JP3355780B2 - Thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic elastomer composition.

[0002]

2. Description of the Related Art Conventionally, thermoplastic elastomers are widely used in household goods, automobile parts, toys, and other miscellaneous goods, taking advantage of the manufacturing advantage that a vulcanization step is not required for both injection molding and extrusion molding. I have.

[0003] The thermoplastic elastomer referred to here is:
(1). Soft polyvinyl chloride resin (hereinafter referred to as soft PVC), which is a polyvinyl chloride resin containing a plasticizer that has been widely used since the oldest, (2). JP-A-48-2683
No. 8, an olefin-based thermoplastic elastomer (hereinafter referred to as TPO) comprising an ethylene-propylene-diene-based copolymer and a polyolefin,
(3). JP-A-50-21472 discloses a block copolymer having a polystyrene / polybutadiene / polystyrene structure (hereinafter referred to as SBS) and a styrene-based thermoplastic elastomer such as SEBS obtained by hydrogenating this SBS (hereinafter referred to as SBS). , TPS) are well known. Recently, (4). As disclosed in JP-A-3-72512, hydrogenated styrene-butadiene rubber (hereinafter referred to as S-SBR) produced by solution polymerization and hydrogenated styrene-butadiene rubber and hydrogenated styrene. An olefin resin blended with butadiene rubber and an olefin resin, hydrogenated styrene, butadiene, and rubber alloy have been newly developed. As a specific example of these, see Polyfile Vol.
DYNARON HSBR and DYNARON ALLOY (H series) of Nippon Synthetic Rubber Co., Ltd. listed on the page can be mentioned.

[0004]

A comparison of the physical properties of such conventional thermoplastic elastomers shows that soft PVC
Despite having excellent surface properties such as good gloss and resistance to scratches and dirt, the lower the hardness, the greater the amount of plasticizer compounded, causing the plasticizer to migrate to contact parts. There is.

[0005] Recently, with the growing awareness of global environmental issues, the generation of harmful chlorine-based gases during combustion, which is a property common to polyvinyl chloride resins, has been regarded as a problem. Switching is desired.

On the other hand, both TPO and TPS do not contain materials such as halogen elements and sulfur which cause harmful gas generation during combustion in their basic constituent materials, and are considered as alternatives to soft PVC from the viewpoint of global environmental problems. Excellent material.

[0007] However, both have a defect that they are poor in gloss and are easily scratched as compared with soft PVC, and they have a sticky and sticky feeling on the surface or a slimy feeling with a greasy surface. .

[0008] For this reason, it is easy to be stained by dust and the like, and it has drawbacks in visual and finger touch such that it is difficult to remove the adhered stains. .

As a countermeasure against these drawbacks, there is an actual example in which a chlorinated olefin-based or urethane-based paint is applied, but there is a problem that the cost is greatly increased.

[0010] Japanese Patent Application Laid-Open No. 60-215164 and
As disclosed in JP-A-292342, there is a method in which various lubricants are blended with TPO or TPS to reduce stickiness and sliminess, all of which prevent blocking of molded articles and prevent mutual interaction between pellets. The effect of preventing adhesion was recognized.

However, it has almost no effect from the viewpoint of improvement of the finger touch feeling, and the finger touch feeling is very poor especially when compared with soft PVC having the same hardness.

Further, as disclosed in Japanese Patent Application Laid-Open No. 4-272944, there is suggested a gloss improving treatment method by blending a polyoxyethylene polyol or the like with a vulcanized rubber composition. And its gloss improving effect is not remarkable.
It was very poor in gloss as compared with.

[0013] The present invention has a surface property free from problems of glossiness, scratch resistance, stain resistance, and tackiness such as stickiness and wetness due to the smoothness of the surface, and a main resin component. An object of the present invention is to provide a thermoplastic elastomer composition which does not contain an element which generates harmful combustion gas therein and has excellent workability excellent in global environment resistance and which can be easily subjected to injection molding / extrusion molding. It is.

[0014]

A novel thermoplastic elastomer composition for achieving the above object is a random copolymer of a polymer block (A) of a vinyl aromatic compound, a conjugated diene and a vinyl aromatic compound. 80 to 50 parts by weight of a block copolymer (a) with the block (B),
It is obtained by blending 0.2 to 5.0 parts by weight of a higher fatty acid amide with 100 parts by weight of a mixed composition with 20 to 50 parts by weight of a propylene copolymer (b).

[0015]

According to the thermoplastic elastomer composition of the present invention, the block copolymer of a polymer block (A) of a vinyl aromatic compound and a random copolymer block (B) of a conjugated diene and a vinyl aromatic compound is used. 80 to 50 parts by weight of the combined (a) and 20 to 5 parts of the ethylene / propylene copolymer (b)
By blending 0 parts by weight, physical properties with good touch feeling and excellent surface properties are obtained, and furthermore, by blending 0.2 to 5.0 parts by weight of higher fatty acid amide, harmful gas during combustion can be reduced. It does not contain an element that causes generation, and provides excellent physical properties with excellent workability and excellent environmental resistance.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, the feature of the present invention is that a block copolymer of a polymer block (A) of a vinyl aromatic compound and a random copolymer block (B) of a conjugated diene and a vinyl aromatic compound is used. a: This is hereinafter referred to as a hydrogenated diene copolymer.) 80 to 50 parts by weight of a mixed composition 10 of 20 to 50 parts by weight of an ethylene / propylene copolymer (b)
The thermoplastic elastomer composition is obtained by blending 0.2 to 5.0 parts by weight of higher fatty acid amide with 0 parts by weight.

Here, specific examples of the higher fatty acid amide include saturated amides such as lauric amide, palmitic amide, stearic amide, behenic amide, oleic amide, elaidic amide, erucic amide, and hydroxystearic amide. Unsaturated fatty acid amides such as fatty acid amide, bridic acid amide ricinoleic acid amide, N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide Saturated fatty acid bisamides such as substituted amides such as methylenebisstearic acid amide, ethylenebisstearic acid amide, ethylenebiscapramide, hexamethylenebisbehenic acid amide, ethylenebisoleic acid amide, N.
Unsaturated fatty acid bisamides such as N'-dioleyl sebacic amide and aromatic fatty acid bisamides such as m-xylylene bisstearic acid amide are conceivable.

These higher fatty acid amides are used alone or as a mixture in an amount of 0.2 to 5.0 parts by weight, based on 100 parts by weight of the mixed composition of the ethylene / propylene copolymer and the hydrogenated diene copolymer. It is to be blended.

It is more preferable that the higher fatty acid amide is used in an amount of 0.3 to 4.5 parts by weight.

The hardness of the mixture composition of the ethylene / propylene copolymer and the hydrogenated diene copolymer is preferably 50 to 90 in Shore hardness.

It should be noted here that the effect of improving the surface properties is poor when the compounding ratio is less than the above-mentioned ratio, and conversely, even when the compounding ratio is higher, the sticky feeling and the slimy feeling are further improved. Hardly any effect,
Rather, on the contrary, a sticky feeling or a slimy feeling may be developed, or the physical properties of the composition itself, such as a decrease in heat resistance or tensile strength, may be reduced.Therefore, the mixing ratio must be carefully determined. Must.

Of the higher fatty acid amides described above, particularly preferred higher fatty acid amides have a melting point of 70 ° C. to 1 ° C.
Higher fatty acid amides at 00 ° C are preferred, and primary fatty acid amides of unsaturated fatty acids are more preferred.

Next, a block copolymer (a) of a polymer block (A) of a vinyl aromatic compound and a random copolymer block (B) of a conjugated diene and a vinyl aromatic compound.
Is a hydrogenated diene copolymer (1). (A)-(B) block copolymer comprising a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene; ). The above (A)-(B) block copolymer comprises, as required, a vinyl aromatic compound and a tapered block (C) in which the vinyl aromatic compound of the conjugated diene gradually increases. (C) a block copolymer, (3). The above (A)-(B) block copolymer can be composed of a (A)-(B)-(A) block copolymer comprising a vinyl aromatic polymer block (A).

In these hydrogenated diene copolymers, the ratio of the vinyl aromatic compound to the conjugated diene is 5 to 5 by weight.
60/95 to 40, wherein the content of the vinyl aromatic compound in the component (A) and the component (C), which is optional, is 3 to 50% by weight of the total monomers; and Hydrogen is added to the block copolymer in which the vinyl aromatic compound in the component (A) has a bond content of at least 3% by weight and the vinyl bond content in the conjugated diene portion in the component (B) exceeds 60%. A hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 600,000 in which at least 80% of the double bond of the conjugated diene portion is saturated is preferred.

A typical example of this is hydrogenated styrene.
It has the structure of butadiene rubber, and is a material called by the abbreviation of HSBR.
N) It is marketed under the trade name HSBR.

Next, as the ethylene / propylene copolymer (b), block polypropylene or random polypropylene obtained by mixing polyethylene or ethylene / propylene copolymer rubber (EPR) with polypropylene can be used.

Here, it is effective to appropriately select an ethylene-propylene copolymer to be blended depending on the desired properties, for example, fluidity, hardness, heat resistance and the like.

In particular, a random polymerization type ethylene-propylene copolymer is suitable for obtaining a low-hardness final composition. Because, the heat resistance of the hydrogenated diene copolymer itself is lower than that of the ethylene / propylene copolymer,
In particular, the dimensional stability after molding is poor.

That is, the higher the compounding ratio of the hydrogenated diene copolymer, the greater the shrinkage when the molded article is left at a high temperature. This can be improved by increasing the blending ratio of the ethylene / propylene copolymer, but at the same time, the hardness of the composition also increases.

Therefore, in order to obtain physical properties as low as possible and as excellent in heat resistance and dimensional stability as possible, random polypropylene, which easily lowers surface hardness and flexural modulus, is preferable. In particular, a random polypropylene having an ethylene content of 4 to 8% by weight is preferable, and a random polypropylene having an ethylene content of 6 to 8% by weight is more preferable.

The composition of the present invention can be prepared by using an extruder, kneader,
It can be obtained by melt-kneading with a Banbury mixer or the like.

In producing the composition of the present invention, the respective components may be mixed at once, or after preliminarily mixing arbitrary components, the remaining components may be added and mixed.

The most preferable production apparatus is a single-screw or twin-screw extruder, which can continuously knead and pelletize efficiently.

It is not always necessary to knead all the components before putting them into the molding machine. In other words, the necessary components are separately melt-kneaded or simply kneaded into both or only one of the hydrogenated diene copolymer and the ethylene / propylene copolymer, and the respective pellets are tumbled or weighed by attaching to a molding machine. The blender may be used as a masterbatch for blending.

Further, the powder component in the compounding component may be spread on the surface of the pellet component and then used in a dry color manner in which the powder component is introduced into a molding machine.

Further, in the present invention, in addition to the above-mentioned basic components, if necessary, stabilizers, antioxidants, ultraviolet absorbers, copper damage inhibitors, antistatic agents, pigments, fillers, flame retardants,
An antibacterial agent, a fungicide and the like can be added.

Then, the obtained pellets are subjected to injection molding / extrusion molding to be processed into a desired shape.

The thermoplastic elastomer composition obtained by the present invention can be used in various packings, bumpers, belts, skin materials, cushioning materials, caps and sealing materials, non-slip bottom parts, hoses and the like. Miscellaneous goods such as home appliances, toys, stationery, tubes and cords,
It can be applied to automobile parts and the like.

Hereinafter, the specific contents of the present invention will be described with reference to Tables 1 and 2, but the present invention is not specifically limited to these Examples.

[0040]

[Table 1]

[0041]

[Table 2]

First, physical characteristics in the examples and comparative examples and test methods used for measuring the physical characteristics will be described.

(1). Hardness The hardness was based on ASTM D-2240 (A hardness).

(2). 100% tensile stress The 100% tensile stress was based on JIS K-6301 (No. 3 dumbbell, tensile speed 200 mm / min).

(3). Tensile permanent elongation Tensile permanent elongation was measured by fixing the dumbbell for 10 minutes in a state where the No. 3 dumbbell was stretched to 100%, then releasing the load and leaving it to stand for 10 minutes to measure the distance between the marked lines. The elongation rate from the distance between lines was calculated.

(4). Dynamic Slip Resistance The dynamic slip resistance is measured by applying a load of 50 g to an R0.5 mm sapphire needle in such a manner that the sapphire needle comes into contact with a mirror-finished injection-molded product in a vertical direction. And the resistance generated during the movement was measured.

(5). Blocking properties Blocking properties were measured at a mold temperature of 50 ° C and a resin temperature of 220 ° C.
Immediately after molding, five JIS K-6301 No. 3 dumbbells molded at ± 20 ° C. were piled up so that they adhere closely, left at room temperature for 1 hour, peeled off one by one, and judged as follows: did.

：: Easy peeling without any problem and no trace of adhesion on the peeled surface.

Δ: Although peeling is possible, traces of adhesion remain on the peeled surface.

×: Completely fused and impossible to peel off.

(6). Finger touch The touch was classified as follows by directly touching the clean product with a finger.

：: Neither sticky nor slimy feeling.

Δa: There is a sticky feeling.

Δb: There is a slimy feeling.

Xa: Stickiness is large.

× b: Large sliminess.

(7). Scratching property Scratching property was measured by contacting a 0.75 mm diamond needle with a load of 50 g under a load of 50 g so as to vertically hit the mirror-finished injection molded product and moving it horizontally at 1 mm / sec. Scratches in a straight line, expands the scratches using a surface profiler, measures the depth of the scratches, and compares the depth of the scratches with the degree of the scars visually observed as follows: Ranked.

：: The depth of the scratch is less than 2 μm.

Δ: The scratch depth is 2 μm or more and less than 8 μm.

×: The depth of the scratch is 8 μm or more.

(8). MFR MFR is based on ASTM D1238, 230 ° C,
It was measured under a load of 2.16 kg.

Next, the materials used in this embodiment will be described using symbols in the table.

(1). Symbol in the table: D-1 The hydrogenated diene copolymer used in this example is DYNARON 1320P manufactured by Nippon Synthetic Rubber Co., Ltd. This is based on styrene as a vinyl aromatic compound.
It is a hydrogenated diene copolymer (HSBR) blended at 15%, and more preferably a blended styrene at 8 to 12% is used. The MFR is a grade of 3.5 (g / 10 minutes).

(2). Symbol in the table: P-1 The block polypropylene used as the ethylene / propylene copolymer component in this example was manufactured by Showa Denko KK
Showaromer MK541.

(3). The symbol in the table: P-2 The block polypropylene used as the ethylene / propylene copolymer component in this example was manufactured by Ube Industries, Ltd.
UBE Polypro J830HV.

(4). Symbol in the table: P-3 The random polypropylene used in this example had an ethylene content of 6 to 7% by weight and an MFR of 30 (g / 10 min).
It is a sample of.

(5). Symbol in the table: P-4 The random polypropylene used in this example had an ethylene content of 6 to 7% by weight and an MFR of 2 (g / 10 min).
It is a sample of.

(6). Symbol in the table: A-1 As the higher fatty acid amide used in this example, stearic acid amide was used as a saturated fatty acid amide.

(7). Symbol in the table: A-2 As the higher fatty acid amide used in this example, oleic amide was used as the unsaturated fatty acid amide.

(8). Symbol in the table: A-3 As the higher fatty acid amide used in this example, erucamide was used as the unsaturated fatty acid amide.

(9). Symbol in the table: A-4 As the higher fatty acid amide used in this example, methylene bisstearic acid amide was used as a saturated fatty acid bisamide.

(10). Symbol in the table: C-1 As an example of a soft PVC as a comparative example of a conventional material having the same hardness as the composition of the example, Mitsubishi Kasei Vinyl Co., Ltd.
# 6840 was used.

(11). Symbol in the table: C-2 Mirastomer 7030N manufactured by Mitsui Petrochemical Industry Co., Ltd. was used as an example of a TPO as a comparative example of a conventional material having the same hardness as the composition of the example.

(12). Symbol in the table: F-1 Tenlo 7 manufactured by San Nopco Co., Ltd. was used as a spreading and dispersing agent for spreading and dispersing the components used in this example.
0 was used.

(13). Symbol in the table: F-2 Titanium dioxide was used as the coloring agent used in this example.

(14). Symbol in the table: F-3 2 (4 Triazole-H-benzimidazole was used as a fungicide and fungicide used in this example.

(15). Symbol in the table: F-4 As a fungicide and fungicide used in this example, 2.3.
5.6 Tetrachloro-4 (methylsulfonine) pyridine was used.

(16). Symbol in the table: F-5 As the ultraviolet absorber used in this example, 2- (2'hydroxy-3 ', 5'-di-t-amylphenyl) -benzotriazole was used.

Example 1 Dynaron (DYNARO)
N) 1320P (symbol: D-1 in the table), 0.9 parts by weight of erucamide (symbol: A-3) and 70% by weight of Tenlo 70 (symbol: F-1) per 70 parts by weight. And 0.05 parts by weight were mixed by rotation in a cooler mixer.

Next, Showaromer MK541 (symbol: P-1 in the table) was added to 70.95 parts by weight of this mixture.
0 parts by weight was further added and the mixture was further rotated and mixed.

The mixture was kneaded and extruded for 1 minute at a rotational speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a paddle-type twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

Example 2 Show Allomer MK541
(Symbol in the table: P-1) is 0.9 parts by weight of erucamide (Symbol in the table: A-3) per 30 parts by weight and Tenlo 70
(Symbol in the table: F-1) and 0.05 parts by weight were rotationally mixed in a cooler mixer.

This mixture was kneaded and extruded at a rotation speed of 80 rpm and a melting temperature of 200 ± 10 ° C. for 2 minutes using a single screw kneading extruder of a Dal-Mage type screw to form pellets.

For 30.95 parts by weight of the pellets,
A pellet of 70 parts by weight of DYNARON 1320P (symbol: D-1 in the table) is rotated at 20 rpm using a tumbler.
For 5 minutes. A test piece was prepared from the mixed pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Embodiment 3] DYNARON 132
0.9 parts by weight of erucamide (symbol: A-3) and titanium dioxide (symbol: F-1) as a colorant per 70 parts by weight of 0P (symbol: D-1). 0.3 parts by weight and 2- (2'-hydroxy-
0.5 parts by weight of 3 ', 5'-di-t-amylphenyl) -benzotriazole (symbol: F-5 in the table) and 0.05 parts by weight of Tenlo 70 (symbol: F-1 in the table) And were rotated and mixed in a cooler mixer.

Next, 30 parts by weight of show aroma MK541 (symbol: P-1 in the table) was added to 71.75 parts by weight of the mixture, and the mixture was further rotated and mixed.

The mixture was kneaded and extruded for 1 minute at a rotational speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a twin-screw kneading extruder with a paddle type screw to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Example 4] DYNARON 132
0.9 parts by weight of erucamide (symbol: A-3) per 70 parts by weight of 0P (symbol: D-1 in the table), fungicide,
0.3 parts by weight of 2 (4-triazole-1-Hbenzimidazole) (symbol in the table: F-3) as an antibacterial agent and
2.3.5.6 Tetrachloro-4 (methylsulfonyl) pyridine (symbol in the table: F-4) was 0.2 parts by weight, and Tenlo 70 (symbol in the table: F-1) was 0.05 parts by weight. Was tumbled in a cooler mixer.

Next, 30 parts by weight of Showaromer MK541 (symbol: P-1 in the table) was added to 71.45 parts by weight of the mixture, and the mixture was further rotated and mixed.

The mixture was kneaded and extruded for 1 minute at a rotational speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a paddle type screw twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Embodiment 5] DYNARON 132
0.6 parts by weight of erucamide (symbol: A-3) and 70% by weight of TP (symbol: F-1) per 70 parts by weight of 0P (symbol: D-1 in the table). And 0.5 parts by weight in a cooler mixer.

Next, 30 parts by weight of Showaromer MK541 (symbol: P-1 in the table) was added to 70.65 parts by weight of the mixture, followed by further rotational mixing.

The mixture was kneaded and extruded for 1 minute at a rotation speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a paddle-type screw twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Embodiment 6] DYNARON 132
0.3 parts by weight of erucamide (symbol: A-3) and 70% by weight of 0P (symbol: D-1 in the table) and 70 parts by weight of Tenlo 70 (symbol: F-1 in the table) were added. And 0.5 parts by weight in a cooler mixer.

Next, 30 parts by weight of Showaromer MK541 (symbol: P-1 in the table) was added to 70.35 parts by weight of the mixture, followed by further rotational mixing.

This mixture was kneaded and extruded for 1 minute at a rotation speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a twin-screw kneading extruder of a paddle type screw to pelletize. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Example 7] DYNARON 132
0.9 parts by weight of erucamide (symbol: A-3) and TENRO 70 (symbol: F-1) were added in an amount of 0.9 parts by weight per 70 parts by weight of 0P (symbol: D-1). And 0.5 parts by weight in a cooler mixer.

Next, 30 parts by weight of UBE polypro J830HV (symbol: P-2 in the table) was added to 70.95 parts by weight of the mixture, and the mixture was further rotated and mixed.

The mixture was kneaded and extruded at a rotational speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. for 1 minute using a paddle type screw twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Embodiment 8] DYNARON 132
0.9 parts by weight of erucamide (symbol: A-3) and TENRO 70 (symbol: F-1) in 0.6 parts by weight per 65 parts by weight of 0P (symbol: D-1 in the table). And 0.5 parts by weight in a cooler mixer.

Next, based on 65.95 parts by weight of this mixture, 35 parts by weight of ethylene was contained in an amount of MF of 6 to 7% by weight.
Random polypropylene (P-3) having an R of 30 (g / 10 minutes) was added, and the mixture was further rotationally mixed.

This mixture was kneaded and extruded for 1 minute at a rotation speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a paddle type screw twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Embodiment 9] DYNARON 132
0.9 parts by weight of erucamide (symbol: A-3) and TENRO 70 (symbol: F-1) were added in an amount of 0.9 parts by weight per 65 parts by weight of 0P (symbol: D-1 in the table). And 0.5 parts by weight in a cooler mixer.

Next, with respect to 65.95 parts by weight of this mixture, 35 parts by weight of ethylene was contained in an amount of 6 to 7% by weight and MF
Random polypropylene having a R of 2 (g / 10 minutes) (symbol: P-4 in the table) was added, and the mixture was further rotationally mixed.

The mixture was kneaded and extruded for 1 minute at a rotation speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a paddle-type screw twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

Example 10 DYNARON 13
20P (symbol: D-1 in the table) is 0.9 per 65 parts by weight.
Parts by weight of stearamide (symbol: A-1 in the table);
Tenlo 70 (symbol: F-1 in the table) and 0.05 parts by weight were rotationally mixed in a cooler mixer.

Next, with respect to 65.95 parts by weight of this mixture, the ethylene content of 35 parts by weight was 6 to 7% by weight and the MF
Random polypropylene having an R of 30 (g / 10 minutes) (symbol: P-3 in the table) was added, and the mixture was further rotationally mixed.

This mixture was kneaded and extruded at a rotational speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. for 1 minute using a paddle-type twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Example 11] DYNARON 13
20P (symbol: D-1 in the table) is 0.9 per 65 parts by weight.
Parts by weight of oleic acid amide (symbol: A-2 in the table) and 0.05 parts by weight of Tenlo 70 (symbol: F-1 in the table) were rotationally mixed in a cooler mixer.

Next, with respect to 65.95 parts by weight of this mixture, 35 parts by weight of ethylene was contained in an amount of 6 to 7% by weight and MF
Random polypropylene having an R of 30 (g / 10 minutes) (symbol: P-3 in the table) was added, and the mixture was further rotationally mixed.

This mixture was kneaded and extruded for 1 minute at a rotational speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a twin-screw kneading extruder of a paddle type screw to pelletize. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Example 12] DYNARON 13
20P (symbol: D-1 in the table) is 0.9 per 65 parts by weight.
Parts by weight of methylenebisstearic acid amide (symbol in the table:
A-4) and Tenlo 70 (symbol: F-1 in the table) are 0.0.
5 parts by weight were rotationally mixed in a cooler mixer.

Next, with respect to 65.95 parts by weight of this mixture, the ethylene content of 35 parts by weight was 6 to 7% by weight and the MF
Random polypropylene having an R of 30 (g / 10 minutes) (symbol: P-3 in the table) was added, and the mixture was further rotationally mixed.

The mixture was kneaded and extruded for 1 minute at a rotation speed of 1200 rpm and a melting temperature of 200 ± 10 ° C. using a paddle-type screw twin-screw kneading extruder to form pellets. A test piece was prepared from the pellet at a molding temperature of 220 ± 20 ° C. using an injection molding machine.

[Comparative Example 1] DYNARON 132
0P (symbol: D-1 in Table) per 65 parts by weight, ethylene content of 35 parts by weight is 6 to 7% by weight, and MFR is 30 (g).
/ 10 min) random polypropylene (symbol: P in the table)
-3) was pellet-mixed at 20 rpm for 5 minutes using a tumbler.

The mixture was kneaded and extruded for 2 minutes at a rotation speed of 80 rpm and a melting temperature of 200 ± 10 ° C. by using a single screw kneading extruder of a dalmage type screw to form pellets. The pellets were molded at an injection temperature of 2 using an injection molding machine.
Test specimens were prepared at 20 ± 20 ° C.

[Comparative Example 2] # manufactured by Mitsubishi Kasei Vinyl Co., Ltd.
A test piece of 6840 (symbol: C-1 in the table) was prepared at a molding temperature of 180 ± 10 ° C. using an injection molding machine.

[Comparative Example 3] A test piece was prepared at a molding temperature of 220 ± 20 ° C from a Mirastomer 7030N (C-2 in the table) manufactured by Mitsui Petrochemical Industry Co., Ltd. using an injection molding machine.

From the above results, when the composition of the composition of Example 8 was compared with the composition of Comparative Example 1 containing no higher fatty acid amide based on the same resin composition, the hardness, tensile stress, permanent elongation, etc. Without affecting the basic material properties as a thermoplastic elastomer, the dynamic slip resistance is reduced by 93% or more, and no blocking occurs immediately after molding, and there is no sticky or slimy feeling. It can be seen that excellent surface characteristics with good finger touch and scratch resistance are obtained.

The ethylene / propylene copolymer used in Example 9 has almost the same rigidity because of substantially the same ethylene content as that of Example 8, but differs only in fluidity. This has the same properties as the resulting composition, but can be used for both extrusion and injection molding.

Examples 10, 11 and 12 are compositions in which the type of higher fatty acid amide to be blended is different from that in Example 8. In each case, the effect of improving the surface characteristics is observed as compared with Comparative Example 1, but not as excellent as Example 8.

However, the evaluation criteria in Table 2 are relative, and it is needless to say that these compositions can be used in accordance with the actual use environment of molded articles using these compositions. For example, when applied to a product having a high use environment temperature, blending a higher fatty acid amide having a higher melting point has less adverse effects on the basic physical properties of the material and can maintain the effect for a long period of time.

Examples 1 to 7 have a flexural modulus according to ASTM D790 of 23,000 to 13,000 (13,000 to 15,000 (compared to the random polypropylene used in Examples 8 to 12). kg / cm ² ) of block polypropylene.

Example 2 in which all of the components were previously melt-kneaded, and other additive components were melt-kneaded only in the ethylene / propylene copolymer (Show Allomer MK541), and then pellets of DYNARON 1320P Comparing Example 1 with mixing, it can be seen that the properties of the composition obtained are almost the same, and similar effects can be obtained by any of the production methods.

Examples 3 and 4 are examples in which a pigment and a function-imparting additive (here, a fungicide, an antibacterial agent or an ultraviolet absorber) are blended based on the resin composition and the production method of Example 1. The composition characteristics obtained in this example are the same, and the same excellent surface characteristics as in Example 1 are exhibited.

Examples 5 and 6 are examples in which the amount of higher fatty acid amide blended based on Example 1 is reduced.

As the amount of the fatty acid amide was reduced, the effect of improving surface properties such as dynamic slip resistance, blocking properties, finger touch, and scratch resistance gradually decreased.

As described above, these compositions can be properly used according to the product specifications.

[0129]

As described above, according to the thermoplastic elastomer composition of the present invention, dirt is hardly adhered, there is no problem of transfer of the compounded components to other parts which come into contact, and scratches are hardly caused despite glossiness. It is possible to provide a thermoplastic elastomer composition which has excellent surface characteristics and which does not generate harmful gas during combustion and has excellent resistance to global environmental pollution.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuo Ishikawa 1-1-1 Higashitaga-cho, Hitachi City, Ibaraki Prefecture Living Equipment Division, Hitachi, Ltd. No. 1-1 In the Living Equipment Division of Hitachi, Ltd. (56) References JP-A-5-140384 (JP, A) JP-A-3-292342 (JP, A) (58) Fields investigated (Int. Cl) . ^7, DB name) C08L 53/02 C08K 5/20 C08L 23/16

Claims (12)

(57) [Claims] 1. A block copolymer (a) of a polymer block (A) of a vinyl aromatic compound and a random copolymer block (B) of a conjugated diene and a vinyl aromatic compound.
A mixture of 0 to 50 parts by weight and 20 to 50 parts by weight of an ethylene / propylene copolymer (b) is mixed with 0.2 to 5.0 parts by weight of a higher fatty acid amide. Thermoplastic elastomer composition. 2. A vinyl aromatic compound polymer block (A)
(A)-(B) block copolymer consisting of a random copolymer block (B) of a conjugated diene and a vinyl aromatic compound, and a taper in which the vinyl aromatic compound of the vinyl aromatic compound and the conjugated diene gradually increases (A)-(B)-(C) block copolymer (a) comprising block (C) 80-
50 parts by weight of ethylene / propylene copolymer (b) 20
A thermoplastic elastomer composition characterized in that 0.2 to 5.0 parts by weight of a higher fatty acid amide is blended with 100 parts by weight of a mixed composition of 50 to 50 parts by weight. 3. A vinyl aromatic compound polymer block (A)
(A)-(B), which is composed of a (A)-(B) block copolymer and a random aromatic polymer block (B) of a conjugated diene and a vinyl aromatic compound, and (A)-(B), which comprises a vinyl aromatic polymer block (A). )-(A) block copolymer (a) 80-50
20 to 5 parts by weight of ethylene / propylene copolymer (b)
A thermoplastic elastomer composition characterized in that 0.2 to 5.0 parts by weight of a higher fatty acid amide is blended with 100 parts by weight of a mixed composition with 0 parts by weight. 4. The method of claim 1 to claim 3, wherein the mixture composition is a thermoplastic elastomer composition characterized by its hardness of 50-90 Shore A hardness. 5. The method of claim 1 to claim 3, wherein the higher fatty acid amide thermoplastic elastomer composition, characterized in that the melting point of the higher fatty acid amides in the range of 70 to 100 ° C.. 6. The method of claim 1 to claim 3, wherein the higher fatty acid amide thermoplastic elastomer composition, which is a primary amide compounds unsaturated fatty acids. 7. The method of claim 6 , wherein said unsaturated fatty acid
A thermoplastic elastomer composition, wherein the unsaturated fatty acid of the amide compound has 17 to 21 carbon atoms. 8. The method of claim 1 to claim 3, the thermoplastic elastomer composition, wherein the ethylene-propylene copolymer is an ethylene-propylene random copolymer. 9. The ethylene / propylene random copolymer according to claim 8 , wherein the ethylene content is 4 to 4.
8% by weight of a thermoplastic elastomer composition. 10. The method of claim 1 to claim 3, wherein the higher fatty acid amide is preferably a thermoplastic elastomer composition characterized in that it is formulated from 0.3 to 4.5 parts by weight. 11. The method of claim 1 to claim 3, at least the (A) - (B) block copolymer (a) is a thermoplastic, characterized in that the styrene content is 5-15% compounded Elastomer composition. 12. The method of claim 11, at least the (A) - (B) block copolymer (a) is a thermoplastic elastomer composition, wherein the styrene content is preferably is formulated 8% to 12% object.