JP2002121309A - Extrusion-foamed thermoplastic elastomer molding and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain extrusion-foamed thermoplastic elastomer moldings which have good soft touch and cold resistance, is thin, and is excellent in recyclability. SOLUTION: A composition prepared by compounding a resin blend at least containing (A) a thermoplastic olefin elastomer, (B) a thermoplastic styrene elastomer, and (C) an ethylene/α-olefin copolymer with a blowing agent is melted, kneaded, and foamed by using an extruder comprising a screw and a cylinder, is formed through a T-die into a sheet, and is stretched with a nip roll, thus giving a soft extrusion-foamed thermoplastic elastomer molding which, though being a foam, is not broken because of its good stretchability, has a good surface state, and has a Shore A hardness of 70 or lower, a density of 0.85 g/cm3 or lower, and a thickness of 1 mm or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an extruded olefinic thermoplastic elastomer foamed thin sheet molded article and a method for producing the same, and more particularly, it has a soft feeling, good cold resistance, and excellent recyclability that enables thinning. The present invention relates to an extruded olefin-based thermoplastic elastomer foam and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, attention has been focused on environmental issues.
Also in the development of materials, there is a demand for materials that are lightweight, contribute to energy saving such as CO ₂ reduction, are easy to recycle, do not generate toxic gases and the like, and are easy to dispose of by incineration. The foam molded product becomes a soft molded product, and the cushioning property is amplified, and the rigid molded product is increased in rigidity, the shock resistance increases because the cell space reduces the propagation as a stress absorber, and it may be damaged by any chance. Have the property that they do not scatter. In addition, since the foamed molded article has improved heat insulating properties and is lighter, the use of energy can be significantly reduced. Furthermore, due to the aging of society, from the interior and exterior materials of cars, to all places such as indoor desks, stairs, bathrooms, toilets, and daily necessities, when falling and hitting with a soft touch However, there is a demand for a material that has no sharpness, such as to prevent injuries.

Conventionally, as such cushioning materials, crosslinked foamed polyurethane, crosslinked foamed polypropylene,
A foam material such as cross-linked foamed polyethylene, cross-linked and non-cross-linked foamed polyvinyl chloride, and a skin material such as polyvinyl chloride, fabric, olefin-based thermoplastic elastomer, and the like have been used. However, there is a problem that the foamed material produced by such a method is cross-linked and difficult to recycle, and a large amount of industrial waste is generated due to a large loss in the production process. Particularly, polyvinyl chloride may generate harmful substances due to low-temperature incineration or the like.

[0004] Crosslinked EPDM or polyurethane is used as a speaker cone edge material requiring durability and vibration absorption performance, but has problems in hydrolyzability and durability. For this reason, some thermoplastic elastomer sheets have been used, but because they are too flexible, especially for bass woofers, vibration absorption performance has been required. Therefore, although a thermoplastic elastomer extruded foam molded article has been eagerly desired for these uses, foaming has been difficult.

[0005] A plastic or glass hollow microsphere dispersed in a plastic-based hard matrix is known as a syntactic foam. But,
Since this syntactic foam disperses hollow microspheres in a plastic-based hard matrix, the molded product has compression resistance, but becomes rigid without flexibility,
Since it does not whiten when bent and does not return to its original shape and does not retain its elastomeric properties, it cannot be used as a door seal material or cushioning material (cushion material).

Further, Polymer Digest 1996,
7, pages 106 to 108, describe that a heat-expandable microcapsule containing isobutane is blended with an elastomer or rubber and is injected and extruded.
This microcapsule has a particle size after expansion of 50 to 120 μm.
It is 100% complete closed cells in m, and when used for thermoplastic elastomers and rubbers, it is described as having excellent surface smoothness, uniform expansion state, and easy complex molding, but is microscopically observed. And heat-expandable microcapsules are not evenly dispersed, so there is a place with extremely weak strength,
There is a problem in physical properties.

In the case of producing a foam by extrusion molding of an olefinic thermoplastic elastomer, the melt viscosity of the olefinic thermoplastic elastomer is low. However, there is a problem that the strength of the foam cannot withstand the stretching in the step (1), the burst of the cell membrane occurs, and a soft thin sheet cannot be manufactured.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a thin, high-strength, extruded thermoplastic elastomer molded article in which foams of uniform size without burst are formed by extrusion foam molding, and a method for producing the same. The purpose is to:

[0009]

Means for Solving the Problems In order to achieve the above object, the present inventors have further studied from the viewpoint of the material, molding and the like. As a result, in adding a thermally decomposable foaming agent to the thermoplastic elastomer and decomposing the foaming agent under heating and melting to produce a foam, without using the olefinic thermoplastic elastomer alone, the olefinic thermoplastic elastomer When styrene-based thermoplastic elastomer and ethylene α-olefin copolymer are mixed and used, it becomes suitable for foaming of thin sheet during molding, and the gas generated by thermal decomposition of the foaming agent is sufficiently and evenly distributed in the melt. And uniform and fine bubbles are uniformly distributed throughout the foam, and the foam film is less ruptured inside the foam and on the surface of the foam, requiring only one step (extrusion foam molding). It has been found that a thermoplastic elastomer extruded foamed product can be obtained with less energy consumption and less loss. The obtained thermoplastic elastomer extruded foamed article has excellent mechanical properties due to a good foamed structure, and further has good softness and cold resistance, is thin, has excellent recyclability, and is low in cost. Therefore, it has been found that the extruded thermoplastic elastomer molded article can be effectively used in a wide range of fields by utilizing these various properties.

That is, the extruded thermoplastic elastomer molded article of the present invention comprises a component (A) an olefin-based thermoplastic elastomer, a component (B) a styrene-based thermoplastic elastomer, and a component (C) an ethylene α-olefin copolymer. With a Shore-A hardness of 70 or less and a density of 0.8
An extruded thermoplastic elastomer molded article having a thickness of 5 g / cm ³ or less and a thickness of 1 mm or less. In addition, the method for producing a thermoplastic elastomer extruded foamed article of the present invention comprises: a component (A) an olefin-based thermoplastic elastomer; a component (B) a styrene-based thermoplastic elastomer;
Component (C) One or more foaming agents selected from the group consisting of bicarbonates, citrates, diazocarbonamides and hydrazines per 100 parts by weight of the resin composition containing the ethylene α-olefin copolymer. Is added to 0.1 to 10 parts by weight, and the mixture is extruded by heating and extruding using a screw, cylinder, and die.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The extruded foam molded article of the present invention comprises at least a component (A) olefin-based thermoplastic elastomer, a component (B) a styrene-based thermoplastic elastomer, and a component (C) an ethylene α-olefin copolymer. And coalescence. [Component (A) Olefin-based thermoplastic elastomer] As an olefin-based thermoplastic elastomer, Japanese Patent Publication No. Sho 53
-21021, a sequential kneading mixture of an ethylene α-olefin copolymer rubber, a partially crosslinked product and an olefin resin, and a simultaneous kneading mixture of an ethylene α-olefin and an olefin resin known in JP-B-53-34120. Partially cross-linked kneaded products, partially cross-linked products of ethylene α-olefin copolymer rubber known in Japanese Patent Publication No. 62-59139, a partially cross-linked product of an ethylene-based resin, a mixture of a rubbery material and an olefin-based resin, etc. Can be exemplified. As the olefin-based thermoplastic elastomer, at least E
Those obtained by a dynamic crosslinking method in which an organic peroxide is treated while kneading two or more of PDM and PP are particularly preferable.

The olefin-based thermoplastic elastomer has a melt index (hereinafter may be abbreviated as “MI”) of 10 g / 10 mi at 230 ° C. * 10 kg load.
50 g / 10 at 230 ° C * 2.16 kg load over n
Min, preferably 15g at 230 ° C * 10kg load
30g at 230 ° C * 2.16kg load over / 10 min
/ 10 min or less, more preferably 20 g / 10 min or more at 230 ° C. * 10 kg load and 20 g / 10 min or less at 230 ° C. * 2.16 kg load. MI is 230 ℃ * 10
When the load is less than 10 g / 10 minutes under a kg load, the flow of the resin may be deteriorated, the extrusion processability may be deteriorated, and the appearance of the molded product may be deteriorated. The decomposition of the foaming agent cannot be controlled, and the production of molded articles may be difficult. 230 ° C * 2.
When the load is 16 g / 51 g or more at a load of 16 kg, the viscosity is too low to hold the foaming gas, and the cell is broken, the surface is easily broken and a pinhole is generated. The MI here is
It is a measure of the fluidity of a thermoplastic resin when it melts, and is measured by the method described in ASTM D1238.
It is a value measured under the conditions of 0 ° C., 10 kg, and 2.16 kg load.

Further, olefin-based thermoplastic elastomer, 0.87 g / cm ³ density of 0.93 g / cm ³ or less
Min., Preferably 0.87 at 0.92 g / cm ³ or less.
g / cm ³ or more. If the density of the olefin-based thermoplastic elastomer exceeds 0.93 g / cm ³ , the gas generated by the foaming agent cannot be retained, and it is difficult to swell greatly.

Further, the olefinic thermoplastic elastomer has a maximum melting peak temperature by DSC: Tm (° C.)
Is preferably 130 to 170 ° C., more preferably 14 to 170 ° C., from the viewpoint of imparting heat resistance and strength to the obtained foamed sheet.
0-160 ° C. Maximum melting peak temperature of olefin-based thermoplastic elastomer by DSC: Tm (° C) is 1
If the temperature is lower than 30 ° C., it cannot be used for automobile interior parts due to insufficient heat resistance, and the obtained foamed sheet may have poor flexibility and hardness, or may have poor foamability.
If the temperature exceeds 70 ° C., the foaming agent starts to be decomposed in the temperature range and enters the gas release temperature range, so that the foam of the thermoplastic elastomer in the unmelted state may be difficult to foam.

[0015] The olefin-based thermoplastic elastomer includes:
As a commercial product, for example, Mitlastomer 4 manufactured by Mitsui Chemicals, Inc.
010N "and" Milastomer 5010N "," Sumitomo TPE Santoprene "series manufactured by Sumitomo Chemical Co., Ltd.," Santoprene 1 "of" Santoprene "series manufactured by AES
"KS35" of the "CALLOY" series manufactured by Montell, such as "11-45" and "Santoprene 111-55"
3P "and the like. In particular, the above “Milastomer 503
0N "is obtained by a dynamic cross-linking method in which at least two kinds of EPDM and PP are kneaded and treated with an organic peroxide, and has heat resistance, strength and texture like a vehicle interior material. It is suitable for use in which is required.

[Styrene-based thermoplastic elastomer] A styrene-based thermoplastic elastomer is a block copolymer containing styrene and has a Shore-A hardness of 90 or less.
Preferably it is 50-80. As the styrene-containing block copolymer, a hydrogenated styrene / ethylene propylene block copolymer called SEPS and a hydrogenated styrene / isobutylene block copolymer called SEBS are preferable. Further, when the styrene-based thermoplastic elastomer has a Shore-A hardness of more than 90, the foamed thin sheet becomes hard, and it is difficult to obtain a flexible sheet. Commercially available styrene-based thermoplastic elastomers include, for example, Kuraray's `` Septon '' series, Mitsubishi Chemical's `` Lavalon '' series, JSR's `` Dynalon '' series, Asahi Kasei's `` Toughtec '' series, "Clayton G series" manufactured by Shell Chemical Company is included.

[Ethylene / α-olefin copolymer] Examples of the ethylene / α-olefin copolymer include an ethylene-pentene copolymer synthesized under a metallocene catalyst and an ethylene-octene copolymer synthesized under a metallocene catalyst. Coalescence and the like are preferred.

The density of the ethylene / α-olefin copolymer is preferably 0.90 g / cm ³ or less, more preferably 0.88 g / cm ³ or less. If the density exceeds 0.90 g / cm ³ , the gas generated by the foaming agent cannot be retained, and it may be difficult to largely swell, which is not preferable. On the other hand, it is preferable that the density is within a preferable range of 0.90 g / cm ³ or less, since the above-mentioned drawbacks can be avoided and processing can be performed in a wide temperature range.

The ethylene / α-olefin copolymer
MI is preferably 0.5 to 10 g / 10 min, more preferably 1.0 to 7.0 g / 10 min.
0 to 5.0 g / 10 min is particularly preferred. When the MI is 0.
If it is less than 5 g / 10 minutes, the flow of the resin may be deteriorated and the extrusion processability may be deteriorated, and the appearance of the molded product may be deteriorated. The decomposition of the foaming agent cannot be controlled, and the production of molded articles may be difficult. If it exceeds 10.0 g / 10 minutes, the melt tension required for holding the foaming gas cannot be obtained, and the foaming gas will escape. On the other hand, when the MI is within a preferable range, the above-mentioned disadvantages are eliminated, and thus it is preferable in that the foaming processability can be improved. The MI of the ethylene α-olefin in the present invention is a measure of the fluidity of the thermoplastic resin at the time of melting, and was measured at 190 ° C. and 2.16 kg by the method described in ASTM D1238. Value.

The maximum melting peak temperature by DSC of the ethylene / α-olefin copolymer: Tm (° C.) is preferably from 60 to 100 ° C., and more preferably from 60 to 80 ° C. The highest melting peak temperature by DSC is 100
When the temperature exceeds ℃, the foamed sheet obtained is hard and difficult to process, and the obtained foamed sheet becomes hard. On the other hand, when the maximum melting peak temperature by the DSC is within the above-mentioned numerical range, there is no disadvantage, and processing can be performed at a low temperature.

In the ethylene / α-olefin copolymer, the comonomer for ethylene includes butene, pentene, hexene, octene and the like, and the ratio of these comonomer is 20% or more, preferably 21 to 30%.
%, More preferably 22 to 26%. When the ratio of the comonomer to ethylene is less than 20%, a sufficient steric hindrance effect of the comonomer cannot be obtained, the crystallinity increases, and the composition becomes hard. The higher the comonomer ratio, the lower the crystallinity and the more flexible. In addition, the molecules are entangled and the viscosity can be maintained even at a high temperature, and the retention of foaming gas is improved,
The expansion ratio can be increased. However, if it exceeds 30%, it is rubbery, and there is a possibility that the motor load is high and stops during extrusion.

As the ethylene / α-olefin copolymer, an appropriately synthesized product or a commercially available product may be used. These may be used alone or in combination of two or more. The ethylene / α-
The olefin copolymer is preferably used, for example, by a solution polymerization method using a geometrically constrained catalyst containing a metallocene compound, more specifically, a geometrically constrained catalyst (CGC) which is a kind of a single site catalyst (SSC) centered on a metallocene compound. Is obtained. When the geometrically constrained catalyst is used, the molecular chain structure is not disturbed even if the amount of the comonomer is large as compared with the case where a conventional Ziegler catalyst or the like is used, and a large amount of the comonomer can be uniformly introduced, Further, since the molecular weight distribution can be set in a narrow range, it is advantageous in that as a result, a copolymer having a high dependency on the shear rate of the melt viscosity, a high melt tension, and excellent moldability can be obtained. Among the geometrically constrained catalysts, an ethylene-octene copolymer produced by a unique catalyst technology called Insight technology is the most flexible, viscous, and has good foaming gas retention.

Commercially available ethylene / α-olefin copolymers include, for example, “Engage (registered trademark)” manufactured by DuPont Dow Elastomers, “EXACT” series manufactured by Exxon Chemical, and Mitsui Chemicals. Preferable is Evolue manufactured by the company.

[Blending Ratio of Each Elastomer, etc.] In the resin to be foamed, (A) the olefin-based thermoplastic elastomer is
It is 20 to 80% by weight, preferably 40 to 70% by weight, more preferably 50 to 65% by weight. Component (B) the styrene-based thermoplastic elastomer is 1 to 50% by weight, preferably 5 to 20% by weight, more preferably 5 to 15% by weight. The component (C) ethylene α-olefin copolymer includes:
It is 1 to 50% by weight, preferably 5 to 40% by weight, more preferably 20 to 40% by weight. (A) 20 to 80% by weight of the olefin-based thermoplastic elastomer, 1 to 50% by weight of the component (B) of the styrene-based thermoplastic elastomer, and 1 to 50% by weight of the component (C) of the ethylene α-olefin copolymer. Outside the range, all four qualities of foamability, flexibility, heat resistance and workability cannot be balanced well, which is not preferable.

[Blowing agent] The blowing agent can be appropriately selected according to the type of the base resin to be foamed, and is a citric acid-based Eiwa Kasei Kogyo Co., Ltd. which releases carbon dioxide as a gas generated by thermal decomposition. "EE207" and "Unifine P-3" manufactured by Otsuka Chemical Co., Ltd. When a heat-resistant thermoplastic elastomer is mixed, a nitrogen gas release type having a high foaming gas pressure and a large gas amount is preferable. For example, “AZ-H” manufactured by Otsuka Chemical Co., Ltd. is preferably used. The foaming agent is preferably based on the entire resin to be foamed,
It is added in an amount of 0.01 to 10% by weight, more preferably 0.5 to 5% by weight.

(Other additives) In the composition of the present invention, in addition to the above-mentioned materials, a lubricant for preventing sticking during the production of pellets, a light stabilizer for improving light resistance, and a heat resistance and rigidity improving agent. Fillers for coloring, pigments for coloring, and the like can be appropriately added. As the lubricant, it is preferable to use a high melting point type lubricant having little bleed or bloom and excellent in fogging properties. For example, ethylene stearyl amide is suitable. The lubricant is applied to the base resin
Preferably 0.1 to 2% by weight, more preferably 0.2
０．５0.5% by weight. As a light stabilizer, a benzotriazole ring-containing compound of an ultraviolet absorber is already prescribed as a foam retarder, so that it has a light stabilizing effect, but when a further stabilizing effect is required, a synergistic effect with this is required. High hindered amine (HALS) based light stabilizers are preferred. Examples of HALS-based light stabilizers include "Tinuvin 770", "Tinuvin 622LD", and "Kimasorb 944LD" manufactured by Ciba Geigy, and "LA-77" manufactured by Asahi Denka Kogyo.
“LA-62” is preferred. The HALS-based light stabilizer is preferably added in an amount of 0.05 to 1% by weight, more preferably 0.1 to 0.3% by weight, based on the base resin.
Examples of the inorganic filler include calcium carbonate, talc, and mica. These inorganic fillers can be appropriately added within a range that does not hinder foamability. The coloring agent can be colored with titanium white, carbon black, phthalocyanine blue, watching red, quinacridone red, titanium yellow, or the like.

[Method of Forming Extruded Foam Molded Article] The extruded thermoplastic elastomer molded article of the present invention can be obtained by a known extrusion foaming method. The extrusion foaming method includes (A) an olefin-based thermoplastic elastomer,
(B) styrene-based thermoplastic elastomer, component (C) ethylene α-olefin copolymer, foaming agent, and others
A compounded composition containing components to be compounded as needed is melt-kneaded and foamed from a screw and a cylinder by an extruder, rolled into a plate shape by a die called a T-die, and then stretched by a nip roll. The present invention, by this molding method,
Shore-A hardness 70 or less, preferably Shore-A
A hardness 20-65, preferably Shore-A hardness
20 to 55, a density of 0.85 g / cm ³ or less, preferably 0.20 to 0.80 g / cm ³ , more preferably 0.20 to 0.70 g / cm ³ , and a thickness of 1 mm or less,
Preferably, a thin-walled foam sheet having a thickness of 0.20 to 0.60 mm, more preferably 0.20 to 0.50 mm can be obtained.

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
Extrusion foam molding was performed under the following conditions in the evaluation of the examples and comparative examples shown in Table 1. Extrusion foam molding was performed using a raw material having the composition shown in Table 1 using an extrusion foam molding machine “FS65-30” manufactured by Ikegai Co., Ltd.

Extrusion foam molding conditions are as shown below. <Extrusion foam molding conditions> Molding machine; FS65-30 manufactured by Ikegai Co., Ltd .; single screw Screw; diameter 65 mm, L / D = 30, compression ratio 2.
5, rotation speed 60rpm lip width; 1250mm cylinder temperature; 210 ° C die temperature; 200 ° C molded product; width 1180mm, thickness 0.5mm

Example 1 Component (A) -1 Shore-A hardness 40 manufactured by Mitsui Chemicals, Inc. and MI 15
g / 10 minutes (230 ° C * 10 kg / cm ² ) TPV
60% by weight, Component (B) -1 Styrene thermoplastic elastomer Shore manufactured by Kuraray Co., Ltd.
-A hardness is 80 and MI is 100 g / 10 min (200 ° C * 1
0 kg / cm ² ) at 15% by weight, Component (C) -1 MFR of ethylene octene copolymer 5 g / 10 min (190 ° C. * 2.16 kg / c) manufactured by Dupont Dow Elastomers.
m ² ) A density of 0.870 g / cm ³ and a resin ratio of 25% by weight. 20% by weight of a citrine foaming agent manufactured by Eiwa Kasei Co., Ltd. as a blowing agent. 2 parts by weight of a polyethylene kneading master batch, and 20% by weight of pigment carbon black. One part by weight of a polyethylene kneading master batch was charged and extruded and foamed.
As a result, an elastomer foam having the properties shown in Table 1 was obtained. The present invention will be described more specifically with reference to the following experimental examples. [Evaluation Method] (1) Density: Specific gravity was determined by measuring the weight of the foam and the weight of the foam in water. (2) Hardness: Shore-A hardness measurement. (3) Bubble shape: A cell in a cross section cut in the stretching direction was observed with a microscope. In the case of spherical bubbles without tearing, it was evaluated as ○. When there was a breakage and there was a state in which adjacent bubbles were connected, it was evaluated as x.

Example 2 Component (C) -1 was replaced with (C) -2
An ethylene octene copolymer manufactured by DuPont Dow Elastomers Co., Ltd. was used at a low MI of 1.5 g / 10 min (190 ° C. * 2.1
An elastomer foam was obtained in the same manner as in Example 1 except that the density was changed to 0.895 g / cm ³ at 6 kg / cm ² ).

Example 3 Component (A) -1 was replaced with (A) -2
Shore-A hardness 50 manufactured by Mitsui Chemicals and MI 30
g / 10min (230 ° C + 10kg / cm ² ) TP
Except having changed to V, it carried out similarly to Example 1, and obtained the elastomer foam.

Example 4 Component (C) -1 was replaced with (C) -2
An ethylene octene copolymer manufactured by DuPont Dow Elastomers Co., Ltd. was used at a low MI of 1.5 g / 10 min (190 ° C. * 2.1
An elastomer foam was obtained in the same manner as in Example 3 except that the density was changed to 0.895 g / cm ³ at 6 kg / cm ² ).

Example 5 An elastomer foam was obtained in the same manner as in Example 1 except that the resin composition was the same but the number of the foaming agent was increased from 2 parts by weight to 5 parts by weight.

Example 6 An elastomer foam was obtained in the same manner as in Example 3, except that the resin composition was the same but the number of the foaming agent was increased from 2 parts by weight to 5 parts by weight.

Example 7 Ingredient (A) -1 Shore-A hardness 40 manufactured by Mitsui Chemicals Co. and MI 15
g / 10 minutes (230 ° C or 10 kg / cm ² ) TPV
60% by weight, Component (B) -1 Styrene thermoplastic elastomer Shore manufactured by Kuraray Co., Ltd.
-A hardness of 80 and MI of 100 g / 10 min (200 ° C.
* 10 kg / cm ² ) by 10% by weight, Component (B) -2: a styrene-based thermoplastic elastomer Shore-A hardness 41 manufactured by JSR (Japan Synthetic Rubber) Co., and MI of 10 g / 10 m
in (230 ° C * 2.16 kg / cm ² ), Component (C) -1 5 g / 10 min of ethylene octene copolymer MI manufactured by Dupont Dow Elastomers (190 ° C * 2.16 kg)
/ Cm ² ) and a density of 0.870 g / cm ³ at a resin ratio of 25% by weight.
The same operation as in Example 1 was carried out using 7 parts by weight of a polyethylene kneading master batch containing 7% by weight of polyethylene and 1 part by weight of a polyethylene kneading master batch containing 20% by weight of pigment carbon black.

Example 8 Component (A) -1 was replaced with (A) -2
Shore-A hardness 50 manufactured by Mitsui Chemicals and MI 30
g / 10min (230 ° C * 10kg / cm ² ) TP
Except having changed to V, it carried out similarly to Example 7, and obtained the elastomer foam.

Comparative Example 1 Component (A) -1 Shore-A hardness 40 manufactured by Mitsui Chemicals, Inc. and MI of 15 g / 10 mi
n (230 ° C. * 10 kg / cm ² ) 100% by weight of TPV, 2 parts by weight of a polyethylene kneading masterbatch containing 20% by weight of a citrus blowing agent manufactured by Eiwa Kasei Co., Ltd. as a blowing agent, and 2 parts by weight of a polyethylene kneading masterbatch containing 20% by weight of pigment carbon black One part by weight was charged and the same operation as in Example 1 was performed. Almost no bubbles are seen and it is hard.

Comparative Example 2 Component (A) -1 manufactured by Mitsui Chemicals, Inc.
Shore-A hardness of 40 and MI of 15 g / 10 min
(230 ° C * 10kg / cm^Two) Of (A) -2
Shore-A hardness 50 manufactured by Mitsui Chemicals and MI 30
g / 10min (230 ° C * 10kg / cm ^Two) TP
The same operation as in Comparative Example 1 was performed, except that V was changed to V. Comparison
As in Example 1, hardly any air bubbles were observed and the sample was hard.

Comparative Example 3 Component (A) -1 85% by weight of TPV having Shore-A hardness of 40 manufactured by Mitsui Chemicals and MI of 30 g / 10 min (230 ° C. * 10 kg / cm ² ), (B)- 1 Kuraray styrene-based thermoplastic elastomer Shoer-A hardness 80 and MI 100 g / 10 m
in (200 ° C. * 10 kg / cm ² ) to 15% by weight as a foaming agent, 2 parts by weight of a polyethylene kneading master patch containing 20% by weight of a citrus blowing agent manufactured by Eiwa Kasei Co., Ltd. One part by weight was charged and the same operation as in Comparative Example 1 was performed. Almost no bubbles are seen and it is hard.

Comparative Example 4 Component (A) -1 manufactured by Mitsui Chemicals, Inc.
Shore-A hardness of 40 and MI of 15 g / 10 min
(230 ° C * 10kg / cm^Two) Of (A) -2
Shore-A hardness 50 manufactured by Mitsui Chemicals and MI 30
g / 10min (230 ° C * 10kg / cm ^Two) TP
V. Expandable molded body in the same manner as in Comparative Example 1 except that V was changed to V
I got Similar to Comparative Example 1, almost no air bubbles were observed and the sample was hard.

Examples 1 to 7 and Comparative Examples 1 to
Table 1 shows a combination example of Comparative Example 4 and evaluation results.

[0043]

[Table 1]

[0044]

According to the extruded thermoplastic elastomer molded article of the present invention, the foamed article has excellent mechanical properties due to a good foamed structure, and further has a soft feeling, good cold resistance and a reduced thickness.
Excellent recyclability and low cost. Therefore,
The extruded thermoplastic elastomer molded article can be effectively used in a wide range of fields by utilizing these various properties. The thermoplastic elastomer extruded foamed article of the present invention is manufactured by using a non-crosslinked thermoplastic elastomer having good recyclability and foaming in the same process as in the past to produce a thermoplastic elastomer extruded foamed article having the above-mentioned properties. Becomes possible. Incidentally, in the conventional foaming method, for example, in the case of an olefin crosslinked foam, three steps of extrusion + crosslinking + foaming steps are required. In addition, urethane foam is premised on cross-linking, making recyclability difficult.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // B29K 21:00 B29K 21:00 23:00 23:00 25:00 25:00 105: 04 105: 04 F-term (reference) 4F070 AA15 AA16 AB08 AB09 AB11 AB23 AB24 AC35 AC74 AC75 AE08 FA03 FC05 GA05 4F074 AA13B AA17A AA24D AA25D BA02 BA03 BA12 BA13 BA20 CA22 DA32 DA33 4F207 AA03 AA13 AA45 AB02 AB12 BB15 AE10 BN03W BP01X DE206 EF006 EQ016 EQ026 FD326 GT00

Claims (10)

[Claims] Claims 1. A component (A) comprising an olefin-based thermoplastic elastomer, a component (B) a styrene-based thermoplastic elastomer, and a component (C) an ethylene α-olefin copolymer, having a Shore-A hardness of 70 or less and a density of 0.85g /
cm ³ or less, a thermoplastic elastomer extruded foam molded body, wherein the thickness is 1mm or less. 2. The component (A) olefin-based thermoplastic elastomer is produced by a dynamic crosslinking method in which at least two kinds of EPDM and PP are kneaded and treated with an organic peroxide, and has a melt index of 230 ° C. * 10 kg. 230 ° C at a load of 10 g / 10 min or more * 50 g / 10 min or less under a load of 2.16 kg, a density of 0.87 g / cm ³ or more at a density of 0.93 g / cm ³ or less, maximum melting peak temperature by DSC: Tm The extruded thermoplastic elastomer molded article according to claim 1, wherein (C) is in the range of 130 to 170C. 3. The method according to claim 1, wherein the component (B) styrene-based thermoplastic elastomer is a block copolymer containing styrene and has a Shore-A hardness of 90 or less. Extruded thermoplastic elastomer foam. 4. The ethylene (α) -olefin copolymer (C) having a comonomer having at least 5 carbon atoms and a melt index of 190 ° C. * 2.16 kg.
5 to 10.0 g / 10 min, density of 0.90 / cm ³ or less, maximum melting peak temperature by DSC: Tm
The extruded thermoplastic elastomer foam according to any one of claims 1 to 3, wherein (C) is in the range of 55 to 100C, and the comonomer ratio to ethylene is 20% or more. 5. Component (A) 20 to 80% by weight of an olefin-based thermoplastic elastomer, Component (B) 1 to 50% by weight of a styrene-based thermoplastic elastomer, and Component (C) 1% of an ethylene α-olefin copolymer. The extruded and foamed thermoplastic elastomer article according to any one of claims 1 to 4, wherein the molded article is contained in an amount of from 50 to 50% by weight. 6. A resin based on 100 parts by weight of a resin blend containing component (A) an olefin-based thermoplastic elastomer, component (B) a styrene-based thermoplastic elastomer, and component (C) an ethylene α-olefin copolymer. 0.1 to 1 of one or more foaming agents selected from the group consisting of carbonates, citrates, diazocarbonamides and hydrazines
A method for producing an extruded thermoplastic elastomer foam, wherein 0 parts by weight are added, and the mixture is extruded by heating and melting using an extruder comprising a screw, a cylinder and a die. 7. The component (A) olefin-based thermoplastic elastomer is produced by a dynamic crosslinking method in which at least two kinds of EPDM and PP are kneaded and treated with an organic peroxide, and has a melt index of 230 ° C. * 10 kg. 230 ° C at a load of 10 g / 10 min or more * 50 g / 10 min or less under a load of 2.16 kg, a density of 0.87 g / cm ³ or more at a density of 0.93 g / cm ³ or less, maximum melting peak temperature by DSC: Tm The method for producing an extruded thermoplastic elastomer molded article according to claim 6, wherein (° C) is in the range of 130 to 170 ° C. 8. The method according to claim 6, wherein the component (B) styrene-based thermoplastic elastomer is a block copolymer containing styrene and has a Shore-A hardness of 90 or less. A method for producing a thermoplastic elastomer extruded foam molded article. 9. Component (C) ethylene α-olefin copolymer having a comonomer having at least 5 carbon atoms and a melt index of 190 ° C. * 2.16 kg.
5 to 10.0 g / 10 min, density of 0.90 g / cm ³ or less, maximum melting peak temperature by DSC: Tm
The thermoplastic elastomer elastomer foam according to any one of claims 6 to 8, wherein (C) is in the range of 55 to 100C and the comonomer ratio to ethylene is 20% or more. Method. 10. Component (A) 20 to 80% by weight of an olefin-based thermoplastic elastomer, Component (B) 1 to 50% by weight of a styrene-based thermoplastic elastomer, and Component (C) 1% of an ethylene α-olefin copolymer. The method for producing an extruded thermoplastic elastomer foam according to any one of claims 6 to 9, wherein the content is from 50 to 50% by weight.