JPH07233306A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful for a household electric appliance, a part of automobile, etc., hardly being stained, not emitting a poisonous gas during combustion by adding an ethylene.propylene copolymer and a higher fatty acid amide to a specific hydrogenated diene-based copolymer. CONSTITUTION:This thermoplastic elastomer composition is obtained by blending 100 pts.wt. of mixed composition of (A) 80-50 pts.wt. of a hydrogenated diene- based copolymer composed of a polymer block of a vinyl aromatic compound and a random copolymer of a conjugated diene and a vinyl aromatic compound and (B) 20-50 pts.wt. of an ethylene/propylene copolymer with (C) 0.2-5.0 pts.wt., preferably 0.3-4.5 pts.wt. of a higher fatty acid amide. The composition has surface characteristics of hardly being stained in spite of its luster, excellent processability and ready injection molding and extrusion molding.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel thermoplastic elastomer composition.

[0002]

2. Description of the Related Art Conventionally, thermoplastic elastomers have been widely used for household goods, automobile parts, toys, and other miscellaneous goods, taking advantage of the fact that no vulcanization process is required for injection molding and extrusion molding. There is.

The thermoplastic elastomer referred to here is
(1). Soft polyvinyl chloride resin (hereinafter referred to as soft PVC), which is a polyvinyl chloride resin blended with a plasticizer that has been widely used since oldest, (2). JP 48-2683
An olefin-based thermoplastic elastomer (hereinafter referred to as TPO) prepared by blending an ethylene / propylene / diene-based copolymer and a polyolefin, as described in Japanese Patent No. 8
(3). 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 SBS as described in JP-A-50-21472 (hereinafter referred to as SBS). , TPS) is well known. Recently (4). As described in JP-A-3-72512, hydrogenated styrene-butadiene rubber and hydrogenated styrene-obtained by hydrogenating a styrene-butadiene rubber (hereinafter referred to as S-SBR) produced by solution polymerization. Olefin resin / hydrogenated styrene / butadiene rubber alloy, which is a mixture of butadiene rubber and olefin resin, has been newly developed. Specific examples of these are polyfile Vol. 29.8 August issue 67.
Examples include DYNARON HSBR and Dynaron Alloy (H series) manufactured by Japan Synthetic Rubber Co., Ltd.

[0004]

Comparing the physical properties of such conventional thermoplastic elastomers, flexible PVC
Has excellent surface characteristics such as good gloss and less scratches and stains, but the lower the hardness, the greater the amount of plasticizer blended, so the problem of migration of plasticizer to contact parts There is.

In addition, recently, with the increase in awareness of global environmental problems, generation of chlorine-based harmful gas during combustion, which is a common property of polyvinyl chloride resins, has been regarded as a problem. Switching is desired.

[0006] On the other hand, both TPO and TPS do not contain halogen elements, sulfur, etc., which cause the generation of harmful gases during combustion, in their basic constituent materials, and as a substitute for soft PVC from the viewpoint of global environmental problems. It is an excellent material.

However, both of them have defects such as less gloss and more easily scratched than soft PVC, sticky tacky surface, or greasy feeling of greasy surface. .

For this reason, it has a visual / finger touch defect that it is easily contaminated by dust and the like, and that the adhered stain is difficult to remove, so that it cannot be applied to exterior parts, especially products that can be touched by hands. .

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

In addition, JP-A-60-215164 and JP-A-3-215164
As disclosed in Japanese Patent No. 292342, there is a treatment method in which various lubricants are mixed with TPO or TPS to reduce stickiness or sliminess. The effect of preventing adhesion was recognized.

However, in terms of improving the feel of the finger, it has almost no effect, and the feel of the finger is very poor as compared with the soft PVC having the same hardness.

Further, as disclosed in Japanese Patent Application Laid-Open No. 4-272944, a method of improving gloss by adding polyoxyethylene polyol or the like to a vulcanized rubber composition has been suggested, but it has an adverse effect on the feeling of sliminess. In addition to the above, the effect of improving the gloss is not remarkable, and especially soft PVC with the same hardness.
It had a very low gloss as compared with.

The present invention has surface characteristics which are free from problems such as gloss, scratch resistance, stain resistance due to the smoothness of the surface, finger touch feeling such as sticky feeling and slimy feeling, and a main resin component. An object of the present invention is to provide a thermoplastic elastomer composition which does not contain an element that causes harmful combustion gas therein, has excellent global environment resistance, has good processability, and can be easily injection-molded / extruded. 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 the block copolymer (a) with the block (B), and ethylene.
It is obtained by adding 0.2 to 5.0 parts by weight of higher fatty acid amide to 100 parts by weight of a mixed composition with 20 to 50 parts by weight of propylene copolymer (b).

[0015]

According to the thermoplastic elastomer composition of the present invention, the block copolymerization of the polymer block (A) of vinyl aromatic compound and the random copolymer block (B) of conjugated diene and vinyl aromatic compound is carried out. 80 to 50 parts by weight of the combined product (a) and 20 to 5 ethylene / propylene copolymer (b)
By blending with 0 part by weight, physical characteristics having a good feel to the touch and having excellent surface characteristics can be obtained. Further, by blending 0.2 to 5.0 parts by weight of higher fatty acid amide with this, harmful gas during combustion can be eliminated. It is possible to obtain physical properties that are excellent in global environment resistance and do not contain elements that cause generation, and that have good workability.

[0016]

The features of the present invention are, as described above, 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 ( a: Hereinafter, this is referred to as a hydrogenated diene-based copolymer.) 80 to 50 parts by weight and a mixed composition 10 of 20 to 50 parts by weight of an ethylene / propylene copolymer (b).
A thermoplastic elastomer composition obtained by blending 0 to 5.0 parts by weight of higher fatty acid amide.

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

Then, 0.2 to 5.0 parts by weight of these higher fatty acid amides are mixed alone or mixed with 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 to add 0.3 to 4.5 parts by weight of the higher fatty acid amide.

Further, the hardness of the mixed composition of the ethylene / propylene copolymer and the hydrogenated diene copolymer is preferably a Shore hardness of 50 to 90.

Attention should be paid here to the problem that the effect of improving the surface characteristics is poor below the above-mentioned mixing ratio, and conversely, even if the mixing ratio is higher than this, the sticky feeling and the slimy feeling are further improved. Almost no effect,
On the contrary, on the contrary, a sticky feeling or a slimy feeling may be exhibited, and the physical properties of the composition itself may be deteriorated such that the heat resistance and the tensile strength are deteriorated.Therefore, the blending ratio should be carefully determined. I have to.

Of the above-mentioned higher fatty acid amides, a particularly preferable higher fatty acid amide has a melting point of 70 ° C. to 1 ° C.
Higher fatty acid amides at 00 ° C are preferable, and unsaturated fatty acid primary amides are more preferable.

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.
The hydrogenated diene-based copolymer of (1). (A)-(B) block copolymer comprising a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a vinyl aromatic compound and conjugated diene random copolymer block (B), (2) ). The above (A)-(B) block copolymer comprises a vinyl aromatic compound and a tapered block (C) in which the vinyl aromatic compound in the conjugated diene gradually increases (A)-(B)- (C) block copolymer, (3). The above (A)-(B) block copolymer may be composed of a (A)-(B)-(A) block copolymer composed of a vinyl aromatic polymer block (A).

In these hydrogenated diene-based copolymers, the ratio of vinyl aromatic compound and conjugated diene is 5 to 5 by weight.
60 / 95-40, the bond content of the vinyl aromatic compound in the above-mentioned component (A) and the above-mentioned component (C) that is optionally constituted is 3 to 50% by weight of all monomers, and Hydrogen is added to the block copolymer in which the content of the vinyl aromatic compound in the component (A) is at least 3% by weight and the content of vinyl bond in the conjugated diene moiety 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 bonds in the conjugated diene moiety are saturated is added is preferable.

As a typical example of this, hydrogenated styrene
Adopted the structure of butadiene rubber, a material called HSBR abbreviated from Japan Synthetic Rubber Co., Ltd.
N) It is marketed under the brand name of HSBR.

Next, as the ethylene / propylene copolymer (b), block polypropylene, random polypropylene or the like in which polypropylene or polyethylene or ethylene / propylene copolymer rubber (EPR) is blended can be used.

Here, it is effective to appropriately select the ethylene / propylene copolymer to be blended depending on the desired characteristics such as fluidity, hardness, heat resistance and the like.

Particularly, in order to obtain a final composition having a low hardness, a random polymerization type ethylene / propylene copolymer is suitable. Because the heat resistance of the hydrogenated diene copolymer itself is lower than that of the ethylene / propylene copolymer,
This is because the dimensional stability after molding is particularly poor.

That is, the higher the blending ratio of the hydrogenated diene copolymer, the greater the shrinkage rate when the molded article is left at a high temperature. In order to improve this, it can be achieved 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 having low hardness and excellent heat resistance and dimensional stability as much as possible, random polypropylene, which is easy to reduce surface hardness and flexural modulus, is preferable. In particular, random polypropylene having an ethylene content of 4 to 8% by weight is preferable, and further, random polypropylene having an ethylene content of 6 to 8% by weight is preferable.

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

When the composition of the present invention is produced, the respective components may be mixed together, or the optional components may be premixed in advance and then the remaining components may be added and mixed.

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

Further, it is not always necessary to knead all the components before introducing them into the molding machine. That is, both or only one of the hydrogenated diene copolymer and the ethylene / propylene copolymer are separately melt-kneaded or simply kneaded with the necessary components, and the respective pellets are tumbled or attached to a molding machine for weighing. It may be used as a master batch for blending with a mixer.

Further, the powder component in the blended component may be put into the molding machine in a state of being spread on the surface of the pellet component, and may be used as a dry color.

Furthermore, 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,
Antibacterial agents, antifungal agents, etc. 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 for various packings, bumpers, belts, skin materials, cushion materials, caps and sealing materials, bottom lining parts for slip prevention, hoses and the like. Household goods such as tubes and cords, toys, stationery and other miscellaneous goods,
It can be applied to automobile parts.

Specific contents of the present invention will be described below with reference to Tables 1 and 2, but the present invention is not limited to these examples.

[0040]

[Table 1]

[0041]

[Table 2]

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

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

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

(3). Tensile Permanent Elongation Ratio The tensile permanent elongation ratio is determined by measuring the distance between marked lines after fixing the dumbbell for 10 minutes with the No. 3 dumbbell stretched to 100% and then leaving the load open for 10 minutes. The elongation rate from the distance between the lines was calculated.

(4). Dynamic slip resistance Dynamic slip resistance is 1 mm / sec in the horizontal direction by contacting a R0.5 mm sapphire needle with a load of 50 g so that it hits the injection-molded product of the mirror surface of the mold vertically. And the resistance force generated during the movement was measured.

(5). Blocking property Blocking property is that the mold temperature is 50 ° C and the resin temperature is 220.
Immediately after molding, 5 pieces of JIS K-6301 No. 3 dumbbells molded at ± 20 ° C were stacked so as to be in close contact with each other, left at room temperature for 1 hour, and then peeled off one by one, and judged as follows. did.

◯: Can be easily peeled off without any problem, and no trace of adhesion is left on the peeled surface.

Δ: Peeling is possible, but a trace of adhesion remains on the peeled surface.

X: Completely fused and cannot be peeled off.

(6). Tactile sensation The tactile sensation was classified as follows by directly touching the clean product with a finger.

B: Neither sticky nor slimy.

Δa: There is a sticky feeling.

Δb: There is a slimy feeling.

Xa: Large stickiness.

Xb: Large sliminess.

(7). Scratchability Scratchability is obtained by contacting a R0.75mm diamond needle with a load of 50g so that it hits the injection-molded product of the mirror surface of the mold vertically and moving it horizontally at 1mm / sec. Make a linear scratch, magnify the scratch using a profilometer, measure the depth of the scratch, and compare the depth of the scratch with the degree of the trace of the scratch that you see with your eyes as follows. It was ranked.

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

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

X: The depth of scratches is 8 μm or more.

(8). MFR MFR complies with ASTM D1238, 230 ℃,
It was measured at a load of 2.16 kg.

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

(1). Symbol in the table: D-1 The hydrogenated diene-based copolymer used in this example is DYNARON 1320P manufactured by Nippon Synthetic Rubber Co., Ltd. This is a vinyl aromatic compound containing 5 to 5 styrene.
It is a hydrogenated diene-based copolymer (HSBR) containing 15% of styrene, more preferably 8 to 12% of styrene. The MFR is a grade of 3.5 (g / 10 minutes).

(2). Symbol in the table: P-1 Block polypropylene used as an ethylene / propylene copolymer component in this example is a product of Showa Denko KK
Manufactured by Show Allomer MK541.

(3). Symbol in the table: P-2 The block polypropylene used as the ethylene / propylene copolymer component in this example is Ube Industries, Ltd.
UBE Polypro J830 HV manufactured by UBE.

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

(5). Symbol in the table: P-4 The random polypropylene used in this example has an ethylene content of 6 to 7% by weight and an MFR of 2 (g / 10 minutes).
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 the saturated fatty acid amide.

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

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

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

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

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

(12). In the table: F-1 Spreading of the compounding ingredients used in this example, spreading for the purpose of dispersing, as a dispersant, Tenro 7 manufactured by San Nopco Ltd.
0 was used.

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

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

(15). Symbol in the table: F-4 As the antifungal and antibacterial agent used in this example, 2.3.
5.6 Tetrachloro 4 (methylsulfonin) 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] DYNARO
N) 1320P (symbol in the table: D-1) per 70 parts by weight, 0.9 part by weight of erucic acid amide (symbol in the table: A-3) and tenro 70 (symbol in the table: F-1) are 0. .05 parts by weight were tumbled in a cooler mixer.

Next, to 70.95 parts by weight of this mixture, 3 parts of Show Allomer MK541 (symbol in the table: P-1) was added.
An additional 0 part by weight was added and further mixed by rotation.

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

[Example 2] Show allomer MK541
(Symbol in the table: P-1) is 0.9 part by weight per 30 parts by weight of erucamide (Symbol in the table: A-3) and Tenro 70.
(Symbol in Table: F-1) was rotatively mixed with 0.05 part by weight 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 by using a single screw kneading and extruding machine of a dullage type screw to form pellets.

With respect to 30.95 parts by weight of this pellet,
70 parts by weight of DYNARON 1320P (symbol in the table: D-1) pellets were used at 20 rpm using a tumbler.
Pellet mix for 5 minutes. A test piece was prepared from the mixed pellet using an injection molding machine at a molding temperature of 220 ± 20 ° C.

[Example 3] DYNARON 132
0P (symbol in the table: D-1) is 0.9 parts by weight of erucic acid amide (symbol: A-3 in the table) and titanium dioxide (symbol: F-1 in the table) as a coloring agent per 70 parts by weight. 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 Tenro 70 (symbol: F-1 in the table). And were tumbled in a cooler mixer.

Next, to 71.75 parts by weight of this mixture, 30 parts by weight of Show Allomer MK541 (symbol: P-1 in the table) was added and further mixed by rotation.

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 using an injection molding machine at a molding temperature of 220 ± 20 ° C.

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

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

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 pelletize the mixture. A test piece was prepared from the pellet using an injection molding machine at a molding temperature of 220 ± 20 ° C.

[Embodiment 5] DYNARON 132
0P (Symbol in the table: D-1) per 70 parts by weight, 0.6 parts by weight of erucic acid amide (Symbol in the table: A-3) and Tenro 70 (Symbol in the table: F-1) were added in an amount of 0. 05 parts by weight were tumbled in a cooler mixer.

Next, to 70.65 parts by weight of this mixture, 30 parts by weight of Show Allomer MK541 (symbol in the table: P-1) was added and further mixed by rotation.

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 using an injection molding machine at a molding temperature of 220 ± 20 ° C.

[Embodiment 6] DYNARON 132
0.3 parts by weight of erucic acid amide (symbol in the table: A-3) and Tenro 70 (symbol in the table: F-1) per 0.3 part by weight of 0P (symbol in the table: D-1). 05 parts by weight were tumbled in a cooler mixer.

Next, to 70.35 parts by weight of this mixture, 30 parts by weight of Show Allomer MK541 (symbol in the table: P-1) was added and further mixed by rotation.

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 pelletize the mixture. A test piece was prepared from the pellet using an injection molding machine at a molding temperature of 220 ± 20 ° C.

[Embodiment 7] DYNARON 132
0P (symbol in the table: D-1) per 70 parts by weight, 0.9 parts by weight of erucic acid amide (symbol in the table: A-3) and Tenro 70 (symbol in the table: F-1) were added in an amount of 0.9. 05 parts by weight were tumbled in a cooler mixer.

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

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 pelletize the mixture. A test piece was prepared from the pellet using an injection molding machine at a molding temperature of 220 ± 20 ° C.

[Embodiment 8] DYNARON 132
For each 65 parts by weight of 0P (symbol in the table: D-1), 0.9 parts by weight of erucic acid amide (symbol in the table: A-3) and Tenro 70 (symbol in the table: F-1) were added. 05 parts by weight were tumbled in a cooler mixer.

Then, with respect to 65.95 parts by weight of this mixture, 35 parts by weight of the ethylene content is 6 to 7% by weight, and MF is added.
Random polypropylene (P-3) with R of 30 (g / 10 minutes) was added and further mixed by rotation.

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 pelletize the mixture. A test piece was prepared from the pellet using an injection molding machine at a molding temperature of 220 ± 20 ° C.

[Embodiment 9] DYNARON 132
For each 65 parts by weight of 0P (symbol in the table: D-1), 0.9 parts by weight of erucic acid amide (symbol in the table: A-3) and Tenro 70 (symbol in the table: F-1) were added. 05 parts by weight were tumbled in a cooler mixer.

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

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 pelletize the mixture. A test piece was prepared from the pellet using an injection molding machine at a molding temperature of 220 ± 20 ° C.

[Embodiment 10] DYNARON 13
20P (symbol in the table: D-1) is 0.9 per 65 parts by weight.
Parts by weight of stearic acid amide (symbol in the table: A-1),
Tenro 70 (symbol: F-1 in the table) and 0.05 part by weight were rotationally mixed in a cooler mixer.

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

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

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

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

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 using an injection molding machine at a molding temperature of 220 ± 20 ° C.

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

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

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 pelletize the mixture. A test piece was prepared from the pellet using an injection molding machine at a molding temperature of 220 ± 20 ° C.

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

This 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 / extruding machine of a dullage type screw to pelletize it. This pellet is molded at a molding temperature of 2 using an injection molding machine.
Test pieces were prepared at 20 ± 20 ° C.

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

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

From the above results, when the composition of Example 8 is compared with the composition characteristics of Comparative Example 1 containing no higher fatty acid amide based on the same resin composition, hardness, tensile stress, permanent elongation, etc. It does not affect the basic material properties as a thermoplastic elastomer, the dynamic slip resistance is reduced by 93% or more, blocking does not occur immediately after molding, and there is no sticky feeling or slimy feeling. It can be seen that excellent surface characteristics are obtained, which have a good feel to the touch and are less likely to be scratched.

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

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

However, it goes without saying that the evaluation criteria in Table 2 are relative and can be used depending on the actual use environment of the molded article using these compositions. For example, when it is applied to a product having a high temperature of use environment, the addition of a higher fatty acid amide having a high melting point has less adverse effect on the basic physical properties of the material, and the effect can be maintained for a long time.

In Examples 1 to 7, the flexural modulus according to ASTM D790 is 2 to 3 times that of the random polypropylene used in Examples 8 to 12 (13,000 to 15,000). kg / cm ² ) of block polypropylene was blended.

Example 2 in which all of the compounding ingredients were melt-kneaded in advance, and other additive components were melt-kneaded only in the ethylene / propylene copolymer (SHOAROMER MK541), and then pellets and pellets of DYNARON 1320P were prepared. Comparing the mixed Example 1, it can be seen that the characteristics of the obtained composition are almost the same, and that the same effect can be obtained by any manufacturing method.

Examples 3 and 4 are examples in which pigments and function-imparting additives (in this case, fungicides, antibacterial agents or ultraviolet absorbers) were added based on the resin composition and manufacturing 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.

[0126] Examples 5 and 6 are cases in which the amount of higher fatty acid amide compounded based on Example 1 was reduced.

As the blending amount of the fatty acid amide was decreased, the effect of improving the surface properties such as dynamic slip resistance, blocking property, touch feeling, scratch resistance, etc. gradually decreased.

These compositions can also be used according to the specifications of the product as described above.

[0129]

As described above, according to the thermoplastic elastomer composition of the present invention, stains are unlikely to occur, there is no problem of transfer to other parts where the compounding components come into contact, and scratches are unlikely to occur despite having gloss. It is possible to provide a thermoplastic elastomer composition having such excellent surface characteristics that it does not generate harmful gas during combustion and has excellent resistance to global environmental pollution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masao Sunagawa 1-1-1 Higashitaga-cho, Hitachi-shi, Ibaraki Hitachi Ltd. Living Equipment Division

Claims (13)

[Claims] 1. A block copolymer (a) 8 comprising a polymer block (A) of a vinyl aromatic compound, a random copolymer block (B) of a conjugated diene and a vinyl aromatic compound.
0 to 50 parts by weight and 100 parts by weight of a mixed composition of 20 to 50 parts by weight of the ethylene / propylene copolymer (b) are blended with 0.2 to 5.0 parts by weight of higher fatty acid amide. Thermoplastic elastomer composition. 2. 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
0.2 to 50 parts by weight of the (A)-(B) block copolymer (a) and 20 to 50 parts by weight of the ethylene / propylene copolymer (b) are mixed with 100 parts by weight of the higher fatty acid amide. A thermoplastic elastomer composition, characterized in that the thermoplastic elastomer composition is blended in an amount of up to 5.0 parts by weight. 3. 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) consisting of block (C) 80-
50 parts by weight of ethylene / propylene copolymer (b) 20
A thermoplastic elastomer composition comprising 100 parts by weight of a mixed composition of 100 parts by weight to 50 parts by weight of 0.2 to 5.0 parts by weight of a higher fatty acid amide. 4. 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)-(B consisting of a vinyl aromatic polymer block (A). )-(A) block copolymer (a) 80-50
Ethylene / propylene copolymer (b) 20 to 5 parts by weight
A thermoplastic elastomer composition comprising 100 parts by weight of a mixed composition of 0 parts by weight and 0.2 to 5.0 parts by weight of a higher fatty acid amide. 5. The thermoplastic elastomer composition according to claim 1, wherein the mixed composition has a Shore A hardness of 50 to 90. 6. The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the higher fatty acid amide is a higher fatty acid amide having a melting point in the range of 70 to 100 ° C. 7. The thermoplastic elastomer composition according to claim 1, wherein the higher fatty acid amide is an unsaturated fatty acid first amide compound. 8. The first unsaturated fatty acid according to claim 7,
The thermoplastic elastomer composition, wherein the unsaturated fatty acid of the amide compound has 17 to 21 carbon atoms. 9. The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the ethylene / propylene copolymer is an ethylene / propylene random copolymer. 10. The ethylene content of the ethylene / propylene random copolymer according to claim 9,
A thermoplastic elastomer composition, characterized in that it is from 8 to 8% by weight. 11. The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the higher fatty acid amide is preferably added in an amount of 0.3 to 4.5 parts by weight. 12. The thermoplastic resin according to claim 1, wherein at least the (A)-(B) block copolymer (a) has a styrene content of 5 to 15%. Elastomer composition. 13. The thermoplastic elastomer composition according to claim 12, wherein at least the (A)-(B) block copolymer (a) has a styrene content of preferably 8 to 12%. object.