JPH08253634A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic elastomer composition having excellent flexibility, heat-softening resistant property, destructive strength property, and further waterproof property, weatherability and heat-fusible property, and to obtain a waterproof sheet composed of this composition. CONSTITUTION: This thermoplastic elastomer composition contains 90-10 pts.wt. of a polyolefinic thermoplastic resin containing a polypropylene.homopolymer resin and a random copolymer resin composed of at least two kinds of constituting units selected from ethylene, propylene and α-olefin, wherein the weight ratio of the homopolymer resin to the random copolymer resin is 1:9 to 9:1 and 10-90wt.% of an ethylene.propylene-based copolymer rubber composition and/or a butyl-based rubber composition, and at least a part of the ethylene.propylene-based copolymer rubber composition and/or a butyl-based rubber composition is dynamically cured by a curing agent and forms a dispersing phase, and a composition comprising this composition added with carbon black, and a waterproof sheet composed of these compositions are obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition having excellent flexibility, heat softening resistance and high breaking strength. In particular, it relates to a thermoplastic elastomer composition used for a waterproof sheet such as a waterproof sheet for a waste disposal site, which is excellent in waterproofness, weather resistance and heat-sealing property in addition to the above properties. It also relates to the waterproof sheet.
Here, the waterproof sheet is used as a general term for various types of waterproof sheets and waterproof sheets. In the following, unless otherwise specified, the waterproof sheet is a general term for various water-blocking and waterproof sheets.

[0002]

2. Description of the Related Art Conventionally, ethylene / propylene / diene copolymer rubber (EPD) has been used as a material used for a waterproof sheet for a waste disposal site or a waterproof sheet for construction and civil engineering.
M) -based vulcanized rubber compositions and the like are excellent in flexibility and weather resistance, but have drawbacks such as insufficient mechanical strength and heat fusion. In addition, high density polyethylene (HDP
Resins such as E) have high breaking strength, but lack flexibility and have heat fusion properties, but are hard to be fused even when heat is applied, resulting in poor workability during execution. There are drawbacks. Further, a thermoplastic elastomer composed of a so-called hard block / soft block such as a styrene / ethylene / butadiene copolymer is flexible, but has a drawback that it is easily softened by heat and is easily broken in direct sunlight. Therefore, in order to solve such a problem, a thermoplastic elastomer composition comprising a polypropylene resin (PP) and an EPDM rubber composition, which is a rubber composition subjected to dynamic vulcanization, is used. The physical properties have been controlled by controlling the ratio and further by compounding agents such as a vulcanizing agent, a plasticizer and a softening agent for the rubber composition.

For example, in JP-A-59-58043, a method in which a plastic such as polypropylene and an ethylene-propylene copolymer rubber composition are blended and dynamically vulcanized is 2000 seconds ^-1 or more. It describes a method of vulcanizing during kneading at a shear rate to vulcanize in a short time to prevent deterioration of rubber and resin, but the breaking strength is not yet satisfactory for the above purpose, and there is a problem. There is. Here, the shear rate is calculated by dividing the product obtained by multiplying the circumference of the circle drawn by the tip of the screw by the rotation speed of the screw for 1 second by the gap between the tips. In other words, shear rate is the tip velocity divided by the tip gap. Also, the residence time in the portion where dynamic vulcanization is performed is calculated by multiplying the total volume of the portion where dynamic vulcanization is performed by the filling factor and dividing it by the volumetric flow rate.

Further, in JP-A-2-235949, an ethylene-α / olefin / non-conjugated diene copolymer rubber composition, a crystalline polyolefin resin and, if necessary, a mineral softener are used with a phenolic vulcanizing agent. It describes a thermoplastic elastomer composition which is obtained by dynamic vulcanization and has good moldability while maintaining shape recovery properties such as oil resistance, high temperature mechanical properties and compression set. Then, as the crystalline polyolefin resin, a crystalline propylene / α-olefin copolymer is exemplified, but this is a block copolymer and has a problem of low breaking strength.

Further, in JP-A-2-283743, (a) an ethylene-α / olefin copolymer rubber graft-polymerized with a carboxyl group or an acid anhydride group,
(B) A crystalline polyolefin resin is dynamically crosslinked in the presence of a metal oxide or the like at a temperature equal to or higher than the melting point of (b) to form mechanical properties, oil resistance, heat aging resistance, weather resistance, permanent elongation, etc. Although a method for obtaining a thermoplastic elastomer composition which has recoverability and is resistant to discoloration by heat and light is described, there is no disclosure of a composition having both flexibility, heat-softening resistance and high fracture properties.

In JP-A-6-107878, molding of a film made of a thermoplastic synthetic resin based on a partially crystalline ethylene-propylene-diene-terpolymer, an alkene homo- and / or copolymer and a polymer modifier. Although it is described that the body is excellent in deep-drawing moldability and scar formation, the document describes a resin composition having flexibility and high breaking strength and waterproofness, weather resistance and adhesiveness, and a molded body thereof. Is not disclosed.

On the other hand, the water-blocking sheet used for a waste disposal site has flexibility and high breaking strength at the same time, and further has waterproof property and long-term weather resistance, and further, it can be bonded on site. It has to be possible. That is, it is necessary that the bonding surfaces of the sheets have the same adhesiveness. Generally, in the construction of the water-impervious sheet, a sheet having a certain area is directly carried in on the ground that has been leveled, and the seam is heated (heat-bonded) or coated with an adhesive to bond the seam. Then, at the time of joining, in order to join the sheets laid on the ground having a certain degree of unevenness so that the liquid is completely impermeable so that the liquid does not permeate, the sheet itself is enough to follow the unevenness of the ground. It must be flexible and then the sheets should have good adhesion to each other when heated. Furthermore, when the waste is thrown onto the sheet after the sheet is constructed, it has high breaking strength that does not damage it and heat-resistant softening that does not cause deformation due to softening even when exposed to direct sunlight. There is a need. If the water-blocking sheet is damaged or deformed excessively, it will cause water leakage and become a serious problem.
However, at present, a sheet having excellent flexibility has a low breaking strength, and has a high heat-softening resistance, and a sheet having a high breaking strength is poor in flexibility, so that the breaking strength, flexibility, and heat-softening resistance are both excellent, and No sheet material is known that is excellent in waterproofness, weather resistance and heat-sealing property.

[0008]

Therefore, the sheet used for such an application is made of a material having high flexibility, that is, high construction reliability and at the same time high breaking strength.
In addition, it is essential to have heat softening resistance and long-term weather resistance. However, since high breaking strength and heat-softening resistance are contradictory to flexibility, there is no composition having both properties in a highly balanced manner.

[0009]

The inventors of the present invention, in view of the above circumstances, have made diligent studies in order to improve these problems of the thermoplastic elastomer composition. As a result, as a resin component, At least a part of a resin composition in which a polypropylene resin (homopolymer) and an ethylene / propylene random copolymer resin (random polymer) are used together is a so-called matrix, and an ethylene / propylene copolymer rubber composition and / or a butyl rubber composition is used. By dispersing the material, forming at least a part of the domain, and further dispersing the rubber composition, by dynamically vulcanizing,
The inventors have found that fracture strength (tensile strength, elongation at break, tear strength, etc.) can be improved without impairing flexibility and heat softening resistance, and have completed the present invention.

That is, the object of the present invention is to contain a polypropylene homopolymer resin and a random copolymer resin having at least two or more units selected from ethylene, propylene and α-olefin as a constituent component. The weight ratio of the resin to the random copolymer resin is 1: 9-
9: 1 polyolefin thermoplastic resin 90 to 10
And 10 to 90 parts by weight of an ethylene / propylene copolymer rubber composition and / or a butyl rubber composition, and at least one of an ethylene / propylene copolymer rubber composition and / or a butyl rubber composition. Part
Provided is a thermoplastic elastomer composition in which a domain (dispersed phase) is dispersed in the polyolefin-based thermoplastic resin matrix, and at least a part of the domain is dynamically vulcanized by a vulcanizing agent. The composition of the composition is changed to a composition suitable for the required properties depending on the use. In particular, as a waterproof sheet used for civil engineering and construction, its weather resistance is also an important factor, and carbon black is the most suitable additive for improving it. By adding carbon black to the composition, ultraviolet rays and the like are shielded, so that deterioration of the polymer is suppressed. As a result, the tensile strength and elongation at break do not decrease even after long-term outdoor exposure. Further, the shielding effect of this carbon black is similarly observed even when carbon black is added to the rubber composition and / or the resin composition. Although the present invention comprises a rubber composition and a resin composition, the factor affecting the actual weather resistance lies in the resin composition. Therefore, the second object of the present invention is to use the above-mentioned first object in applications requiring weather resistance.
The polypropylene / homopolymer resin composition and the random copolymer resin composition of the thermoplastic elastomer composition for achieving the object of (3) are 0.3 to 300 parts by weight of carbon black based on 100 parts by weight of the total resin content. The thermoplastic elastomer composition according to claim 1, which comprises: Further, a third object of the present invention is to provide a thermoplastic elastomer composition which achieves the above first or second object,
An ethylene / propylene copolymer rubber composition and / or a butyl rubber composition provides a thermoplastic elastomer composition containing 0 to 400 parts by weight of carbon black based on 100 parts by weight of the total rubber content. . Also,
A fourth object of the present invention is to provide a waterproof sheet made of the above thermoplastic elastomer composition.

The present invention will be described in more detail below.
The thermoplastic elastomer composition of the present invention contains (i) an ethylene / propylene copolymer rubber and / or a butyl rubber component, which is a rubber component, based on 90 to 10 parts by weight of a thermoplastic polyolefin resin, which is a resin component. 10 to rubber
Contains 90 parts by weight. If the ratio of the resin component and the rubber component is within this range, any ratio may be used, but more preferably (i) :( ii) is 85 to 15 parts by weight: 15.
~ 85 parts by weight. If the amount of the rubber component is larger than this range, the content of the resin component that should form the matrix phase will be reduced as a result, sufficient thermoplasticity cannot be obtained, and the product cannot be processed and molded, and the breaking strength will be reduced. Further, if it is too small, the flexibility and the heat softening resistance will be insufficient.

(I) Resin Component (Polyolefin Thermoplastic Resin) The polyolefin thermoplastic resin used in the present invention is
(A) Polypropylene resin which is a homopolymer, and (b)
A random copolymer resin, which is a random polymer and has at least two types of units selected from ethylene, propylene, and α-olefin as a constituent, is used in combination.

(A) Homopolymer Polypropylene resin homopolymer is a polymer having isotactic, syndiotactic, and atactic stereochemical structures containing propylene as a unit portion. The polypropylene resin used preferably has a heat distortion temperature of 150 ° C. or higher according to JIS K7207, 230 ° C. according to JIS K6758, and a melt flow rate (MFR) of 0.5 to 40 g / 10 minutes at 2.16 kg.

(B) Random Polymer The random polymer used in the present invention comprises at least two kinds of units selected from ethylene, propylene and α-olefin as a constituent component. For example, ethylene / propylene / random copolymer and ethylene / α-olefin. A random copolymer, a propylene / α-olefin / random copolymer, or a ternary random copolymer of ethylene / propylene / α-olefin, which may be used in combination. As a commercial product, EZ manufactured by Showa Denko KK
112 etc. can be illustrated. α-olefin is
An unsaturated hydrocarbon having 4 to 20 carbon atoms, 1-butene,
Examples include α-olefins such as 1-pentene, 1-hexene, and 1-octene, and random copolymers thereof. Further, those having an ethylene unit, a propylene unit, or both an ethylene unit and a propylene unit as a main component are preferable, and those having a propylene unit are preferable, and particularly, an ethylene / propylene / random copolymer resin is preferable. . When these are not contained as the main components, as a result, the α-olefin having low or no crystallinity becomes the main component, the softening temperature is lowered, and the effect of improving the heat softening resistance is low. Particularly, as the α-olefin, those containing vinyl acetate, acrylic acid ester such as methyl acrylate, etc., have a large decrease in the softening temperature,
Since it does not have the effect of improving the heat softening resistance when used alone, it is preferably used in combination with the other random copolymer. It is not preferable to use a block copolymer instead of the random copolymer because the blend system (thermoplastic elastomer composition) of the present invention has no effect in improving the breaking strength. Further, when only the random copolymer is used alone, the softening temperature is lowered, and the heat softening resistance is impaired.

The proportion of propylene component in the random copolymer is preferably 98 to 50% by weight, even 9%.
It is 7 to 70% by weight. Furthermore, when the ethylene component is contained, the ratio of the ethylene component is preferably 2 to 40% by weight, more preferably 3 to 30% by weight. The MFR (melt flow rate) of such a random copolymer at 230 ° C. and 2.16 kg is preferably 0.5 to 40 g / 10 minutes.

Furthermore, the mixing ratio by weight of the homopolymer and the random copolymer is 1: 9 to 9: 1, more preferably 1.5: 8.5 to 8.5: 1.5. preferable. If the proportion of the homopolymer is less than this, the heat softening resistance is impaired. If the ratio of the random copolymer is less than this, there is no effect of improving the breaking strength. Also,
The homopolymer and the random copolymer used have similar melt viscosities at the time of kneading, that is, the viscosity ratio of the two is 1
It is preferable to select one close to the above from the viewpoint of dispersibility at the time of kneading.

(Ii) Rubber Component Examples of the rubber component used in the present invention include ethylene / propylene copolymer rubber, butyl rubber, and a mixture of both. The ethylene / propylene copolymer rubber is
It is a compound represented by the following formula (1) and is a copolymer rubber (EPDM) comprising ethylene, propylene and a third component X. As a commercial product, Mitsui Petrochemical Co., Ltd. Mitsui EPT
4070 etc. can be illustrated. The propylene content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%. Examples of the third component X include ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene. Among them, ethylidene norbornene having a high vulcanization rate is preferable. The amount of the third component X is
The iodine value is preferably 3 to 25, more preferably 5 to 20.

[0018]

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As the rubber that can be used as the butyl rubber used in the present invention, butyl rubber (IIR), chlorinated butyl rubber, brominated butyl rubber and the like are preferably exemplified, and among them, particularly, an average molecular weight of about 350,000 to 450,000, Chlorination rate 1.1〜
Chlorinated butyl rubber of about 1.3% is preferred. further,
As one embodiment of the butyl rubber, a copolymer rubber having an isobutylene unit and a p-halogenated methylstyrene unit represented by the following formula (2), and an isobutylene unit and p-halogen represented by the following formula (3). A copolymer rubber having a methylated methylstyrene unit and a p-methylstyrene unit is also preferably exemplified (hereinafter, these copolymer rubbers are referred to as X-
IPMS). Exxon Chemical Co., Ltd.
XP-50-90-10 (brominated isobutylene-p
-Methylstyrene copolymer rubber) can be exemplified. These copolymer rubbers are excellent in stability when kneading the thermoplastic resin and the rubber component described later.

[0020]

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A plurality of these rubbers may be blended and used.

(Iii) Vulcanization System (Crosslinking Agent, Vulcanizing Agent) The thermoplastic elastomer composition of the present invention further comprises a vulcanizing system such as a vulcanizing agent, a vulcanization accelerator, and a vulcanization aid. A vulcanizing agent is added during the kneading of the resin component and the rubber component and vulcanized during the kneading, that is, dynamically vulcanized and crosslinked. As the vulcanizing agent used in the present invention, all vulcanizable vulcanizing systems can be used. However, when EPDM is used as the rubber composition, a vulcanizing resin (modified alkylphenol resin), sulfur-based or organic A vulcanization system using a peroxide-based vulcanizing agent; when a butyl rubber is used as the rubber composition, a vulcanization resin (modified alkylphenol resin), a sulfur-based or quinonedioxime-based, zinc white, A vulcanization system using a mixture of zinc white and stearic acid, a metal stearate such as zinc stearate, a zinc salt of dithiocarbamate, a combination of thiuram and thiazole, and an EPDM / butyl rubber. In the case of a mixture composition, a vulcanizing resin (modified alkylphenol resin) or a vulcanizing system using a sulfur-based or quinonedioxime-based vulcanizing agent is preferable; It is shown. Furthermore, when using chlorobutyl rubber, an alkylphenol resin can be used as a vulcanization aid.

Here, the vulcanization system of these rubbers is appropriately added as a crosslinking agent (vulcanizing agent) in the process of dynamic vulcanization described later, and at least a part of the vulcanization system serves as domains in the resin forming the matrix. It is used to obtain the desired thermoplastic elastomer composition by dynamic vulcanization in which vulcanization proceeds while kneading at a temperature that promotes vulcanization until vulcanization of the dispersed rubber phase is completed. It is sufficient that the amount of the vulcanizing agent used in the present invention is 0.1 to 20 parts by weight, particularly 0.5 to 15 parts by weight, based on 100 parts by weight of the ethylene / propylene copolymer rubber. Get the degree of cross-linking,
It is preferable in terms of ensuring the heat softening resistance.

The vulcanization accelerator and vulcanization aid used in the present invention include fatty acids such as stearic acid and lauric acid, metal salts such as zinc salts of these fatty acids, metal oxides such as zinc white, and tetramethyl. Thiuram Mono Sulfide (TMT
M), tetramethylthiuram disulphide (TMT
D), thiuram accelerators such as dipentamethylene thiuram tetrasulfide (DPTS) and dipentamethylene thiuram hexasulfide (DPTHS), thiazole accelerators such as dibenzodithiazyl disulfide, N
Examples include sulfenamide-based accelerators such as -cyclohexyl-2-benzothiazoylsulfenamide (CBS) and dithiocarbamate-based accelerators such as zinc dimethyldithiocarbamate (ZnMDC).

(Iv) Carbon black In applications where weather resistance is particularly required, the polypropylene / homopolymer resin composition and the random copolymer resin composition in the composition of the present invention have a total weight of 100 parts by weight. 0.3 to 300 parts by weight, preferably 0.5 to 100 parts by weight, of carbon black is included in the parts. With 0.3 part by weight or more of carbon black, the composition has further excellent long-term weather resistance due to the aforementioned shielding effect. When the amount of carbon black contained in the resin composition (matrix) exceeds 300 parts by weight, the composition itself tends to become brittle, so the content of carbon black is preferably 300 parts by weight or less. The carbon black may be present in the resin component, the rubber component, or both in the thermoplastic elastomer composition of the present invention. Further, the ethylene / propylene copolymer rubber composition and / or the butyl rubber composition may be contained in an amount of 400 parts by weight or less of carbon black based on 100 parts by weight of the total rubber content. The inclusion of carbon black in the rubber component has the effect of blocking ultraviolet rays. 400 parts by weight or less means that the rubber content in the rubber composition containing carbon black is 20.
This is because the rubber-like elasticity is lost when the content is less than wt%. Preferably, the carbon black is 0 to 300, particularly 0 based on 100 parts by weight of the total rubber content in the rubber composition.
~ 200 parts by weight. The grade of carbon used is not particularly specified, but the smaller the particle size, the better,
SRF, HAF and ISAF can be preferably used. The addition method is also not particularly specified, but a method of preparing a mixture of a resin and carbon black in advance as a masterbatch, and adding it at the time of kneading the resin composition and the rubber composition, or a roll to a rubber component, a Banbury mixer, etc. Other methods such as blending with a compounding agent can be used.

(V) Other components In the thermoplastic elastomer composition of the present invention, other than the above, a filler, a reinforcing agent such as white carbon, and a plasticizer may be added, if necessary, within a range not impairing the gist of the present invention. Agent, softener,
Antiaging agents, processing aids, pigments, colorants, nucleating agents, antistatic agents, ultraviolet absorbers and the like may be contained. In particular, it is preferable to add a softening agent and / or a plasticizer because the flexibility of the thermoplastic elastomer composition can be improved, and it is preferable to form a sheet. When it is added to the rubber composition, paraffinic oils, particularly paraffinic oils having heat resistance, are preferably exemplified because of their compatibility with EPDM and / or butyl rubber. The addition amount is not particularly limited, but the rubber component 10 in the rubber composition is added.
50 to 150 parts by weight is preferable with respect to 0 parts by weight. The content of the rubber component in the rubber composition used in the present invention is 20 to 99.5% by weight, more preferably 25 to 97% by weight. When the rubber composition contains a compounding agent such as a reinforcing agent, a plasticizer, a softening agent and an extender oil, the compounding agent can be contained in a total amount of up to 400 parts by weight with respect to 100 parts by weight of rubber. At this time, the content of the rubber component in this rubber composition is 20% by weight. When the content of the rubber component in the rubber composition is less than 20% by weight, that is, when the compounding agent is compounded in excess of 400 parts by weight with respect to 100 parts by weight of rubber, the rubber composition exhibits rubber-like elasticity. Lost,
Even when mixed with a thermoplastic resin, it becomes difficult to produce a thermoplastic elastomer composition having excellent flexibility, which is the object of the present invention. Here, since the amount of the vulcanizing agent, the vulcanization accelerator and the like is relatively small compared to the amounts of the rubber component and the compounding agent, the amount of the vulcanizing agent and the like can be ignored and calculated.

On the contrary, the rubber composition with respect to the rubber component,
When the compounding agent other than 0.3% by weight of carbon black other than the extender oil is not contained, the minimum amount of the vulcanizing agent or vulcanization accelerator capable of forming the vulcanized rubber is 100 parts by weight of the rubber composition. On the other hand, it is 0.5 part by weight. At this time, the content of the rubber component in this rubber composition was 99.2% by weight. When the compounding amount of the rubber component in the rubber composition exceeds 99.5% by weight, that is, the vulcanization system is less than 0.
If it is less than 5% by weight, a vulcanized rubber cannot be formed, and even if it is mixed with a thermoplastic resin, it becomes difficult to produce an excellent thermoplastic elastomer composition intended by the present invention. Furthermore, when the rubber / polymer / softening agent system is previously kneaded with a rubber kneading machine such as a Banbury mixer, carbon black or other reinforcing agent used as necessary is blended in such a range that workability is not impaired in practical use. It is more preferable to add.

The thermoplastic elastomer composition of the present invention comprises
Both the resin component and the rubber component may contain a composition other than a polymer, and at least a part of the thermoplastic elastomer composition constitutes a continuous phase as a matrix and at least a part of the rubber component and the rubber component are discontinuous phases ( Dispersed phase)
Since it is determined by the composition ratio of the rubber composition constituting the above, it is difficult to clearly indicate the relative ratio of the essential resin component and the polymer of the rubber component. However, since the relative ratio of the polymer and the composition ratio of the continuous phase and the discontinuous phase show a correlation, the ratio of the resin component to the rubber component, the vulcanizing agent, the softening agent and / or
Alternatively, the amount of the plasticizer added and the like are substantially effective, and the above range gives effective results for the purpose of the present invention.

The thermoplastic elastomer composition of the present invention comprises
At least a part of the rubber component is dynamically vulcanized by the vulcanizing agent. That is, at least a portion of the vulcanized rubber composition is contained in an amount sufficient to impart rubber-like elasticity to the thermoplastic elastomer composition.

The thermoplastic elastomer composition of the present invention comprises
At least a part of the rubber component is dispersed in the thermoplastic resin. That is, the thermoplastic resin constitutes at least a continuous phase, and at least a part of the rubber component constitutes a discontinuous phase and is dispersed in the thermoplastic resin phase. A so-called salami structure in which a thermoplastic resin is further dispersed in the discontinuous phase (rubber phase) may be used.

Generally, such a thermoplastic elastomer composition is prepared by using a Banbury mixer, a Brabender mixer, or a kneading extruder of some kind (a twin-screw kneading extruder) to melt a resin and a rubber composition. Are kneaded in these devices to finely disperse the rubber composition in the thermoplastic resin phase, and then further add a crosslinking agent (vulcanizing agent),
It is produced by masticating at a temperature that promotes vulcanization until the rubber is completely vulcanized. That is, the thermoplastic elastomer composition produced in this manner allows vulcanization of the rubber to proceed while masticating the thermoplastic resin and the rubber composition, so to speak, dynamic vulcanization that dynamically advances the vulcanization. Sulfur (Dy
It is a thermoplastic elastomer composition produced by dynamic cure or dynamic cure). By using such a production method, the resulting thermoplastic elastomer composition has a vulcanized rubber phase in which at least a part becomes a discontinuous phase finely dispersed in a thermoplastic resin phase in which at least a part becomes a continuous phase. The thermoplastic elastomer composition exhibits the same behavior as the vulcanized rubber, and at least the continuous phase is the thermoplastic resin phase. Is possible.

The kneading conditions, the vulcanizing agent to be used, the vulcanizing conditions (temperature, etc.) may be appropriately determined according to the type and amount of the rubber composition to be added, and are not particularly limited. For example, when kneading and dynamic vulcanization are performed using a biaxial kneading extruder, the kneading temperature of the thermoplastic resin and the rubber composition during dynamic vulcanization may be about 160 to 300 ° C. Furthermore, suitable manufacturing conditions will be described later.

Such a thermoplastic elastomer composition comprises at least a part of the thermoplastic resin as a continuous phase and at least a part of the rubber composition as a discontinuous phase, and the vulcanized rubber composition is a discontinuous phase. The particle size is preferably 50 μm or less, and more preferably 10 to 1 μm.

Here, the thermoplastic elastomer composition of the present invention preferably has the following physical properties. That is, the value measured according to the test method described in ASTM D638 and D1566, 1. Tension set is less than 160%, preferably 15
0% or less, 2. The compression set at 120 ° C. for 72 hours is 50% or less, and Young's modulus (initial tensile modulus) as a measure of flexibility
Is 25 kgf / mm ² or less, and 4. It has rubber elasticity up to about 120 ° C. That is, the thermoplastic elastomer composition of the present invention is
STM standard V. Those meeting the definition for rubbers shown on page 28, page 756 (D1566) are preferred.

The method for producing a thermoplastic elastomer composition of the present invention is as follows: (1) Melt kneading a preblended resin (homopolymer and random copolymer) and a rubber composition with a twin-screw kneading extruder or the like, and kneading A rubber is dynamically vulcanized by adding a vulcanizing agent in (2), or (2) a homopolymer and / or a random copolymer, or a part of the resin and a rubber composition are mixed with a twin-screw kneading extruder or the like. This can be carried out by melt-kneading, adding a vulcanizing agent under kneading, dynamically vulcanizing the rubber, and then adding the other resin or the remaining resin and kneading.

The compounding agent containing carbon black in the rubber component may be added during the above-mentioned kneading, but it is preferable that the compounding agents other than the vulcanizing agent be mixed in advance before the above-mentioned kneading.
The compounding agent containing carbon black in the resin component may be mixed in advance before the kneading, or may be added during the kneading. The kneading machine used is not particularly limited, and includes a screw extruder, a kneader, a Banbury mixer,
A biaxial kneading extruder and the like can be mentioned. Above all, it is preferable to use a twin-screw kneading extruder for kneading the resin component and the rubber component and dynamically vulcanizing the rubber component. Further, two or more kinds of kneaders may be used and kneading may be sequentially performed. The melt kneading conditions may be such that the temperature is equal to or higher than the temperature at which the polyolefin-based thermoplastic resin component is melted, for example, 160 to 300.
C., especially 160 to 250.degree. C., the shear rate after addition of the vulcanizing agent is 500 to 7500 sec.sup.- ¹ , especially 1000 to 5
It is preferably 000 sec ^-1 .

The total melt-kneading time is 30 seconds to 10 minutes,
The vulcanization time after adding the vulcanizing agent is preferably 15 seconds to 5 minutes. In the obtained thermoplastic elastomer composition of the present invention, the ethylene / propylene copolymer rubber and / or the butyl rubber form domains (dispersed phase) in the composition by dynamic vulcanization. As a result, the thermoplastic elastomer composition of the present invention exhibits thermoplasticity, and is excellent in heat softening resistance, flexibility, and high breaking strength while maintaining water impermeability, weather resistance, and heat fusion resistance. Therefore, it can be used as a member that requires water impermeability, weather resistance, and heat softening resistance, and that requires a material that is flexible and has high breaking strength.

Further, the examples of the above-mentioned two manufacturing methods will be given and specifically described. Note that these examples do not particularly limit the manufacturing method. The first method is pre-blended resin (homopolymer and random copolymer)
And the rubber are melt-kneaded by a twin-screw kneading extruder or the like, and a vulcanizing agent is added under the kneading to dynamically vulcanize the rubber. When this method is carried out using a twin-screw kneading extruder, it has a charging port for charging at least a resin component and a rubber component simultaneously or separately and a charging port for charging a vulcanizing agent. A kneading screw part for heating and kneading the resin component and the rubber component and a kneading screw part for performing dynamic vulcanization after charging the vulcanizing agent are configured between the charging port and the vulcanizing agent charging port. The temperature of the part where heat kneading and dynamic vulcanization are performed is 1
The temperature is preferably 60 to 250 ° C. It is preferable to adjust the screw configuration, volumetric flow rate, etc. so that the residence time in the portion where dynamic vulcanization is performed is 15 to 120 seconds. The screw rotation speed is preferably adjusted so that the shear rate is 1000 to 5000 sec ^-1 . Here, the residence time in the portion where dynamic vulcanization is performed is calculated by multiplying the total volume of the portion where dynamic vulcanization is performed by the filling factor and dividing it by the volumetric flow rate.

The shear rate is calculated by dividing the product obtained by multiplying the circumference of the circle drawn by the tip of the screw by the number of rotations of the screw for 1 second by the gap between the tips. That is, the shear rate is the tip speed divided by the tip gap. In the twin-screw kneading extruder configured as described above, first, the thermoplastic resin as the continuous phase is pelletized, charged from the resin component charging port, heated and melted, and kneaded. Then, the unvulcanized rubber composition containing components other than the vulcanizing agent is pelletized, charged from the rubber component charging port, and kneaded to finely disperse it in the thermoplastic resin phase forming the continuous phase. Let After the rubber composition is dispersed in the thermoplastic resin, vulcanize the vulcanizing agents (crosslinking agents, vulcanization accelerators, vulcanization aids, and other additives necessary for the crosslinking reaction) while kneading the two. The rubber component (rubber composition) is dynamically vulcanized while being charged from the agent charging port and kneading. If necessary, components such as an antioxidant can be added and kneaded at the same time as or separately from the resin component, the rubber component and the vulcanizing agent.

The thermoplastic elastomer composition of the present invention is obtained by holding it in the twin-screw kneading extruder until the dynamic vulcanization is completed, and immediately discharging and cooling after the dynamic vulcanization is completed. By performing dynamic vulcanization in this way, a state in which the rubber composition is sufficiently dispersed in the thermoplastic resin is obtained,
In addition, since the rubber composition is vulcanized, the dispersed state can be stably maintained without changing even after kneading. Moreover, since the kneading time is short, the resin,
Little rubber deterioration.

Therefore, since the structure of the obtained thermoplastic elastomer composition does not change even by heat molding, it can be molded using a molding machine such as a usual resin extruder or injection molding machine. Therefore, the molded product has rubber elasticity without being subjected to a vulcanization step.

In the second method, one or both of the homopolymer and the random copolymer and the rubber composition are melt-kneaded by a twin-screw kneading extruder or the like, and the vulcanizing agent is kneaded under kneading. After the rubber composition is added and the rubber composition is dynamically vulcanized, the other resin or the remaining resin is further added and kneaded. A thermoplastic elastomer composition (composition of the resin component is incomplete) is obtained by the same process as in the first method using a biaxial kneading extruder except that the resin component to be added is selected. Further, the obtained thermoplastic elastomer composition (the composition of the resin component is unfinished) and the rest of the resin component are heated and melted by a twin-screw kneading extruder or a single-screw extruder and kneaded to obtain the desired thermoplasticity. An elastomer composition can be obtained.

The second method is effective in the case of producing several kinds of thermoplastic elastomers having different properties, reducing the product change (stage change) in the twin-screw kneading extruder and improving the productivity. Is the way.

At the time of kneading the resin composition and the rubber composition in a twin-screw kneader, a mixture of the resin and carbon black prepared in advance as a masterbatch and blended in a predetermined amount with the resin composition is further mixed. Then, the method of kneading is an effective method for improving the productivity.

The thermoplastic elastomer composition of the present invention comprises
It can be used for belts, rolls, molds, hoses, tubes, electric wires, cables, building materials, civil engineering materials, agricultural or construction or civil engineering sheets or films, and packaging films. In particular, water-blocking sheets for waste disposal sites or waterproof sheets used for construction roofs and tunnel construction methods (the above-mentioned water-blocking sheets and waterproof sheets can be collectively referred to as "water-proof sheet", Then, unless otherwise specified, the “waterproof sheet” is a generic material). When the thermoplastic elastomer composition of the present invention is used as a material for such a water-blocking sheet, it is flexible and thus has high construction reliability, and since it has high breaking strength, damage accidents due to falling objects and the like are unlikely to occur. Further, since it is also excellent in heat softening resistance, it has sufficient breaking strength even if the sheet surface temperature rises due to exposure to direct sunlight. further,
Since it has excellent weather resistance, it retains sufficient breaking strength even if it is exposed to direct sunlight and rainwater for a long time.

As a construction method of such a water-blocking sheet, a T-die extruder, a calender molding machine, a blow molding machine, an inflation molding machine or the like is used to obtain a thickness of 0.5 to 3 mm, preferably 1.0 to 2.0 mm. It can be carried out by heat-melt-bonding the formed sheet to an appropriate width in advance, if necessary, laying it on site, and heat-melt-bonding the joint by a usual method. That is, the composition of the present invention is a composition that is sufficiently flexible, has excellent heat-softening resistance, and has breaking strength at high temperatures, and is particularly excellent as a waterproof sheet such as a waterproof sheet for waste disposal sites. Available.

The present invention provides a composition suitable for a sheet which requires conformability to deformation at high temperature. For example, the water-blocking sheet is exposed to direct sunlight and has a surface temperature of more than 90 ° C., but it is necessary that even under such a condition, breakage or molding does not occur due to unevenness on the bottom surface of the sheet or waste. For this purpose, a material having a high breaking strength, a decrease in breaking strength due to thermal softening, and a flexibility capable of following deformation is required. If the conformability to deformation is poor, local deformation may cause floating of the entire sheet, which is not preferable.

The composition of the present invention has high fracture strength (tensile strength: large, elongation at break: large, tear strength: large), flexibility (Young's modulus: small, hardness: small), heat softening resistance ( It provides a material that highly balances high fracture strength at high temperature: decrease in tensile strength: small, decrease in elongation at break: small, decrease in tear strength: small, decrease in Young's modulus: small. The following high-temperature deformation followability test was conducted as a test index for sheet products showing the flexibility, heat-resistant softening property and high breaking strength of the composition of the present invention. That is,
A sheet having a thickness of 1.5 mm was fixed to a flange having an inner diameter of 20 cm, and at a temperature of 120 ° C., one end of an iron cylinder having a diameter of 4 cm and a length of 15 cm was processed into a hemisphere having a radius of 2 cm. Press the sheet so that the center of the sheet hits, lower the iron cylinder by 8 cm from the surface of the sheet, and follow the deformation (the degree of familiarity at a position 4 cm from the tip, that is, if the iron cylinder is in close contact, good followability). , Generally, if the gap is visible, it is considered that the followability is poor.
The presence or absence of damage was evaluated. The evaluation was × ... damaged. (Low breaking strength) Δ: No damage, but poor followability. (Poor flexibility) ○… No damage and good followability.

On the other hand, the following formula (4) was evaluated as an index of the basic breaking strength, flexibility and heat softening resistance of the thermoplastic elastomer composition obtained in the present invention, and the above high temperature deformation follow-up test and measured value Based on the above, the correlation with the following formula (4) was evaluated.

[0050]

[Equation 1]

[0051]

EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited thereby.

(Examples 1-27 and Comparative Examples 1-1)
2) A thermoplastic elastomer composition having the composition shown in Tables 1-1 to 1-5 below was produced by the above-mentioned first method. That is, first, prepare a predetermined amount of each resin component in pellet form,
The pellets were blended to obtain a resin component having a composition ratio in which each pellet was uniformly dispersed. In addition, as the rubber component, a predetermined amount of compounding components shown in Tables 1-1 to 1-5 excluding the vulcanizing agent component is prepared and kneaded with a Banbury mixer for rubber that is usually used, and ethylene containing no vulcanizing agent is added. A propylene-based copolymer rubber (EPDM) composition was formed into a sheet with a rubber lab roll, and then pelletized with a rubber pelletizer to a length of about 3 mm and a diameter of about 2 mm.

Next, the preblended resin component and the pellets of the ethylene / propylene copolymer rubber (EPDM) containing no vulcanizing agent are fed from the first and second charging ports of the twin-screw kneading extruder. Each was successively and continuously charged and kneaded by heating to disperse the rubber composition as a discontinuous phase in the continuous phase of the thermoplastic resin. Next, while maintaining this dispersed state, a vulcanizing agent is further continuously charged through the third charging port to dynamically disperse the dispersed rubber composition as a discontinuous phase in the continuous phase of the thermoplastic resin. Vulcanized The kneading conditions are as follows: the temperature is 200 ° C., and the residence time of the portion for dynamic vulcanization is 41
Sec, shear rate is 4560 sec ^-1 . After completing the dynamic vulcanization,
It was continuously discharged in a strand form from the twin-screw kneading extruder, cooled with water, and cut into a length of about 3 mm (diameter of about 2 mm) with a cutter to obtain a pellet-shaped thermoplastic elastomer composition.

Then, the pellets of the thermoplastic elastomer composition were treated with a conventional press molding machine for resin to give 20
The sample was molded into a sheet having a thickness of 2 mm at 0 ° C. for 5 minutes at a pressure of 30 kgf / cm ^{2 to} obtain a JIS standard No. 3 dumbbell shape, tear B type (JIS K6301) test piece. Regarding the obtained test piece, in accordance with JIS K6301, 2
Tensile strength at 0 ° C., elongation at break, Young's modulus, tear strength B and JIS hardness (A type) were measured, and the results are shown in Table 1 below.
1 to 1-5. Furthermore, the tensile strength, elongation at break, Young's modulus and tear strength B were measured in the same manner in a constant temperature bath at 120 ° C., and the balance index was calculated based on the formula (4) for the value obtained for each composition. .

Further, the obtained resin composition was used in a single-screw extruder for resin, and a T-die for sheeting molding was attached to the tip of the extruder to obtain a sheet-shaped molded product having a thickness of 1.5 mm and a width of 40 cm. The above high-temperature deformation follow-up test was conducted using a sheet, and it was recorded as × ..., without breakage but with poor followability ... △, without breakage and with good followability ... The correlation with the index was contrasted.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[0062]

[Table 7]

[0063]

[Table 8]

[0064]

[Table 9]

[0065]

[Table 10]

Note) The amount of each composition is shown in parts by weight. PP (homo): polypropylene resin (EA110 manufactured by Showa Denko KK, MFR = 1.2, heat distortion temperature: 115 ° C.) EP (random): ethylene / propylene / random copolymer resin Ethylene content: 3.5 Weight% (EZ112 manufactured by Showa Denko KK, MFR = 1.7, heat distortion temperature: 87 ° C.) EP (block): ethylene / propylene / block copolymer resin (MK112 manufactured by Showa Denko KK, MFR = 2.0, heat distortion temperature: 108 ° C.) EPDM: ethylene / propylene / diene copolymer rubber (Mitsui Petrochemical Co., Ltd., Mitsui EPT 4070, third component: ethylidene norbornene)

Paraffin oil: Sunper 2280 (manufactured by Nippon San Oil Co., Ltd.) Alkylphenol resin: Takkyroll 1501 (manufactured by Taoka Chemical Co., Ltd.) Cl-IIR: chlorinated butyl rubber (Chlorobutyl 1066 manufactured by Exxon Chemical Co., Ltd.)

As shown in Table 1-1, EPDM was used as a rubber component, and a polypropylene resin homopolymer / ethylene / propylene / random copolymer blend was used as a resin component, and an EPDM composition forming a domain layer with the resin blend. The ratio of the product was 60/40. However, the ratio of homopolymer and random copolymer of the resin blend was changed, and the balance index calculated from the obtained physical properties and the extruded sheet molding were used. The high temperature deformation follow-up test was compared. From this result, under the rubber / resin ratio, there is a correlation between the balance index in the ratio of the homopolymer and the random copolymer and the high temperature deformation follow-up test. When the copolymer content is 10% or less, or 90% or more, the followability is poor, and only in such a case, the balance index based on the formula (4) calculated as a measure of flexibility and fracture resistance at room temperature and heat. Is less than 1000, and there is a correlation between the two.

In Table 1-2, the combination of materials used is the same as in Table 1-1, but the kneading ratio of the rubber component and the resin blend is larger in the rubber component, that is, 60/40.
Similarly, the influence of the composition ratio of the polypropylene resin, the homopolymer component and the random copolymer component was confirmed by the same method. In the system of the present invention, the homopolymer / random copolymer ratio is in the range of 35/5 to 5/35 (that is, the random copolymer is 12.5% to 12.5% in the resin component).
It can be seen that the heat followability is good in the range of 87.5%) and the balance index exceeds 1000 and has a good correlation. On the other hand, it can be seen that the homopolypropylene resin component alone or the random copolymer alone is unsatisfactory in the high temperature follow-up test, and the balance index is less than 1000 only in such a case.

In the evaluation in Table 1-3, the rubber component / resin component ratio was changed in the range of 85/15 to 4/96, and the homopolypropylene / random copolymer ratio in the resin component was 10 /. The effect of the rubber component was confirmed by fixing the ratio to 50. From this result, it can be seen that there is a correlation even in the rubber / resin ratio, and the limit of the rubber / resin ratio on the smaller rubber component side is 10/90 in this correlation. On the other hand, on the rubber multi-component side, when the rubber component was more than 80/20, the thermoplastic elastomer composition having a resin as a matrix and a rubber component as a domain had a limit because it could not be kneaded, which was unfavorable. .

Table 1-4 is the same as the case of Table 1-3, but in this evaluation system, the rubber component / resin component ratio was examined as follows.
The homopolypropylene / random copolymer ratio in the resin component was 10/10, and there were many random components. As a result, in spite of the change of the random ratio, the results obtained in this range showed that the correlation between the balance index and the thermal deformation followability of the product was the same, and the range of the rubber / resin ratio was also the same.

In Table 1-5, in a similar blend system, the ratio of homopolypropylene / random copolymer resin in the resin component was 50/10, which was high in homopolypropylene.
And the resin system is used and the rubber / resin ratio is changed with the same formulation. It can be seen that also in this system, quite similar results are obtained in relation to the rubber / resin composition.

(Comparative Examples 13 to 17) Thermoplastic elastomer compositions having the compositions shown in Table 2 below were produced by the above-mentioned first method. That is, a pelletized thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that the amounts of polypropylene resin (homopolymer), rubber component, paraffin oil and vulcanizing agent shown in Table 2 below were used. It was Further, pellets of the thermoplastic elastomer composition were molded into a sheet having a thickness of 2 mm by a press molding machine in the same manner as in Example 1, and were formed into JIS No. 3 dumbbell shape and tear B type (JIS K6301). The test piece was used. About the obtained test piece, according to JIS K6301, 20
Tensile strength, elongation at break, Young's modulus, tear strength and JIS hardness (A type) at ℃ and 120 ℃, and using the thermoplastic elastomer material obtained, thickness 1.5mm,
A sheet having a width of 40 cm was formed, and this sheet was used for the high temperature deformation followability test.

[0074]

[Table 11]

[0075]

[Table 12]

Note) The amount of each composition is shown in parts by weight. PP (homo): polypropylene resin (Showa Denko KK, MFR = 1.2, heat distortion temperature: 115 ° C.) EPDM: ethylene / propylene / diene copolymer rubber (Mitsui Petrochemical Co., Ltd., Mitsui EPT 4070) , Third component: ethylidene norbornene)

Paraffin-based oil: Sunper 2280 (manufactured by Nippon San Oil Co., Ltd.) Alkylphenol resin: Takkyroll 1501 (manufactured by Taoka Chemical Co., Ltd.) Cl-IIR: chlorinated butyl rubber (Chlorobutyl 1066 manufactured by Exxon Chemical Co., Ltd.)

In Table 2, EPDM as a rubber component,
If homopolypropylene alone is used as the resin component and the rubber / resin composition is changed, the results of the high temperature deformation follow-up test are unsatisfactory with homopolymer alone at any mixing ratio, and The balance index is always
It can be seen that it is below 1000.

Comparative Example 18 A thermoplastic elastomer composition having the composition shown in Table 3 below was produced by the above-mentioned first method. That is, a pellet-like thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that the resin component was an ethylene / propylene / block copolymer resin.
Further, pellets of the thermoplastic elastomer composition were molded into a sheet having a thickness of 2 mm by a press molding machine in the same manner as in Example 1, and the JIS standard No. 3 dumbbell shape,
A tear B type (JIS K6301) test piece was used. Regarding the obtained test piece, according to JIS K6301,
The tensile strength at 20 ° C. and 120 ° C. was measured, a sheet was prepared by the same method, and a high temperature deformation follow-up test was carried out.

[0080]

[Table 13]

Note) The amount of each composition is shown in parts by weight. PP (homo): polypropylene resin (EA110 manufactured by Showa Denko KK, MFR = 1.2, heat distortion temperature: 115 ° C.) EP (random): ethylene / propylene / random copolymer resin Ethylene content: 3.5 Weight% (EZ112 manufactured by Showa Denko KK, MFR = 1.7, heat distortion temperature: 87 ° C.) EP (block): ethylene / propylene / block copolymer resin (MK112 manufactured by Showa Denko KK, MFR = 2.0, heat distortion temperature: 108 ° C.) EPDM: ethylene / propylene / diene copolymer rubber (MK112 manufactured by Mitsui Petrochemical Co., Ltd., Mitsui EPT 4070, third component: ethylidene norbornene)

Paraffin-based oil: Sunper 2280 (manufactured by Nippon San Oil Co., Ltd.) Alkylphenol resin: Tackylol 1501 (manufactured by Taoka Chemical Co., Ltd.) Cl-IIR: chlorinated butyl rubber (Chlorobutyl 1066 manufactured by Exxon Chemical Co., Ltd.)

In Table 3, similarly, homopolymers, random copolymers, and block copolymers alone as polypropylene were also unsatisfactory in the high temperature follow-up test for any resin material, and the balance index thereof was always 1000. It turns out that it is below.

(Examples 28-33 and Comparative Examples 19-
26) Resin components in the amounts shown in Tables 4-1 and 4-2 below,
Melt-kneading and dynamic vulcanization were performed in the same manner as in Example 1 except that a rubber component and a softening agent were used, and then the mixture was molded into a sheet by a press molding machine, JIS standard No. 3 dumbbell shape, tear B type. (JIS K6301) test piece. The tear strength, the breaking elongation, the Young's modulus, the tear strength and the JIS hardness (A type) at 20 ° C. and 120 ° C. of the obtained test piece were measured according to JIS K6301, and JIS K720 was used.
The heat distortion temperature was measured according to 7-1983. The results are shown in Tables 4-1 and 4-2 below.

[0085]

[Table 14]

[0086]

[Table 15]

[0087]

[Table 16]

[0088]

[Table 17]

Note) The amount of each composition is shown in parts by weight. PP (homopolymer): polypropylene resin (EA110, Showa Denko KK, MFR = 1.2, heat distortion temperature: 115 ° C.) EP (random copolymer): ethylene / propylene / random copolymer resin Ethylene content: 3 0.5 wt% (EZ112 manufactured by Showa Denko KK, MFR = 1.7, heat distortion temperature: 87 ° C.) EPDM: ethylene / propylene / diene copolymer rubber (Mitsui Petrochemical Co., Ltd., Mitsui EPT 4070, Third component: ethylidene norbornene)

Paraffin oil: Sunper 2280 (manufactured by Nippon San Oil Co., Ltd.) Alkylphenol resin: Tackylol 1501 (manufactured by Taoka Chemical Co., Ltd.) Cl-IIR: chlorinated butyl rubber (Chlorobutyl 1066 manufactured by Exxon Chemical Co., Ltd.)

In Table 4-1, when the ratio of the rubber component / resin component was 40/60, and the rubber component was a chlorinated butyl rubber composition, its characteristics were examined by the dynamic vulcanization recipe. . As in the case where the rubber component is the EPDM rubber component,
Only when the ratio of the homopolypropylene / random copolymer in the resin component is 50/10 to 10/50, it is found that the good high temperature deformation follow-up test results and the correlation with the balance index can be maintained.

It can be seen from Table 4-2 that similar results can be obtained even when the rubber component is an EPDM / Cl-IIR mixed system as in Table 4-1.

Examples 34 to 36 After melt-kneading and dynamically vulcanizing in the same manner as in Example 1 except that the amounts of homopolymer, random copolymer and paraffin oil shown in Table 5 below were used, Formed into a sheet with a press molding machine, and
IS standard No. 3 dumbbell shape, tear B type (JISK63
The test piece of 01) was used. Regarding the obtained test piece, JI
According to SK6301, tear strength at 20 ° C. and 120 ° C., breaking elongation, Young's modulus, tear strength and JIS hardness (A type) were measured, and the heat distortion temperature was measured according to JIS K7207-1983. Was measured. The results are shown in Table 5 below.

(Example 37) As the vulcanizing agent (b) in the amount shown in Table 5 below, 0.2 part by weight of sulfur, 0.4 part by weight of ZnMDC accelerator, 0.2 part by weight of DPTS accelerator, CBS 0 0.6 parts by weight Melt kneading and dynamically vulcanizing in the same manner as in Example 5 except that a total of 1.4 parts by weight was used, and then molded into a sheet by a press molding machine, and then subjected to JI.
S standard No. 3 dumbbell shape, tear B type (JISK630
The test piece of 1) was used. Regarding the obtained test piece, JIS
Tear strength at 20 ° C. and 120 ° C., elongation at break, Young's modulus, tear strength and JIS hardness (A type) were measured according to K6301, and the heat deformation temperature was measured according to JIS K7207-1983. It was measured. The results are shown in Table 5 below.

Example 38 A thermoplastic elastomer composition having the composition shown in Table 5 below was produced by the second method described above. That is, first, a predetermined amount of pelletized polypropylene resin (homopolymer) was prepared as a resin component.
Further, as the rubber component, a predetermined amount of a compounding component excluding the vulcanizing agent component is prepared, and is kneaded with a commonly used rubber Banbury mixer to obtain a vulcanizing agent-free ethylene / propylene copolymer rubber (EPDM), After making a sheet with a rubber lab roll, it was made into pellets with a length of about 3 mm with a rubber pelletizer.

Next, the resin component and the vulcanizing agent-free ethylene / propylene copolymer rubber (EPD) are used.
The pellets of M) were sequentially and continuously charged from the first and second charging ports of the twin-screw kneading extruder, and kneaded by heating to disperse the rubber composition as a discontinuous phase in the continuous phase of the thermoplastic resin.
Next, while maintaining this dispersed state, a vulcanizing agent is further continuously charged through the third charging port to dynamically disperse the dispersed rubber composition as a discontinuous phase in the continuous phase of the thermoplastic resin. Vulcanized The kneading conditions are as follows:
° C, residence time 41 seconds for dynamic vulcanization, shear rate 4
It is 560 seconds- ¹ . After completing the dynamic vulcanization, the mixture was continuously discharged in a strand form from the twin-screw kneading extruder, cooled with water, and cut into a length of about 3 mm with a cutter to obtain a pellet-shaped thermoplastic elastomer composition.

Further, this thermoplastic elastomer and Table 5
A predetermined amount of the ethylene / propylene / random copolymer resin shown in was blended in the form of pellets. This blend was charged into a single-screw extruder, and the temperature was 200 ° C. and the shear rate was 830.
The mixture was kneaded for ¹ second, then continuously discharged in a strand form from a single-screw extruder, cooled with water, and cut into a length of about 3 mm with a cutter to obtain a pellet-shaped thermoplastic elastomer composition having a predetermined composition. .

Then, the pellets of the thermoplastic elastomer composition were treated with a commonly used resin press molding machine at 20
The sample was molded into a sheet having a thickness of 2 mm at 0 ° C. for 5 minutes at a pressure of 30 kgf / cm ^{2 to} obtain a JIS standard No. 3 dumbbell shape, tear B type (JIS K6301) test piece. The obtained test pieces were evaluated in the same manner.

[0099]

[Table 18]

[0100]

[Table 19]

Note) The amount of each composition is shown in parts by weight. PP (homo): polypropylene resin (EA110 manufactured by Showa Denko KK, MFR = 1.2, heat distortion temperature: 115 ° C.) EP (random): ethylene / propylene / random copolymer resin Ethylene content: 3.5 Weight% (EZ112 manufactured by Showa Denko KK, MFR = 1.7, heat distortion temperature: 87 ° C.) EP (block): ethylene / propylene / block copolymer resin (MK112 manufactured by Showa Denko KK, MFR = 2.0, heat distortion temperature: 108 ° C.) EPDM: ethylene / propylene / diene copolymer rubber (Mitsui Petrochemical Co., Ltd., Mitsui EPT 4070, third component: ethylidene norbornene)

Paraffinic oil: Samper 2280 (manufactured by Nippon San Oil Co., Ltd.) Alkylphenol resin: Takkyroll 1501 (manufactured by Taoka Chemical Co., Ltd.) Cl-IIR: chlorinated butyl rubber (Chlorobutyl 1066 manufactured by Exxon Chemical Co., Ltd.)

Accelerator ZnMDC: zinc dimethyldithiocarbamate Nocceller PZ accelerator manufactured by Ouchi Shinko Kagaku Co., Ltd. DPTS: dipentamethylene thiuram tetrasulfide Sancellar RA accelerator manufactured by Sanshin Kagaku Co., Ltd. CBS: N-cyclohexyl- 2-benzothiazolesulfenamide Nocceller CZ manufactured by Ouchi Shinko Chemical Co., Ltd.

In Table 5, the rubber / resin component ratio is 4
When the rubber component is 0/60 and the rubber component is EPDM, the breaking strength of the composition is naturally lowered when the paraffinic oil contained is changed to 0 to 80 parts with the total amount of the rubber component and the resin component being 100 parts. In the range of the softening agent, good results are obtained, and it is understood that the softening agent is not affected.

(Examples 39-42 and Comparative Examples 27-
30) Melt-kneading and dynamic vulcanization were performed in the same manner as in Example 1 except that the amounts of random copolymers shown in Table 6-1 below were used, and thereafter, the mixture was molded into a sheet by a press molding machine, and the JIS standard No. 3 dumbbell shape, tear B type (JIS K630
The test piece of 1) was used. Regarding the obtained test piece, JIS
Tear strength at 20 ° C. and 120 ° C., elongation at break, Young's modulus, tear strength and JIS hardness (A type) were measured according to K6301, and the heat deformation temperature was measured according to JIS K7207-1983. It was measured. The results are shown in Table 6-2 below.

[0106]

[Table 20]

[0107]

[Table 21]

Note) The amount of each composition is shown in parts by weight. PP (homo): polypropylene resin (EA110 manufactured by Showa Denko KK, MFR = 1.2, heat distortion temperature: 115 ° C.) EP (random): ethylene / propylene / random copolymer resin Ethylene content: 3.5 % By weight (Showa Denko KK EZ112, MFR = 1.7, heat distortion temperature: 87 ° C.) EPDM: ethylene / propylene / diene copolymer rubber (Mitsui Petrochemical Co., Ltd., Mitsui EPT 4070, No. 3) Component: ethylidene norbornene) Cl-IIR: chlorinated butyl rubber (Chlorobutyl 1066 manufactured by Exxon Chemical Co., Ltd.)

Paraffin oil: Sunper 2280 (manufactured by Nippon Sun Oil Co., Ltd.)

Accelerator DPTHS: dipentamethylene thiuram hexasulfide Tetron A manufactured by DuPont Brominated X-IPMS: XP-50-90-10 manufactured by Exxon Chemical Co.

In Table 6, the rubber component / resin ratio is 6
0/40, as a rubber component, brominated X-IPMS
(XP-50-90-10, manufactured by Exxon Chemical Co., Ltd.) also shows the same results as the chlorinated butyl rubber when the modified butyl rubber is used.

(Examples 43 to 48, Comparative Example 31) Thermoplastic elastomer compositions having the compositions shown in Table 7 below were produced by the above-mentioned first method. That is, a pelletized thermoplastic elastomer composition was obtained in the same manner as in Example 1 except for the amounts of carbon black shown in Table 7 below. further,
In the same manner as in Example 1, pellets of the thermoplastic elastomer composition were molded into a sheet having a thickness of 2 mm by a press molding machine, and a JIS No. 3 dumbbell shape and a tear B type (JIS K6301) test piece were used. did. The obtained test piece was measured at 20 ° C. and 1 according to JIS K6301.
The tensile strength at 20 ° C., elongation at break, Young's modulus, tear strength and JIS type (A type) were measured to calculate the balance index. Further, the obtained thermoplastic elastomer material was used to form a sheet having a thickness of 1.5 mm and a width of 40 cm, and the high temperature deformation follow-up test was carried out using this sheet. In addition, in accordance with JIS A6008, accelerated exposure test using a sunshine weatherometer (condition: 63 ° C
× 1000 hours, 18 minutes in 120 minutes of spray cycle)
Also for the test piece (No. 3 dumbbell shape) after the treatment of No. 3, the tensile strength at 20 ° C. and the elongation at break were measured according to JIS K6301, and the results were obtained for the test piece not treated. Then, the retention rate was obtained. This test is particularly applicable to applications that require weather resistance, such as water barrier sheets. It may take several years after the sheet is installed at the waste disposal site until it is buried in the soil due to the severe exposure conditions on the surface. Therefore, sunshine
We measured the tensile properties after processing the weatherometer for 1000 hours (corresponding to actual exposure for about 5 years) and calculated the retention rate.
Those having a value of 60% or less are considered to have poor weather resistance, which is a required characteristic of the water-impermeable sheet. It is easily imagined that the material constituting the sheet, especially polypropylene homopolymer resin and random copolymer resin, deteriorates considerably when the retention rate becomes 60% or less, and not only the tensile properties and other physical properties This is because adverse effects such as being more susceptible to the effects of microorganisms in the soil will occur. As a result, from Table 7 and FIG. 1, when the carbon black exceeds 0.3 with respect to the resin component 100, the flexibility and the heat softening resistance are excellent (high temperature deformation follow-up test,
In addition to (from the result of the balance index), the retention rate after the sunshine weatherometer treatment also exceeds 60%, which shows that it has good weather resistance. In particular, when it exceeds 0.5, the retention rate exceeds 80% in both TB (tensile strength) and EB (elongation at break), which shows that the retention rate is very good.

[0113]

[Table 22]

Note) The amount of each composition is shown in parts by weight. PP (homo): polypropylene resin (EA110 manufactured by Showa Denko KK, MFR = 1.2, heat distortion temperature: 115 ° C.) EP (random): ethylene / propylene / random copolymer resin Ethylene content: 3.5 % By weight (Showa Denko KK EZ112, MFR = 1.7, heat distortion temperature: 87 ° C.) EPDM: ethylene / propylene / diene copolymer rubber (Mitsui Petrochemical Co., Ltd., Mitsui EPT 4070, No. 3) Ingredients: ethylidene norbornene) Paraffinic oil: Sunper 2280 (manufactured by Nippon San Oil Co., Ltd.) Alkylphenol resin: Takkyrol 1501 (manufactured by Taoka Chemical Co., Ltd.) Cl-IIR: chlorinated butyl rubber (manufactured by Exxon Chemical Co., Ltd., chlorobutyl 1066) ) Carbon black: HAF grade (Showblade Co., Ltd., Show Black N330T)

[0115]

According to the present invention, flexibility, heat-softening resistance,
A thermoplastic elastomer composition excellent in high breaking strength can be obtained. Further, the waterproof sheet using the obtained thermoplastic elastomer composition also has weather resistance and water impermeability,
Construction work is easy because it is flexible, waterproof reliability after construction is high, and strength is high, so damage accidents such as falling objects do not occur easily.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the amount of carbon black added and the tensile properties after sunshine weatherometer treatment.

Claims (4)

[Claims] 1. A homopolymer resin containing a polypropylene homopolymer resin and a random copolymer resin having at least two kinds of units selected from ethylene, propylene and α-olefin as a constituent. 90 to 10 parts by weight of a thermoplastic polyolefin resin having a resin weight ratio of 1: 9 to 9: 1; and 10 to 90 parts by weight of an ethylene / propylene copolymer rubber composition and / or a butyl rubber composition At least a part of the ethylene / propylene-based copolymer rubber composition and / or the butyl-based rubber composition is dynamically vulcanized by a vulcanizing agent to form a dispersed phase. Plastic elastomer composition. 2. The polypropylene homopolymer resin composition and the random copolymer resin composition contain 0.3 to 300 parts by weight of carbon black based on 100 parts by weight of the total resin content. The thermoplastic elastomer composition according to. 3. The ethylene / propylene copolymer rubber composition and / or butyl rubber composition contains 0 to 400 parts by weight of carbon black based on 100 parts by weight of the total rubber content. The thermoplastic elastomer composition according to 1 or 2. 4. A waterproof sheet comprising the thermoplastic elastomer composition according to claim 1.