the melting point of the polyolefin resin even if the surface is worn.

[0002]

2. Description of the Related Art Conventionally, a sheet-like molded article having a complex uneven pattern such as a grain or a stitch on the surface has been used as a skin material for an automobile interior part or the like. As such a molded article, a molded article obtained by powder-molding a powder obtained by pulverizing an olefin-based thermoplastic elastomer has been proposed as an alternative to the conventional molded article of a vinyl chloride resin (see, for example, Japanese Patent Application Laid-Open No. Hei 5 (1993) -107). -1183 and JP-A-5-5050). However, since the molded article obtained by such a method is harder than a vinyl chloride resin molded article and has a property of being easily whitened when bent, the molded article is manufactured and then molded. When the mold is removed or when the molded body is previously formed into a desired shape, the bent portion tends to whiten, resulting in poor appearance, resulting in poor productivity.
JP-A-7-82433 describes a powder resin composition comprising a polyolefin resin and a hydrogenated styrene / butadiene random copolymer rubber having a styrene content of 20% by weight or less. The molded product obtained by powder molding the powder resin composition is not used as a painted powder molded product whose surface is coated with a paint because the bent portion does not whiten when bent, but has poor abrasion resistance. (JP-A-2000-1584)
No. 63).

When such a coated powder compact is used, for example, as a skin material for interior materials of automobiles, when dust or the like is present on the surface, a treatment for removing the dust or the like using a dry cloth or the like is frequently performed. At this time, the coating film formed by the coating treatment on the surface may be partially dropped due to abrasion. In such a state, the coated powder compact is heated to a temperature lower than the melting point of the polyolefin resin from about 80 ° C. When heated to a low temperature, it is not practical as a skin material for automobile interior materials, etc., because there is a problem that the surface where the coating film has fallen has a significant gloss on the surface. It has been known that the temperature of the surface of an automobile interior material such as a ment panel rises to about 80 to 120 ° C.).

[0004]

Under these circumstances, an object of the present invention is to provide a thermoplastic elastomer composition containing a polyolefin resin and a hydrogenated diene copolymer having a specific structure as essential components. Even if the surface is worn, it is not glossy when heated to a temperature lower than the melting point of the polyolefin resin from about 80 ° C. even if the surface is worn. Are present in a coated powder molded body that has been coated with a paint.

[0005]

That is, the present invention provides the following:
(I) 100 parts by weight and (II) 10 to 1000 parts by weight
Consisting of a thermoplastic elastomer composition containing
Pertaining to a coated powder compact that has been coated with paint
It is. (I): Polyolefin resin (II): Hydrogenated die that satisfies all of the following conditions
-Based copolymer: The hydrogenated diene-based copolymer has the following structure (A) or (B):
(A): vinyl aromatic compound polymer block (B): selected from the following (B1), (B2) and (B3)
(B1): random of vinyl aromatic compound and conjugated diene
A block obtained by hydrogenating a copolymer block (B2): a block composed of a vinyl aromatic compound and a conjugated diene.
Tapered block with gradually increasing vinyl aromatic compound
Is a hydrogenated block (B3): a conjugated diene polymer block is hydrogenated
Block: Totally vinyl aromatic contained in hydrogenated diene copolymer
The compound unit content (T) is 10 to 18% by weight: all vinyl aromatic compounds in the hydrogenated diene copolymer
Vinyl aromatic compound of the above (A) with respect to the content of
The unit content ratio (S: percentage) is 3% or more: all hydrogenated conjugated dienes in the hydrogenated diene copolymer
Hydrogenated having side chains with 2 or more carbon atoms per unit number
The ratio of the number of conjugated diene units (V: percentage) exceeds 60%
That  : The above (T) in the hydrogenated diene copolymer and the above
(S) and the relationship with the above (V) satisfy the following equation (1).
Satisfaction V ≦ 0.375 × S + 1.25 × T + 40 (1): Concentration of conjugated diene unit in hydrogenated diene copolymer
80% or more of the double bonds are hydrogenated: the number average molecular weight of the hydrogenated diene copolymer is 50,000 to 40
Be a million

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (I) in the thermoplastic elastomer composition used in the coated powder molded product of the present invention is a polyolefin resin and is selected from homopolymers or copolymers of olefins having high crystallinity. At least one type. Examples of the olefin include olefins having 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene. Said (I)
Are polyethylene, polypropylene, poly (1-
Butene), a copolymer of propylene and ethylene, and a copolymer of propylene and another α-olefin (eg, 1-butene). When (I) is a propylene-ethylene copolymer resin or a propylene-1-butene copolymer resin, the thermoplastic elastomer composition of the present invention can provide a molded article having excellent heat resistance and flexibility. It is preferred in that respect. The crystallinity of (I) needs to be 50% or more, and preferably 60% or more.
Here, the crystallinity is determined by an X-ray structure analysis method.

A copolymer obtained by copolymerizing two or more monomers selected from ethylene and an α-olefin having 3 to 8 carbon atoms in two or more stages can also be used. 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. In addition, from the viewpoint of the strength of the molded body obtained by the powder molding method, JIS K-7 of (I)
The melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kgf in accordance with No. 210 is usually 20 to 5
00 g / 10 min, preferably 50 to 300 g / 10
Min, particularly preferably in the range of 100 to 300 g / 10 min. In addition, as (I), a highly fluidized product obtained by decomposition using an organic peroxide or the like can also be used.

(II) in the thermoplastic elastomer composition used in the molded article of the present invention is a hydrogenated diene copolymer which satisfies all of the above conditions.
Examples of the conjugated diene used in the production of (II) include, for example, 1,3-butadiene, isoprene (2-methyl-
1,3-butadiene), 1,3-pentadiene, 2,3
-Dimethyl-1,3-butadiene, 2-methyl-1,3
And conjugated dienes having 4 to 8 carbon atoms such as pentadiene. Among them, 1,3-butadiene is easily available industrially, has excellent cold impact resistance, and even at a low temperature of −20 ° C. or less, the coating film formed by the coating treatment can be easily formed from the coated powder compact. This is preferable because it is difficult to fall off.

The vinyl aromatic compound has one of the vinyl groups.
The 2- or 3-position may be substituted with an alkyl group such as a methyl group. Examples of vinyl aromatic compounds include styrene, p-methylstyrene, α-methylstyrene, t-
Examples thereof include vinyl aromatic compounds having 8 to 12 carbon atoms, such as butylstyrene, divinylbenzene, and vinylpyridine. Among them, styrene is preferably used from an industrial viewpoint.

(II) is a hydrogenated diene copolymer containing the following structural units (A) and (B). (A): vinyl aromatic compound polymer block (B): at least one type of block selected from the following (B1), (B2) and (B3) (B1): random copolymerization of vinyl aromatic compound and conjugated diene Block (B2): a block formed by hydrogenation of a vinyl aromatic compound and a conjugated diene, and a block formed by hydrogenating a tapered block in which a vinyl aromatic compound is gradually increased (B3): a conjugated diene polymer block Is hydrogenated block

(II) is usually represented by the general formula [(A)-(B)]
n, [(A)-(B)] n- (A), [(B)-
(A)] n- (B) (where n is an integer of 1 or more;
When there are a plurality of (A) and (B), each of the plurality of (A) and (B) may be the same or different. ), For example, [(A)-(B
1)] n- (A), [(A)-(B2)] n- (A),
Or [(A)-(B3)] n- (A) (where n is an integer of 1 or more and repeating units (A), (B1) and (B2)
And (B3) may be the same or different. )).

Among them, (A)-(B1)-(A),
(A)-(B2)-(A) or (A)-(B3)-
The hydrogenated diene copolymer represented by (A) is preferable in that it is industrially easy to produce, and is preferably a hydrogenated product of a styrene-butadiene / styrene-styrene copolymer or a water-soluble styrene-butadiene-styrene copolymer. Hydrogenated product of styrene-isoprene-styrene-styrene copolymer, styrene-
Hydrogenated isoprene-styrene copolymers are preferred in that they can be industrially easily produced. In particular, the hydrogenated product of styrene-butadiene-styrene copolymer has excellent strength and cold impact resistance of the obtained coated powder molded product, and the coating film formed by the coating treatment easily falls off from the coated powder molded product. The hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms with respect to the number of all hydrogenated conjugated diene units of the hydrogenated diene-based copolymer described below is difficult. This is preferable in that even if there is a slight “run-out” in the production of the number ratio (V: percentage), it is hardly affected. Note that "-" indicates a boundary between blocks, and "-" indicates that two or more compounds are used in combination in one block.

The total vinyl aromatic compound unit content in (II) must be in the range of 10 to 18% by weight (conditions), and is preferably in the range of 12 to 17% by weight. Total vinyl aromatic compound unit content is 18
When the content is more than 10% by weight, the coated powder molded article of the present invention tends to be hard. Further, when the total vinyl aromatic compound unit content is less than 10% by weight, there is a problem that the powder of the obtained thermoplastic elastomer composition has tackiness.
The total vinyl aromatic compound unit content can be determined by ¹ H-NMR measurement at a frequency of 90 MHz or higher using a solution of (II) such as carbon tetrachloride.

The ratio (S: percentage) of the vinyl aromatic compound unit content of the (A) vinyl aromatic compound polymer block to the total vinyl aromatic compound unit content of (II) is as follows:
3% or more (condition) is required, and 30 to 1
It is preferably 00%, more preferably 50 to 100%. If the proportion is less than 3%, there is a problem that the powder of the thermoplastic elastomer composition has tackiness. The ratio was determined by using a solution of carbon tetrachloride (II) in a solution of ¹ H-
It can be determined by NMR measurement.

In (II), the ratio of the number of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to the number of all hydrogenated conjugated diene units of the conjugated diene copolymer (V: percentage ) Needs to be 60% or more (conditions), and is preferably 60 to 85%, and particularly preferably 65 to 80%. The ratio is 60
%, The obtained coated powder molding becomes hard,
When bent, the bent portion is easily whitened. In addition, such a ratio can be obtained by a Morello method using infrared analysis.

The total vinyl aromatic compound unit content (T) in (II), the ratio of the vinyl aromatic compound unit content of the vinyl aromatic compound polymer block (A) to the total vinyl aromatic compound unit content (S : Percentage) and the ratio (V: percentage) of the number of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to the number of all hydrogenated conjugated diene units of the hydrogenated diene copolymer. It is necessary that the relationship satisfy the following expression (1) (condition). V ≦ 0.375 × S + 1.25 × T + 40 (1) In the expression (1), when the value on the left side exceeds the value on the right side,
80 ° C. after the surface of the obtained coated powder compact is worn
When heated to a temperature lower than the melting point of the polyolefin-based resin, the coated powder molded article has a problem that it emits gloss.

It is necessary that 80% or more of the double bond of the conjugated diene unit in (II) is hydrogenated (condition), and 90% or more, particularly 96% or more is hydrogenated. preferable. If the degree of hydrogenation is less than 80%, there is a problem that the light resistance of the obtained coated powder molded body is reduced.

It is necessary that the (II) has a number average molecular weight of 50,000 to 400,000 (conditions) in order to obtain a molded article having excellent appearance and strength, and the number average molecular weight should be in the range of 100,000 to 300,000. preferable. When the number average molecular weight is less than 50,000, the powder of the thermoplastic elastomer is easily aggregated, and the adhesiveness between the paint and the powder molded body before being coated with the paint tends to be insufficient. There is. When the number average molecular weight exceeds 400,000, the meltability of the thermoplastic elastomer composition of the present invention is inferior, so that a coated powder molded product having sufficient appearance and strength cannot be obtained. The number average molecular weight is measured by a GPC method.

The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kgf according to JIS K-7210 of (II) is preferably 1 to 200 g / 10 min, and more preferably 5 to 100 g / 10 min. Minutes
This is preferable in that a coated powder compact having sufficient appearance and strength can be obtained.

The compound (II) of the present invention may be modified with a functional group, and comprises at least one functional group selected from an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an isocyanate group and an epoxy group. A modified functional group having the same may also be used. When these are used, for example, when the obtained coated powder molded body is bonded to a polyurethane foam layer to produce a two-layer molded body or a multilayer molded body, it is possible to obtain an advantage that the adhesiveness is improved. .

Such (II) is disclosed in, for example,
JP-A-725512, JP-A-5-271325, JP-A-5-271327, JP-A-6-287365
Can be manufactured by the method described in Japanese Patent Application Publication No.

The thermoplastic elastomer composition used in the molded article of the present invention contains (III) an ethylene-α-olefin copolymer in addition to the essential components (I) and (II). May be. When (III) is contained, the powder moldability of the thermoplastic elastomer powder and the whitening resistance of the bent portion when the molded body obtained by powder-molding the powder is bent can be reduced. Further, when heated at a temperature of from about 80 ° C. to less than the melting point of the polyolefin resin after the surface is worn, a coated powder compact which does not emit gloss and has excellent cold impact resistance is provided.

(III) 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 has almost no crystallinity. A polymer having no or a crystallinity of less than 50%. Here, the crystallinity is a value used by the X-ray structure analysis method. Here, as the α-olefin, propylene, 1-butene, 3
Α- having 3 to 10 carbon atoms such as -methyl-1-butene
When the olefin is a non-conjugated diene, it has 5 to 15 carbon atoms such as dicyclopentadiene, 5-2ethylidene norbornene, 1,4-hexadiene, 1,5-cyclooctadiene, and 5-methylene-2-norbornene. Examples thereof include conjugated dienes. Such ethylene-α
-As the olefin copolymer, for example, ethylene-
Propylene copolymer, ethylene-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer and ethylene-propylene-5-ethylidene norbornene copolymer (hereinafter referred to as “EPDM”) ). Such an ethylene-α-olefin-based copolymer may be crosslinked.

The α-olefin unit content in (III) is preferably 5 to 40% by weight, more preferably 10 to 40% by weight.
It is in the range of 35% by weight, and the ethylene unit content is usually 60 to 95% by weight, preferably 65 to 90% by weight. The α-olefin unit content and the ethylene unit content can be determined by ¹³ C-NMR method, infrared absorption spectroscopy, or the like. In addition, from the viewpoint of the strength of the coated molded article of the present invention, the Mooney viscosity of this ethylene-α-olefin-based copolymer measured at 100 ° C. according to ASTM D-927-57T ｛ML _{1 + 4} (100 ° C. ) Is preferably in the range of 10 to 350, more preferably 15 to 300.

When (III) is used, the amount of (III) is
(I) not more than 250 parts by weight per 100 parts by weight;
Preferably it is 20 to 200 parts by weight. If the amount of (III) is too large, the obtained thermoplastic elastomer powder may be liable to agglomerate.

[0026] The thermoplastic elastomer composition used for the coated powder molded product may further comprise (IV) a styrene-based thermoplastic elastomer other than the above (II) in addition to the essential components (I) and (II). May be contained within a range that does not reduce the effects of the present invention. Examples of (IV) include, for example, hydrogenated diene-based copolymers containing the same structural units (A) and (B) as described in (II) above, and hydrogenated vinyl aromatic compound-conjugated diene random copolymers. Things and the like. (IV)
As a hydrogenated diene copolymer containing the same structural units (A) and (B) as described in the above (II), a hydrogenated diene which does not satisfy at least one of the above conditions (II) System copolymers.

For example, when the conditions are not satisfied and a hydrogenated diene copolymer satisfying and is used (when the relational expression of V> 0.375 × S + 1.25 × T + 40 is satisfied), bending is performed. This gives a coated powder compact that is less likely to whiten.

When a hydrogenated diene copolymer which does not satisfy the conditions is used (water having a side chain having 2 or more carbon atoms with respect to the total number of hydrogenated conjugated diene units in the hydrogenated diene copolymer) is used. When a hydrogenated diene-based copolymer in which the ratio of the number of added conjugated diene units (V: percentage) is 60% or less is used, a coated powder molded article excellent in cold impact resistance is provided.

When (IV) is used, the amount of (IV) is
(I) not more than 250 parts by weight per 100 parts by weight;
Preferably it is 20 to 200 parts by weight. If the content of (IV) is excessive, the adhesion to the paint may be reduced when the surface is subjected to the coating treatment after the powder molding.

The thermoplastic elastomer composition used in the coated powder molded product of the present invention may be a hydrogenated polymer of a conjugated diene polymer, or a rubbery polymer such as natural rubber, butyl rubber, chloroprene rubber, epichlorohydrin rubber, or acrylic rubber. , Ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and saponified product thereof, ethylene-methyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl acrylate-vinyl acetate It may contain other polymer components such as a copolymer.

As the hydrogenated product of the conjugated diene polymer rubber,
Examples include hydrogenated polybutadiene and hydrogenated polyisoprene. The ratio (V: percentage) of the number of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to the total number of hydrogenated conjugated diene units in these hydrogenated diene polymers may exceed 60%. The hydrogenated product of the conjugated diene polymer may be composed of two or more blocks having different ratios, although it is preferable from the viewpoint of flexibility of the coated powder molded product of the present invention. When a hydrogenated conjugated diene polymer is used, the amount is (I)
It is not more than 250 parts by weight, preferably 20 to 200 parts by weight, per 100 parts by weight. If the content is excessive, the molded product obtained by the powder molding method may have a sticky feeling, and may have poor adhesion to the paint during the coating treatment.

The thermoplastic elastomer composition used for the coated powder compact of the present invention may be, for example, a mineral oil-based softening agent, a phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based, amide-based or the like. It may contain various additives such as heat stabilizers, weather stabilizers, antistatic agents, pigments, metallic soaps, waxes, fungicides, antibacterial agents, and fillers.

When the thermoplastic elastomer composition used for the coating powder molded article of the present invention contains a mineral oil-based softening agent, the thermoplastic elastomer composition powder having excellent melting properties and the coating powder molded article having excellent flexibility. Can be obtained.

When the thermoplastic elastomer composition used in the coating powder molded product of the present invention contains a pigment, it is possible to obtain a coating powder molded product which is hardly discolored even when wiped with an organic solvent such as hexane, benzene, toluene or the like. it can. Examples of pigments include organic pigments such as azo-based, phthalocyanine-based, sulene-based and dye lakes, oxides such as titanium oxide, molybdic acid chromate, selenium sulfide compounds, ferrocyanide compounds, and inorganic pigments such as carbon black. Used.

As the pigment, any of a liquid substance and a powdery substance can be used. When a powdery material is used, the primary particle size is preferably 300 nm or less from the viewpoint of uniformity of coloring. When a powdery pigment is used, a pigment supported on a carrier such as calcium carbonate, metal soap, or magnesium oxide can also be used. In this case, the primary particle size of the carrier is usually 10 μm or less, preferably 1 to 5 μm. In this case, the weight ratio of the powder pigment to the carrier is usually 20:80 to 80:20, preferably 2:80.
5:75 to 75:25.

The thermoplastic elastomer composition used for the coated powder molded article of the present invention contains the above (I) and (II) as essential components, and if necessary, at least one of (III) and (IV) Contains one kind. The content of (II)
(I) 10 to 1000 parts by weight per 100 parts by weight of (I)
It is necessary to contain them by weight, and preferably 40 to 200 parts by weight. When the content of (II) is less than 10 parts by weight with respect to 100 parts by weight of (I), the flexibility of the coated powder molded article of the present invention is poor, and the bent portion is liable to whiten when bent. When the amount is more than the weight part, the adhesion between the obtained powder molded body and the coating material is reduced, and the heat resistance and light resistance are insufficient.

The heat-resistant material used for the coated powder compact of the present invention
The plastic elastomer composition is prepared by the mechanical pulverization method described below.
When the resulting powder is molded into a powder, 2
Complex dynamic viscosity η at 50 ° C^*(1) is 1.5 × 10^Five
Must be less than poise, 1 × 10^Two~ 8 ×
10^FourThe poise range is preferable, and 3 × 10^Two~ 5x
10^FourPoise, especially 3 × 10^Two~ 1 × 10^FourPoise range
It is preferred that it is an enclosure. Where the complex dynamic viscosity η
^*(Ω) refers to the storage at a temperature of 250 ° C. and a vibration frequency of ω.
Using the storage modulus G ′ (ω) and the loss modulus G ″ (ω)
Is a value calculated by the following equation (2).
Dynamic viscosity η^*(1) means at ω = 1 radian / second
Complex dynamic viscosity. η^*(Ω) = ｛[G '(ω)]^Two+ [G "(ω)]^Two｝^1/2
/ Ω (2) η ^*If (1) exceeds the above upper limit,
Melt fluidity of powder of thermoplastic elastomer composition
Inferior, the shear rate during molding such as powder molding is usually 1 second
^-1A molded product must be manufactured by a molding method with a low value as follows.
And tend to be difficult.

When the thermoplastic elastomer composition used for the coated powder molded article of the present invention is powder-formed into a powder obtained by a mechanical pulverization method described below, it is necessary that the Newton viscosity index n is 0.67 or less. And preferably in the range of 0.01 to 0.35, more preferably 0.1 to 0.35.
It is preferably in the range of 03 to 0.25. Here, the Newtonian viscosity index n is the complex dynamic viscosity η ^* (1)
And a complex dynamic viscosity η ^* (100) measured at a temperature of 250 ° C. and an oscillation frequency ω = 100 radians / second, and is a value calculated by the following equation (3). n = {log [eta] ^* (1) -log [eta] ^* (100)} / 2 (3) When the Newton viscosity index n exceeds the above-mentioned upper limit, the mechanical strength of the obtained coated powder molded product is significantly reduced.

The thermoplastic elastomer composition used in the coated powder molded product of the present invention is prepared by the following strand cutting method,
When a powder produced by a die face cut method or a solvent treatment method is powder-molded, the composition has a temperature of 250 ° C.
Is a complex dynamic viscosity η ^* (1) of 1 × 10 ^{2 to} 5 × 10
It is preferably ⁴ poise, and more preferably 3 × 10 ² to 8 ×
It is preferably in the range of 10 ³ poise. In this case, the Newtonian viscosity index n needs to be 0.28 or less, preferably in the range of 0.01 to 0.20, and more preferably in the range of 0.03 to 0.15. Is preferred.

As a method for obtaining the thermoplastic elastomer composition used for the coated powder molded article of the present invention, for example, the following method can be mentioned. That is, (I) and (II) and (III) and (I)
At least one kind of V) may be melt-kneaded. Alternatively, it can be produced by kneading or dynamically cross-linking all or some of the above-mentioned components and then kneading and kneading the unselected components. For example, containing (I), (II), (III) and (IV),
The thermoplastic elastomer composition in which (I) and / or (III) is cross-linked intramolecularly and / or intermolecularly, usually after dynamically cross-linking (I) and (III), further comprises (II) And kneading after adding (IV). Here, for kneading, a single-screw extruder, a twin-screw extruder, a kneader, a roll, or the like can be used. The above-mentioned various additives and various polymers may be blended, for example, by using (I), (II), (III) or (IV) in which these additives are previously blended, or by kneading the above components. It can be performed by blending at the time of dynamic crosslinking.

The dynamic crosslinking of the kneaded mixture can be performed, for example, by kneading the kneaded mixture and a crosslinking agent under heating. As the crosslinking agent, usually, 2,5-dimethyl-2,5-di (tert-butylperoxyno) is used.
Organic peroxides such as hexane and dicumyl peroxide are used. The crosslinking agent is usually at most 1 part by weight, preferably at most 0.1 part by weight, per 100 parts by weight in total of at least one of (I) and (II) and optionally (III) and (IV). It is used in an amount of 1 to 0.8 part by weight, more preferably 0.2 to 0.6 part by weight. When an organic peroxide is used as a cross-linking agent, a coated molded article having excellent heat resistance can be sold by performing dynamic cross-linking in the presence of a cross-linking aid such as a bismaleimide compound. In this case, the amount of the organic peroxide to be used is determined by the sum of the components to be crosslinked among at least one of (I) and (II) and at least one of (III) and (IV) blended as required. 1
Usually, 0.8 parts by weight or less, preferably 0.2 to 0.8 parts by weight, more preferably 0.4 to 100 parts by weight, per 100 parts by weight.
The range is 0.6 parts by weight.

The amount of the crosslinking aid used is 1% of the total of the components to be crosslinked among at least one of (I) and (II) and optionally (III) and (IV).
Usually, 1.5 parts by weight or less, preferably 0.2 to 1 part by weight, more preferably 0.4 to 0.8 part by weight per 100 parts by weight.
It is in the range of parts by weight. The crosslinking aid is preferably added before the addition of the crosslinking agent, and is usually added when the components to be crosslinked are preliminarily kneaded.

The crosslinking of at least one of (I) and (II), and (III) and (IV) used as required, comprises a component to be crosslinked, a crosslinking agent, and if necessary, Further, the crosslinking aid is heated with a single-screw extruder or a twin-screw extruder while heating, for example, 150 to
It can be performed by kneading in a temperature range of 250 ° C. It is also possible to carry out crosslinking by a method such as sulfur crosslinking.

These additives and other polymer components are:
(I) and (II) and optionally used (III)
And (IV) may be used by being contained in advance in at least one of them, or may be blended by kneading or the like during or after the above-mentioned kneading or dynamic crosslinking. In addition,
When using a mineral oil-based softener, the mineral oil-based softener should be (II
When the oil-extended ethylene-α-olefin copolymer previously contained in I) is used, the above-described kneading and dynamic crosslinking can be easily performed.

In order to produce the thermoplastic elastomer composition used in the coated powder compact of the present invention which satisfies the physical properties indicated by the complex dynamic viscosity and the Newtonian viscosity index, the kneading and the dynamic mixing described above are required. The degree of dynamic cross-linking, the type and amount of each component constituting the thermoplastic elastomer composition, the type and amount of the cross-linking agent or cross-linking aid in dynamic cross-linking, the type and amount of additives, and the like. It is appropriately selected. Above all, the shear rate in kneading and dynamic crosslinking greatly affects the above physical properties, and it is preferable to perform kneading and dynamic crosslinking at a shear rate of 1 × 10 ³ sec ⁻¹ or more.

The powder of the thermoplastic elastomer composition used for the coated powder molded article of the present invention may be obtained by a method of mechanically pulverizing the thermoplastic elastomer composition obtained by the above-mentioned method, a strand cutting method, a die face cutting method, or the like. It can be manufactured by a method or a solvent treatment method.

As a method for mechanically pulverizing the thermoplastic elastomer composition, there is a freeze pulverization method or a normal temperature pulverization method. The freeze-pulverization method is a method in which the thermoplastic elastomer composition is cooled to its glass transition temperature or lower, preferably -70 ° C or lower, more preferably -90 ° C or lower, and ground while keeping the cooling state. It is also possible to pulverize the thermoplastic elastomer composition at a temperature higher than its glass transition temperature (normal temperature pulverization method), but the resulting pulverized product has an irregular particle size, making it difficult to perform powder molding described below. Tend to be.

In order to pulverize the thermoplastic elastomer composition while keeping it in a cooled state, the pulverization efficiency is high,
The pulverization is preferably performed by a method that generates less heat. For example, a mechanical pulverization method using an impact pulverizer such as a ball mill is used. The powder of the thermoplastic elastomer composition in this method is usually sized to pass through a Tyler standard sieve 24 mesh (mesh size 700 μm × 700 μm), and preferably 28 mesh (mesh size 590 μm × 5).
90 μm), and more preferably 3 μm.
2 mesh (aperture 500 μm × 500 μm), particularly preferably 42 mesh (aperture 355 μm × 355 μm)
m).

Since the thermoplastic elastomer composition powder is not uniform in shape, the powder fluidity can be improved by coating the surface with a fine powder. As a fine powder, the primary particle size is 1
Fine powder having a size of 0 μm or less is used. As the fine powder, inorganic oxide, vinyl chloride resin for paste, fatty acid metal salt, calcium carbonate, powder pigment (however, when the pigment is contained in the thermoplastic elastomer composition, it is preferable that the pigment has the same color as the pigment. ) And the like. The primary particle size of the fine powder needs to be 10 μm or less, preferably 5 μm or less, and more preferably 5 nm to 5 μm. Here, the primary particle size means that a photograph of the fine powder is taken by a transmission electron microscope (TEM),
It is a value obtained by measuring the diameter of particles by selecting about 000 particles and dividing the diameter of these particles by the number of particles.

As the inorganic oxide, alumina, silica,
Examples include alumina silica and calcium carbonate. Alumina is a fine powder composed mostly of units of the chemical formula Al ₂ O ₃ . Alumina has various crystal forms, and any of the crystal forms 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 the like can be given.

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. OX50 manufactured by Degussa Corporation and the like can be mentioned. Alumina silica is an inorganic oxide containing the aforementioned alumina and silica as main components.

The surface of these inorganic oxides may be coated with dimethyl silicone oil or the like, or may be surface-treated with a trimethylsilyl group or the like.

Examples of powder pigments include organic pigments such as azo, phthalocyanine, sulene, and dye lakes, oxides such as titanium oxide, molybdic acid chromate, selenium sulfide compounds, ferrocyan compounds, and carbon black. Are used.

It is preferable that these fine powders are used alone or in combination of two or more having a primary particle size of 10 μm or less. For example, an inorganic oxide alone can be used, or a powdered pigment and an inorganic oxide can be used in combination. As fine powder, 1
With a secondary particle size of 300 nm or less;
m when used in combination, compared to when each is used alone, and the bulk specific gravity (packing properties)
And a thermoplastic elastomer composition powder having excellent coagulation resistance.

When a powder pigment is used, a pigment supported on a carrier such as calcium carbonate, metal soap, or magnesium oxide can also be used. In this case, the primary particle size of the carrier is usually 10 μm or less, preferably 1 μm to 5 μm. In this case, the weight ratio between the powder pigment and the carrier is usually 2
0: 80-80: 20, preferably 25: 75-75:
25.

The amount of the fine powder is 0.1 to 10 parts by weight based on 100 parts by weight of the powder of the thermoplastic elastomer composition.
Parts by weight, preferably 0.2 to 8 parts by weight. If the amount is less than 0.1 part by weight, good powder flow characteristics and powder moldability cannot be obtained. If the amount exceeds 10 parts by weight, the thermal fusion between the powders of the thermoplastic elastomer composition is reduced, and the strength of the obtained molded article tends to be poor.

The method of blending the fine powder with the powder of the thermoplastic elastomer composition is not particularly limited as long as the fine powder is uniformly adhered on the powder of the thermoplastic elastomer composition. . For example, a method of blending using a blender with a jacket, a high-speed rotary mixer, or the like can be used. Among them, a method of uniformly dispersing the powder by applying a shearing force to prevent cohesion of the powders, such as a Henschel mixer or a super mixer, is preferred. The compounding is usually performed at room temperature.

The powder of the thermoplastic elastomer composition used for the coated powder coating molded article of the present invention can also be produced by the following method. In this case, a powder having excellent powder fluidity can be obtained without blending the aforementioned fine powder, but blending the fine powder can further improve the powder fluidity.

Solvent treatment: The thermoplastic elastomer composition is cooled to its glass transition temperature or lower (usually -70 ° C or lower, preferably -90 ° C or lower) and pulverized. Then, the powder of the thermoplastic elastomer composition produced by the above-mentioned freeze pulverization method, in a solvent having poor compatibility with the thermoplastic elastomer composition, in the presence of a dispersant and an emulsifier,
After stirring at a temperature equal to or higher than the melting temperature of the thermoplastic elastomer composition, preferably 30 to 50 ° C. higher than the melting temperature, the composition is cooled (for example, see 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 1000 per 100 parts by weight of the thermoplastic elastomer composition.
It is used in an amount of preferably from 400 to 800 parts by weight. As the dispersant, for example, ethylene-acrylic acid copolymer, silicic anhydride, titanium oxide and the like are usually 5 to 2 per 100 parts by weight of the thermoplastic elastomer composition.
0 parts by weight, preferably in the range of 10 to 15 parts by weight. As the emulsifier, for example, polyoxyethylene sorbitan monolaurate, polyethylene glycol monolaurate, sorbitan tristearate and the like are usually 3 parts per 100 parts by weight of the thermoplastic elastomer composition.
It is used in an amount of from 15 to 15 parts by weight, preferably from 5 to 10 parts by weight.

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

Die face cutting method: The molten thermoplastic elastomer composition is cut while being extruded from a die into water. In the die face 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. The discharge rate of the thermoplastic elastomer composition per discharge port of the die is usually in the range of 0.1 to 5 kg / hour, preferably 0.5 to 3 kg / hour. The temperature of the water is usually in the range from 30 to 70C, preferably from 40 to 60C.

The powder of the above-mentioned thermoplastic elastomer composition can be applied to various powder molding methods such as a powder slush molding method, a fluid immersion 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 silicon-based release agent on the molding surface of the mold. When powder molding is carried out using a powder of the thermoplastic elastomer composition, the sixth step is carried out. At the time of removal from the mold, there is a case where the adhesion to the inner surface of the mold is strong. Therefore, if the removal is forcibly attempted, the obtained molded body may be broken. Therefore, although not essential, it is preferable that the inner surface of the mold is previously coated with a spray of a silicone-based release agent or a fluorine-based release agent. As a silicone spray, for example, KF96SP (diluted organic solvent) manufactured by Shin-Etsu Silicone Co., Ltd., and as a fluorine-based spray, Daifree GA-6010 (diluted organic solvent) manufactured by Daikin, ME-
413 (water-diluted product).

Second step: a step of supplying the thermoplastic elastomer composition powder onto the molding surface of a mold heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition powder. Above the melting temperature of the composition, usually 160-320 ° C., preferably 2
It is supplied onto the molding surface of a mold heated to 10 to 300 ° C. In this method, the mold is heated by, for example, a gas heating furnace method, a heat medium oil circulation method, a dipping method in heat medium oil or hot fluidized sand, a high-frequency induction heating method, or the like. The heating time for heat-sealing the powder of the thermoplastic elastomer composition is appropriately selected according to the size and thickness of the target molded article.

Third step: a step of heating the powder of the thermoplastic elastomer composition on the molding surface of the second step for a predetermined time, and fusing powders having at least their surfaces fused to each other, on the molding surface. Is heated for a predetermined period of time, so that the powders whose surfaces have at least been fused are fused together.

Fourth step: a step of collecting the unfused powder after a lapse of the predetermined time in the third step. After the lapse of the predetermined time, the unfused powder is collected.

Fifth step: If necessary, a step of further heating the mold on which the powder of the molten thermoplastic elastomer composition is placed. If necessary, the powder of the molten thermoplastic elastomer composition is placed on the mold. The heating mold 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 cooled. Remove from mold. In addition, by adding the above-mentioned lubricant internally during the production of the thermoplastic elastomer composition, there is an effect of reducing the load required for removing the molded article in the above-mentioned sixth step. In this case, the first step described above can be omitted. The amount of the lubricant added is usually 5 parts by weight or less, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the thermoplastic elastomer composition. When the amount of the lubricant exceeds 5 parts by weight, the strength of the obtained molded article is reduced,
Problems such as contamination of the mold surface may occur.

The coated powder compact of the present invention is obtained by subjecting the surface of the powder molded article obtained by powder-forming the powder of the thermoplastic elastomer composition to a coating treatment with a paint.

As the paint, an ordinary acrylic paint, urethane paint or the like is used. As the coating material, an acrylic resin such as an acrylate ester, a urethane resin, or the like, which is generally used, is dissolved in an organic solvent such as toluene, or is dispersed in an aqueous medium. The paint may be a colored product or a transparent product. Examples of the paint include JP-A-5-86237 and JP-A-7-86237.
And Japanese Patent Application Laid-Open No. 11-140206.

If the surface to be coated has dirt, it is also possible to apply a coating treatment after removing the surface dirt from the surface with alcohol such as isopropyl alcohol.

Here, the coating treatment refers to a method in which the above-mentioned paint is applied by a known method such as brushing or spraying, and then dried by distilling off an organic solvent or water as a medium. The coating is usually applied at room temperature.
As a drying method, the coated material is dried at 30 to 90 ° C.
There are a method of storing in an oven heated to a certain degree, and a method of storing in air for a long time. The thickness of the layer formed by coating of the coated powder compact obtained by the coating treatment is usually 10 to 50 μm.

When the adhesion between the obtained powder compact and the paint is poor, a primer layer made of chlorinated polyolefin, saturated polyester, or the like may be formed as an intermediate layer in order to improve the adhesion. By applying a corona discharge treatment to the surface of the molded body on which the coating treatment is performed, the adhesion can be improved. When a primer layer is formed, a chlorinated polyolefin, a saturated polyester, or the like is dissolved in an organic solvent, and a coating process such as brush coating or spray coating is performed at room temperature, and then the same method as the above-described coating method is used. The surface may be dried. When a primer layer is provided, the thickness after drying is usually 5 to 20.
It is in the range of μm.

The coated powder compact of the present invention is useful as a skin material for automobile interior materials and the like, but can also be used as a two-layer compact having a foam layer laminated on one surface side. The two-layer molded body is obtained by a two-layer powder molding method (Japanese Patent Laid-Open No.
No. 3, etc.), and then a two-layer molded body is manufactured, and then the surface on the non-foamed layer side is subjected to a coating treatment.

Further, it can also be manufactured by a method in which a separately manufactured foam is adhered to the skin material obtained by the above-mentioned powder molding method with an adhesive or the like. In this case, the coating treatment may be performed before or after bonding the foam.

In order to produce a two-layer compact by a powder molding method, a two-layer powder slush molding method (see Japanese Patent Application Laid-Open No. 5-473 and the like) is preferably used. In the two-layer powder slush molding method, after heating a mold, which may have a complicated pattern on the molding surface thereof, at or above the melting temperature of the powder of the thermoplastic elastomer composition, the molding is performed on the molding surface of the mold. The powder of the thermoplastic elastomer composition described above is supplied, and after the powders are thermally fused to each other to obtain a sheet-like melt on the molding surface, the excess powder that has not been thermally fused is removed. A powder of a thermoplastic elastomer composition containing a foaming agent on the sheet-like melt (whether a fine powder is blended or not) can be used. ) Is supplied, and the powders are thermally fused to each other to obtain a sheet-like molten material on the molding surface. Then, excess powder that has not been thermally fused is removed, and then further heated and foamed. Foam layer formed That.

Further, it is also possible to form a composite molded article comprising 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.

The powder of the thermoplastic elastomer composition containing a foaming agent can be prepared by previously incorporating the powder into the powder of the thermoplastic elastomer composition, or by using a rotary mixer such as the aforementioned Henschel mixer. Can be manufactured by a method of coating on the surface of powder.

When the above-mentioned fine powder is used, the foaming agent can be added simultaneously with the fine powder. As the foaming agent, a pyrolytic foaming agent is usually used. Examples of such pyrolytic blowing agents include azodicarbonamide, 2,2
Azo compounds such as 2'-azobisisobutyronitrile and diazodiaminobenzene; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, benzene-1,3-sulfonyl hydrazide and p-toluenesulfonyl hydrazide; N, N'-dinitrosopenta Examples include nitroso compounds such as methylenetetramine and N, N'-dinitroso-N, N'-dimethylterephthalamide, azide compounds such as terephthalazide, and carbonates such as sodium bicarbonate, ammonium bicarbonate, and ammonium carbonate. Among them, azodicarbonamide is preferably used. The compounding of the blowing agent is usually performed at a temperature equal to or lower than the decomposition temperature of the blowing agent. Further, the powder of the thermoplastic elastomer composition may contain a foaming aid and a cell conditioner together with the foaming agent.

In the powder of the thermoplastic elastomer composition containing a foaming agent, instead of the thermoplastic elastomer composition, for example, vinyl chloride resin, polyolefin resin, olefin thermoplastic elastomer other than those described in the present invention, etc. Thermoplastic polymer compositions can also be used. Further, as the thermoplastic polymer composition containing a foaming agent, a polyethylene foamable composition used in JP-A-7-228720 can be used. The fine powder described above may be blended with the powder of these thermoplastic polymer compositions.

Also, 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 molded body and a core material described below,
A mixture of a polyol and a polyisocyanate is injected into the gap and foamed under pressure to be molded. In this case, the polyurethane foam may be bonded after applying a coating treatment to the powder molded body obtained by powder-molding the powder of the thermoplastic elastomer composition, or the polyurethane foam may be bonded after coating. Processing may be performed.

Such a coated molded article is suitable as a skin material laminated on a thermoplastic resin core material. For example, in the case of a single powder molded article, a thermoplastic resin is provided on the surface opposite to the surface to be coated. It can be used as a multilayer molded body in which a core material is laminated, and in the case of two layers including a foam layer, it can be used in a multilayer molded body in which a thermoplastic resin core material is laminated on the foam layer side . In this case, the coating treatment can be performed before the thermoplastic core material is laminated, or can be performed after the thermoplastic core material is laminated.

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. Such a multi-layer molded article is supplied, for example, by supplying a thermoplastic resin melt to one surface side of the molded article and applying a pressure or by supplying a thermoplastic resin melt to the foam layer side of the two-layer molded article and applying a pressure. It can be easily manufactured.

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, the above-mentioned powder compact is supplied as a compact between a pair of opened molds, and then one side of the compact and one of the molds opposed thereto are connected. It is sufficient to clamp both molds after or while supplying the thermoplastic resin melt between them, and when using a two-layer molded body as a skin material, two-layer molding is performed between a pair of opened molds. Supply the body,
Next, after supplying or while supplying the thermoplastic resin melt between the foam layer of the molded article and one of the molds facing the mold, both molds may be clamped. Here, the opening / closing direction of the two dies is not particularly limited, and may be a vertical direction or a horizontal direction.

Further, the powder molding die can be used as one of the dies in the production of the multilayer molded product while holding the molded product or the two-layer molded product on the molding surface.
According to this method, the molded article or the two-layer molded article on which the pattern of the mold is transferred is supplied between the molds without being separated from the mold, so that the pattern imprinted on the surface is almost broken. Thus, a desired multilayer molded body can be obtained.

The thermoplastic resin melt may be supplied after both molds have been clamped. 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 the degree of pattern transfer 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.

[0088]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The following methods were used to evaluate the thermoplastic elastomer composition and the molded article. [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 the vibration frequency ω = 1 radian / sec or 100 radian / sec, and the above equation (2) was used. ) Was used to calculate the complex dynamic viscosity η ^* (1) and η ^* (100). The measurement was performed in a parallel plate mode, an applied strain of 5%, and a sample temperature of 250 ° C. Also, η ^* (1) and η
^{* Using} (100), the Newtonian viscosity index n was determined by the above-mentioned equation (3). [2] (II) Total vinyl aromatic compound unit content in the hydrogenated diene copolymer was determined by ¹ H-NMR measurement (frequency: 90 MHz) using a carbon tetrachloride solution of (II). [3] (II) Ratio of the number of hydrogenated conjugated diene units having side chains having 2 or more carbon atoms to the number of all hydrogenated conjugated diene units in the hydrogenated diene-based copolymer (V) red Was determined by the Morero method using external analysis. [4] Ratio of (A) vinyl aromatic compound content in vinyl aromatic compound polymer block to total vinyl aromatic compound content in hydrogenated diene copolymer in (II) tetrachloride of (II) It was determined by ¹ H-NMR measurement (frequency: 90 MHz) using a carbon solution. [5] The degree of hydrogenation of the double bond of the conjugated diene unit in the hydrogenated diene copolymer was determined by ¹ H-NMR measurement (frequency: 90 MHz) using a carbon tetrachloride solution of (II). [6] Gel permeation chromatography (GP) at 38 ° C. using a tetrahydrofuran solution having a number average molecular weight (II) of hydrogenated diene copolymer
It was determined as a polystyrene equivalent value by the method C). [7] Folding and whitening property of a coated powder slush molded article obtained by subjecting a powder of the thermoplastic elastomer composition to powder slush molding and then applying a coating treatment to form a 1 cm thick molded article obtained by the powder slush molding method described below in 1 cm Cut to × 5cm, bending load 1
One minute after bending with kg, the load was removed, and the following criteria were used to evaluate the width of the whitened portion by bending. 1: A whitened portion was observed. 2: No whitened portion was observed. [8] Change in appearance of a coated powder slush molded article after abrasion treatment A 1 mm thick painted powder slush molded article obtained by a powder slush molding method described below is cut into 3 cm x 15 cm, and a friction fastness measuring device (Aoki Seimitsu) Industrial Co., Ltd.
The wear state of the coated molded article after 100 reciprocations using a 0 type, 60 reciprocations / minute (the tip reciprocates 10 cm one way per second), the tip 2 cm × 2 cm, and the load applied to the tip 500 g). It was determined visually. In Comparative Example 2, a molded body that had not been subjected to a coating treatment was used. 1: The surface of the molded article was significantly worn. 2: The surface of the molded body was worn to such an extent that it could be barely discriminated visually. 3: The surface of the molded body was not worn at all. [9] Change in appearance when the coated powder compact is heated after abrasion treatment The coated powder compact evaluated in the above [8] is placed in the tank for 1 hour.
Gear oven controlled at 10 ° C (Tavai Co., Ltd.
Perfect oven, model number PH-200)
Gross values before and after heating and before and after heating were measured by a digital variable angle photometer (manufactured by Suga Test Instruments Co., Ltd., model number UGV-5DI, reflection angle 60 °), and the determination was made based on the difference between the gloss values before and after heating. In Comparative Example 2, a molded body that had not been subjected to a coating treatment was used. 1: The difference in gloss value was larger than 0.6. 2: The difference in gloss value was in the range of more than 0.3 and 0.6 or less. 3: The difference in gloss value was 0.3 or less.

Example 1 [Production of thermoplastic elastomer composition powder] Propylene-ethylene copolymer resin [manufactured by Sumitomo Chemical Co., Ltd., ethylene unit content 5% by weight, MFR = 228 g /
10 minutes] 100 parts by weight and a hydrogenated product of a styrene-butadiene-styrene copolymer (corresponding to the structure of (A)-(B3)-(A)) [total styrene unit content: 15% by weight, total styrene unit content: (A) Part of vinyl aromatic compound unit content to 100%, MFR = 30 g / 10 min, hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms based on hydrogenated total conjugated diene unit The proportion is 80%, the hydrogenation rate is 98%, the number average molecular weight is 130,000] 122 parts by weight, an ethylene-propylene copolymer rubber [Supreto Chemical Industries, Ltd., Esprene V0141, propylene unit content 27]
% By weight, MFR = 0.7 g / 10 min], and 49 parts by weight and 2.6 parts by weight of a brown pigment are kneaded at a temperature of 170 using a biaxial kneader [TEX-44, manufactured by Nippon Steel Corporation]. Composition [η * (1) = 1.2 × 10 ³ poise, n = 0.04]
Was obtained using a cutting machine to obtain pellets.
After cooling the pellets at −120 ° C. using liquid nitrogen,
While maintaining the cooling state, the mixture was pulverized to obtain a pulverized thermoplastic elastomer composition [Tyler Standard Sieve 42 mesh (mesh size 3)
55 μm × 355 μm). [Production of molded article by powder slush molding method] The obtained powder of the thermoplastic elastomer composition is supplied onto a molding surface of a mold (30 cm square) having a grain pattern heated to 280 ° C, and then left for 15 seconds. After that, the excess powder was washed off and stored in an oven at 280 ° C. for 1 minute. Thereafter, a mold on which the thermoplastic elastomer composition powder melted in the form of a sheet was placed was cooled with water, and the sheet was released from the mold to obtain a molded product having a thickness of 1 mm.

[Production of Painted Powder Slush Molded Body] A primer (colorless chlorinated polyolefin-based paint GP-110S-81 manufactured by Tokusekisho Co., Ltd.) was applied to the surface of this molded body.
(00 parts by weight, diluted with 50 parts by weight of a thinner AD-803 manufactured by the company) was applied using a spray gun, and then put into an oven at 80 ° C. for 5 minutes and dried. The thickness of the primer layer after drying was 7 μm.
Next, a beige paint (100 parts by weight of a polyurethane-based paint YUS-7435 manufactured by Tokusekisho Co., Ltd., diluted with 50 parts by weight of a thinner VL-0385 manufactured by the company) is applied, and the mixture is placed in an oven at 80 ° C. atmosphere. Minutes and dried. The thickness of this layer after drying was 30 μm. The above-mentioned evaluation was performed using this painted slush powder compact. The evaluation results are shown in Tables 1 and 2.

Comparative Example 1 Instead of the styrene-butadiene-styrene copolymer used in Example 1, styrene-butadiene-styrene-
Hydrogenated styrene copolymer ((A)-(B1)-(A)
Corresponding to the structure, the total styrene unit content is 9% by weight, the vinyl aromatic compound unit content of part (A) is 48% based on the total styrene unit content, the MFR is 10 g / 10 min, and the total hydrogenated conjugated diene unit is The ratio of the hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms is 80%, and the hydrogenation rate is 98%.
%, Number-average molecular weight 200,000) was used for the evaluation according to Example 1. The evaluation results are shown in Tables 1 and 2.

Comparative Example 2 Evaluation was performed in the same manner as in Example 1 except that the surface of the powder slush molded body was not subjected to a coating treatment. The evaluation results are shown in Tables 1 and 2.

[0093]

[Table 1] Hydrogenated diene copolymer

[0094]

[Table 2] Physical properties of painted powder slush compacts

[0095]

As described above, according to the present invention, a thermoplastic elastomer composition containing a polyolefin-based resin and a hydrogenated diene-based copolymer having a specific structure as essential components is provided. Excellent in abrasion resistance, even if the surface is worn, does not emit gloss when heated to a temperature below about 80 ° C. to the melting point of the polyolefin-based resin. I got the body.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // B29K 9:00 B29K 9:00 27:00 27:00 B29L 31:58 B29L 31:58 F term ( Reference) 4F006 AA04 AA12 AA15 AA58 AB24 AB37 BA15 DA04 4F071 AA12 AA12X AA14 AA22 AA22X AA75 BA01 BA09 BB05 4F205 AA03 AA46J AA47J AC04 AH26 GA12 GB01 GC04 GE02 GE17 GE24 4J002 BB03W01 BB03 BB03 BB03 BB03 BB03 010

Claims (6)

[Claims] 1. The following (I) 100 parts by weight and (II) 10
Thermoplastic elastomer composition containing -1000 parts by weight
Coating powder made of material and the surface of which has been coated with paint
Molded body. (I): Polyolefin resin (II): Hydrogenated die satisfying all of the following conditions
-Based copolymer: The hydrogenated diene-based copolymer has the following structure (A) or (B):
(A): vinyl aromatic compound polymer block (B): selected from the following (B1), (B2) and (B3)
(B1): random of vinyl aromatic compound and conjugated diene
A block obtained by hydrogenating a copolymer block (B2): a block composed of a vinyl aromatic compound and a conjugated diene.
Tapered block with gradually increasing vinyl aromatic compound
Is a hydrogenated block (B3): a conjugated diene polymer block is hydrogenated
Block: Totally vinyl aromatic contained in hydrogenated diene copolymer
The compound unit content (T) is 10 to 18% by weight: all vinyl aromatic compounds in the hydrogenated diene copolymer
Vinyl aromatic compound of the above (A) with respect to the content of
The unit content ratio (S: percentage) is 3% or more: all hydrogenated conjugated dienes in the hydrogenated diene copolymer
Hydrogenated having side chains with 2 or more carbon atoms per unit number
The ratio of the number of conjugated diene units (V: percentage) exceeds 60%
That  : The above (T) in the hydrogenated diene copolymer and the above
(S) and the relationship with the above (V) satisfy the following equation (1).
Satisfaction V ≦ 0.375 × S + 1.25 × T + 40 (1): Concentration of conjugated diene unit in hydrogenated diene copolymer
80% or more of the double bonds are hydrogenated: the number average molecular weight of the hydrogenated diene copolymer is 50,000 to 60
Be a million 2. The method of claim 2, wherein (II) is represented by the general formula [(A)-(B1)]
n- (A), [(A)-(B2)] n- (A),
[(A)-(B3)] n- (A), [(A)-(B
1)] n, [(A)-(B2)] n or [(A)-(B
3)] a hydrogenated diene system represented by n (where n is an integer of 1 or more and repeating units (A), (B1), (B2) and (B3) may be the same or different) The coated powder molded product according to claim 1, which is a copolymer. 3. The coated powder compact according to claim 1, wherein in (II), the conjugated diene is butadiene and the vinyl aromatic compound is styrene. 4. The method according to claim 1, wherein (I) 100 parts by weight of
I) The coated powder compact according to claim 1, which contains 250 parts by weight or less. (III): ethylene-α-olefin copolymer 5. The coated powder compact according to claim 1, wherein the powder compact is a powder slush compact. 6. The coated powder compact according to claim 1, wherein the paint is an acrylic paint or a urethane paint.