JPH05287132A - Olefin-based thermoplastic elastomer composition - Google Patents

Abstract

(57) [Summary] [Structure] (a) 30 to 90 parts by weight of olefin rubber,
(B) Polypropylene resin 10 to 70 parts by weight, (c) Polyethylene resin 0 to 40 parts by weight, (d) Mineral oil-based softening agent 0 to 40 parts by weight (however, the above (a), (b), (c) and (E) Silicone dioxide and (f) Alkaline earth metal fatty acid salt and / or alkaline earth per 100 parts by weight of olefinic thermoplastic elastomer (I) Metal oxides,
(G) basic zeolite and / or optionally contained
Alternatively, an olefin-based thermoplastic elastomer composition comprising an inorganic or organic compound (II) comprising hydrocalumite in an amount of 0.05 to 5 parts by weight. [Effect] It is possible to obtain an olefin-based thermoplastic elastomer composition in which bleeding out of additives and the like is extremely small.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an olefin-based thermoplastic elastomer composition, and more particularly to an olefin-based thermoplastic elastomer composition in which bleed-out of additives and the like is extremely small.

[0002]

BACKGROUND OF THE INVENTION Conventionally, various resins or elastomers have been used in various forms for building interior materials or automobile interior materials. Car door trim,
Sheet-shaped resins or elastomers are used for instrument panels, ceiling materials, etc., but such materials are mainly used because they are easy to mold and have excellent scratch resistance. Vinyl chloride resin is used for.

However, since vinyl chloride resin emits a toxic gas when incinerated as a waste material, in recent years,
From the standpoint of protecting the global environment, various studies have been conducted to replace this vinyl chloride resin with another halogen-free material. Such movements are occurring all over the world, especially in related fields of the automobile industry.

Various resins or elastomers have been investigated as alternative materials to the vinyl chloride resin, and one of them is an olefinic thermoplastic elastomer. The olefin-based thermoplastic elastomer is usually blended with additives such as a heat resistance stabilizer and a weather resistance stabilizer in order to prevent deterioration of physical properties over time. Further, a lubricant may be blended in order to improve moldability, or an antistatic agent may be blended in order to prevent adhesion of dust due to charging. Moreover,
A flame retardant and a flame retardant aid may be blended in order to impart flame retardancy.

However, a problem common to olefin-based materials such as olefin-based thermoplastic elastomers is a so-called bleed-out phenomenon, in which the above-mentioned additive bleeds over the surface of the molded product over time.

When bleeding out of additives occurs, the surface of the molded article looks whitish or the gloss changes, and the appearance deteriorates. As a material for forming a molded body, in particular,
When such deterioration of appearance occurs in olefinic materials used for interior materials for construction or automobiles,
Product value is significantly impaired.

The present inventors have conducted diligent research to solve the above problems, and if a specific amount of a specific inorganic compound is added to an olefinic thermoplastic elastomer, the bleed-out of various additives such as a heat stabilizer is significantly increased. They have found that they can be suppressed, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems associated with the prior art, and an object thereof is to provide an olefinic thermoplastic elastomer composition in which the bleed-out phenomenon is extremely unlikely to occur. I am trying.

[0009]

SUMMARY OF THE INVENTION That is, the olefin thermoplastic elastomer composition according to the present invention comprises (a) 30 to 90 parts by weight of olefin rubber, (b) polypropylene resin 10
To 70 parts by weight, (c) polyethylene resin 0 to 40 parts by weight, and (d) mineral oil-based softener 0 to 40 parts by weight (however, the total of (a), (b), (c) and (d) above. 1
00 parts by weight. ), For example, with respect to 100 parts by weight of the olefinic thermoplastic elastomer (I) formed by mixing
Inorganic composed of (e) silicon dioxide, (f) fatty acid salt of alkaline earth metal and / or oxide of alkaline earth metal, and optionally (g) basic zeolite and / or hydrocalumite Alternatively, the organic compound (II) is contained in an amount of 0.05 to 5 parts by weight.

The olefinic thermoplastic elastomer composition according to the present invention is characterized in that the olefinic thermoplastic elastomer composition further contains a flame retardant (III) in an amount of 1 to 50 parts by weight. There is.

The olefinic thermoplastic elastomer composition according to the present invention has a total of 100 parts by weight of the olefinic thermoplastic elastomer (I) (30 to 99 parts by weight) and the olefinic resin (IV) (70 to 1 parts by weight). The inorganic or organic compound (II) is contained in an amount of 0.05 to 100 parts by weight.
It is characterized in that it is contained in an amount of 5 parts by weight.

The olefinic thermoplastic elastomer composition according to the present invention has a total of 100 parts by weight of 30 to 99 parts by weight of the olefinic thermoplastic elastomer (I) and 70 to 1 parts by weight of the olefinic resin (IV). To the department
The inorganic or organic compound (II) is contained in an amount of 0.05 to 5 parts by weight, and the flame retardant (III) is 1 to 50.
It is characterized in that it is contained in an amount of parts by weight.

In a preferred embodiment of the present invention,
The olefin resin (IV) is polyethylene, polypropylene, polybutene or poly-4-methyl-1.
-Pentene is preferred.

In a preferred embodiment of the present invention,
The olefin rubber (a) is preferably ethylene / α-olefin copolymer rubber, polyisobutylene or butyl rubber.

According to the present invention, there is provided an olefinic thermoplastic elastomer composition in which the bleed-out phenomenon is extremely unlikely to occur.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The olefinic thermoplastic elastomer composition according to the present invention will be specifically described below.

The olefinic thermoplastic elastomer composition of the present invention contains an olefinic thermoplastic elastomer (I) and an inorganic or organic compound (II).

Olefinic Thermoplastic Elastomer (I) The olefinic thermoplastic elastomer (I) contained in the olefinic thermoplastic elastomer composition includes an olefinic rubber (a), a polypropylene resin (b), and a case. Contains a polyethylene resin (c) and a mineral oil-based softening agent (d).

The olefinic thermoplastic elastomer (I) includes a partially crosslinked thermoplastic elastomer (I-
1), non-crosslinked thermoplastic elastomer (I-2) and the like.

First, of the olefinic thermoplastic elastomer (I), the olefinic rubber (a-1) contained in the partially crosslinked thermoplastic elastomer (I-1) will be described. (A) Olefin-based rubber In the present invention, the olefin-based rubber (a-1) contained in the partially crosslinked thermoplastic elastomer is classified into two types, a crosslinked type rubber and a non-crosslinked type rubber. Is an ethylene / α-olefin copolymer rubber, and more specifically, an amorphous elastic rubber mainly composed of ethylene and an α-olefin other than ethylene, such as ethylene / propylene / non-conjugated diene rubber. A copolymer, which is crosslinked by mixing with an organic peroxide and kneading under heating,
Examples of such rubbers are those that have a reduced flowability or that do not flow.

Examples of non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, methylene norbornene and ethylidene norbornene. In the present invention, among these copolymer rubbers, ethylene / propylene copolymer rubber or ethylene / propylene /
A non-conjugated diene copolymer rubber is preferable, and an ethylene / propylene / non-conjugated diene copolymer rubber is more preferable.
More specifically, ethylene / propylene / ethylidene norbornene copolymer rubber or ethylene / propylene / dicyclopentadiene copolymer rubber is preferable.

In the present invention, the above ethylene / propylene copolymer rubber or ethylene / propylene / non-conjugated diene copolymer rubber has a molar ratio of ethylene units to propylene units (ethylene / propylene) of 50/50 to 50%.
It is preferably 90/10, especially when this molar ratio is 5
It is preferably 5/45 to 85/15.

The Mooney viscosity M of this copolymer rubber is also
L _{1 + 4} (100 ° C.) is usually 10 to 250, and particularly preferably 30 to 180. Mooney viscosity is 1
If it is less than 0, only a composition having low tensile strength can be obtained, while 2
When it exceeds 50, the fluidity of the composition tends to be poor, and molding tends to be difficult.

Further, the iodine value (unsaturation) of the copolymer rubber is preferably 16 or less. When such a copolymer rubber having an iodine value is used, the fluidity and the rubber-like properties are well balanced. A thermoplastic elastomer is obtained.

The non-crosslinking type olefin rubber (a-1) used in the present invention is an amorphous elastic polymer other than the above containing olefin as a main component, and is mixed with an organic peroxide and heated. A rubber (non-crosslinking type rubber) that does not crosslink even when kneaded below and does not deteriorate in fluidity is exemplified. Examples of such a non-crosslinked rubber include polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber containing propylene unit in an amount of 70 mol% or more, propylene / 1-butene copolymer rubber, atactic polypropylene. Among them, polyisobutylene or butyl rubber is particularly preferable in terms of performance.

The Mooney viscosity M of this non-crosslinked rubber is also
L _{1 + 4} (100 ° C.) is usually 10 to 250, and particularly preferably 30 to 180. Mooney viscosity is 1
If it is less than 0, only a composition having low tensile strength can be obtained, while 2
If it exceeds 50, the fluidity of the composition tends to be poor, and molding tends to be difficult.

In the present invention, of the two types of rubbers, the crosslinkable rubber and the noncrosslinkable rubber, only the crosslinkable rubber may be used, or the crosslinkable rubber and the noncrosslinkable rubber may be used in combination. You may. However, when only non-crosslinked rubber is used, the tensile strength and heat resistance tend to be inferior. Therefore, in the present invention, the crosslinked rubber should be used in an amount of at least 30% or more of the entire rubber. preferable.

Next, among the olefinic thermoplastic elastomers (I), a non-crosslinking type thermoplastic elastomer (I-
The olefin rubber (a-2) contained in 2) will be described. The olefinic rubber (a- used in the present invention
Examples of 2) include ethylene / α-olefin copolymer rubber. This is a rubber which is an amorphous elastic copolymer mainly composed of ethylene and an α-olefin other than ethylene, such as ethylene / propylene copolymer rubber or ethylene / propylene / non-conjugated diene rubber. Incidentally, the non-conjugated diene, dicyclopentadiene,
1,4-hexadiene, methylene norbornene, ethylidene norbornene and the like.

In the present invention, among these copolymer rubbers, an ethylene / propylene copolymer rubber, an ethylene / butene copolymer rubber or an ethylene / propylene / non-conjugated diene copolymer rubber, wherein ethylene units and propylene are used. The molar ratio of units (ethylene / propylene) is 10 /
90 to 90/10, especially 10/90 to 30 /
70 range, or 55/45 to 85/1
Those in the range of 5 are preferable.

The Mooney viscosity M of this copolymer rubber is also
L _{1 + 4} (100 ° C) is 10 to 250, especially 30 to 180
Is preferred. When the Mooney viscosity is less than 10, only a composition having a low tensile strength can be obtained. On the other hand, when it exceeds 250, the fluidity of the composition is poor and molding tends to be difficult.

As the olefin rubber used in the present invention, secondly, an amorphous elastic polymer containing an olefin as a main component other than the above may be used. Examples thereof include polyisobutylene, butyl rubber, propylene / 1-butene copolymer rubber, and atactic polypropylene. Among them, polyisobutylene or butyl rubber is particularly preferable in terms of performance.

The Mooney viscosity ML of this rubber is also
_{1 + 4} (100 ° C.) is preferably 10 to 250, particularly preferably 30 to 180. When the Mooney viscosity is less than 10, only a composition having a low tensile strength can be obtained. On the other hand, when it exceeds 250, the fluidity of the composition is poor and molding tends to be difficult.

(B) Polypropylene Resin As the polypropylene resin, isotactic polypropylene, a copolymer of propylene and a small amount of other α-olefin, such as a propylene / ethylene copolymer, a propylene / 1-butene copolymer, etc. Is mentioned.

The melt flow rate (MFR) of such polypropylene resin is 0.01 to 50 g / 1.
It is preferably 0 minutes, and further 0.1 to 30 g / 1
It is preferably 0 minutes.

(C) Polyethylene resin As the polyethylene resin, a homopolymer of ethylene or a small amount (10 mol% or less) of α-olefin such as 1-butene, 1-pentene, 1-hexene,
Examples thereof include copolymers with 4-methyl-1-pentene and the like.

In the present invention, among such polyethylene resins, those having a density of 0.88 to 0.98 (g / cm ³ ) are preferable, and 0.90 to 0.95 (g / cm ³ ) are further preferable.
Those which are ³ ) are preferred.

The melt flow rate (MFR) of this polyethylene resin is preferably 0.01 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes.

(D) Mineral oil-based softening agent A mineral oil-based softening agent generally weakens the intermolecular action force of the rubber when rolling the rubber to facilitate the processing, and
A high boiling point petroleum fraction used for the purpose of increasing the flexibility or elasticity by helping to disperse carbon black, white carbon, etc., or decreasing the hardness of the vulcanized rubber. , Paraffin type, naphthene type,
Alternatively, aromatic mineral oil or the like is used.

The mineral oil softener used in the present invention preferably has a viscosity index (VI) of 50 or more, and more preferably 80 or more. When such a mineral oil-based softening agent is used, the hardness of the rubber is lowered by weakening the intermolecular force of the rubber compounded, and the flexibility,
It is possible to increase elasticity and improve moldability.

In the present invention, the olefinic thermoplastic elastomer (I) includes an olefinic rubber (a), a polypropylene resin (b), and optionally a polyethylene resin (c) and a mineral oil softening agent (d). Of the olefinic rubber (a) in a total of 100 parts by weight of
To 90 parts by weight, preferably 40 to 80 parts by weight, the polypropylene resin (b) in an amount of 10 to 70 parts by weight, preferably 20 to 60 parts by weight, the polyethylene resin (c).
Is 0-40 parts by weight, preferably 0-30 parts by weight,
The mineral oil-based softening agent (d) is contained in an amount of 0 to 40 parts by weight, preferably 0 to 30 parts by weight.

In the present invention, in the case where the olefinic thermoplastic elastomer (I) is a partially crosslinked type, in order to partially crosslink the olefinic thermoplastic elastomer in this way, the above-mentioned components (a) to The blend of (d) may be dynamically heat-treated in the presence of the following organic peroxide to partially crosslink. Dynamically heat treating means kneading in a molten state.

In the case of the non-crosslinked type, the blended products of the above components (a) to (d) may be simply heat-treated dynamically. Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2, 5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (te
rt-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide,
Examples thereof include p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide.

Such organic peroxides include (a)-
It is used in an amount of 0.02 to 3% by weight, preferably 0.05 to 1% by weight, based on the entire object (d) to be treated. If this blending amount is less than the above range, the composition has a low degree of crosslinking, and therefore heat resistance, tensile properties, elastic recovery, impact resilience, etc. are not sufficient, and if it is more than the above range, the degree of crosslinking is high. If it is too high, the moldability may be deteriorated.

In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N and N are used in the partial crosslinking treatment with the organic peroxide as described above.
-Peroxy crosslinking aids such as -methyl-N, N'-m-phenylene dimaleimide, or multi-agents such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and acrylic methacrylate. A multifunctional vinyl monomer such as a functional methacrylate monomer, vinyl butyrate, or vinyl stearate may be incorporated.

A uniform and mild crosslinking reaction can be expected by using the compound such as the crosslinking aid. Such a crosslinking aid or a compound such as a polyfunctional vinyl monomer is used in an amount of usually not more than 2% by weight, more preferably 0.3 to 1% by weight, based on the whole object to be treated.

In the present invention, in order to accelerate the decomposition of the organic peroxide, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt and vanadium. Decomposition accelerators such as naphthenates such as copper, calcium, zirconium, manganese, magnesium, lead and mercury may be used.

As a kneading device used for preparing the above-mentioned olefinic thermoplastic elastomer (I), an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer and the like are conventionally used. A more known one is used. In the present invention, among these kneading devices, it is preferable to use a non-release type kneading device, and in particular, using such a non-release type kneading device,
It is preferable to knead under an inert gas atmosphere such as nitrogen or carbon dioxide. Further, in the present invention, the temperature at which the half-life of the organic peroxide is less than 1 minute, that is, usually 150 to 28.
1 to 2 at a temperature of 0 ° C., preferably 170 ° C. to 240 ° C.
The kneading may be performed for 0 minutes, preferably 2 to 10 minutes. The shearing force applied is usually 10 to 10,000 sec -1, preferably 100 to 10
It is preferable to select 5,000 sec-1.

Inorganic or Organic Compound (II) The inorganic or organic compound (II) contained in the olefinic thermoplastic elastomer composition according to the present invention together with the above olefinic thermoplastic elastomer (I) will be described.

The inorganic or organic compound (II) used in the present invention comprises the following silicon dioxide (e) and a fatty acid salt of an alkaline earth metal and / or an oxide of an alkaline earth metal (f). Become. In addition, in the present invention, the inorganic or organic compound (II) contains, in addition to these (e) and (f), the following basic zeolite and / or hydrocalumite (g), if necessary. May be.

(E) Silicon Dioxide The silicon dioxide (e) used in the present invention may be a hydrate or an anhydride, but in any case, the average particle size is 10 μm or less, Preferably 0.1-5
It is preferably μm and is surface-treated to improve dispersibility. As such a surface treatment method,
For example, in addition to coupling treatment with a silane coupling agent, a titanium coupling agent, etc., a surfactant, a higher fatty acid or a metal salt thereof, a derivative of a higher fatty acid such as ester or amide, and a surface modification method with an organic compound, etc. Is mentioned. When such surface treatment is applied to silicon dioxide (e), the affinity with the elastomer (I) can be improved.

(F) Alkaline Earth Metal Fatty Acid Salt and / or Alkaline Earth Metal Oxide The alkaline earth metal fatty acid salt preferably used in the present invention includes Mg or Ca fatty acid salts. Further, the number of carbon atoms of such fatty acid salt is preferably 12 to 30.

Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, aragic acid, heptadecyl acid, behenic acid, oleic acid, elaidic acid, erucic acid, linoleic acid, linoleic acid, ricinoleic acid, Examples thereof include hydroxystearic acid and montanic acid.

Examples of the alkaline earth metal oxide preferably used in the present invention include calcium oxide and magnesium oxide. The average particle size of these oxides of Alcali earth metal is 10 μm or less, preferably 0.1 μm or less.
It is desirable that the surface treatment is performed to improve the dispersibility. Such surface treatment methods include, for example, coupling treatment with a silane coupling agent, a titanium coupling agent, etc., a surfactant, a higher fatty acid or a metal salt thereof, a derivative of a higher fatty acid such as ester or amide, and the like. A surface modification method using an organic compound may be used. By subjecting the alkaline earth metal to the surface treatment in this way, the affinity with the olefinic thermoplastic elastomer (I) can be improved.

(G) Basic Zeolite and / or Hydrocalumite The basic zeolite used in the present invention is represented by the following formula (i). _{pMgO · qCaO · rNa 2 O ·} sAl 2 O 3 · tSiO 2 · uH 2 O ... (i) p In the above described formula (i), q, r, s, t represents an integer of 0 or more. However, all of p, q, r, s, and t never become 0. Further, u represents an arbitrary number of 0 or more.

[0055] As such a basic zeolite represented by formula (i), for example, _{5MgO · CaO · Na 2 O ·} 2SiO 2 · 2.3H 2 O and the like are commercially available.

The hydrocalumite used in the present invention is represented by the following formula (ii). _{xCaO · yAl 2 O 3 · zCaCO} 3 · wH 2 O ...... (ii) x In the above-mentioned formula (ii), y, z represents an integer of 0 or more. However, x, y, and z are not all 0. Further, w represents an arbitrary number of 0 or more.

As the hydrocalumite represented by the above formula (i), for example, 3CaO.Al ₂ O ₃ .CaCO ₃ .10H ₂ O and the like are commercially available.

The average particle size of these basic zeolite and hydrocalumite is 10 μm or less, preferably 0.1.
It is desirable that it is ˜5 μm. In addition, these basic zeolite and hydrocalumite, if necessary,
The surface treatment may be performed by the method as described above.

Such an inorganic or organic compound (II)
It is presumed that the bleed-out component is adsorbed. In the olefinic thermoplastic elastomer composition according to the present invention, the inorganic or organic compound (II) is used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the olefinic thermoplastic elastomer (I). , Preferably 0.1 to 3 parts by weight. If the content of this inorganic or organic compound (II) is less than 0.05 parts by weight, the effect of preventing bleed-out of additives and the like tends to be weak, and if it exceeds 5 parts by weight, the amount of addition is further increased. The effect becomes difficult to appear, the effect as a usual filler becomes remarkable, and the processability and physical properties of the thermoplastic elastomer tend to be affected.

In the present invention, the total amount of the components (e) and (f) is 0.05 to 5 parts by weight, and more preferably 0. 0, based on 100 parts by weight of the olefinic thermoplastic elastomer (I). 1 to 3 parts by weight, particularly preferably 0.3 to 2
The components (e) and (f) are preferably used in combination in an amount such that they are parts by weight. In addition, the component (e)
The olefin-based thermoplastic elastomer (I) 10 itself
0 parts by weight or more, preferably 0.02 to 0 parts by weight
3 parts by weight, more preferably 0.1 to 1 part by weight, and the component (f) is 0 parts by weight or more, preferably 0.02 parts by weight based on 100 parts by weight of the olefinic thermoplastic elastomer (I). To 3 parts by weight, more preferably 0.1 to 1 part by weight, and, if component (g) is used, 0.
It is used in an amount of 05 to 5 parts by weight, preferably 0.1 to 1 part by weight.

An olefinic thermoplastic elastomer composition according to the present invention containing the inorganic or organic compound (II) as shown in (e) to (g) and the above-mentioned olefinic thermoplastic elastomer (I). To prepare
The kneading may be performed under the same conditions using the same device as used in the production of the olefinic thermoplastic elastomer (I). There is no particular limitation on the method of adding the inorganic (organic) compound. It may be added during the production of the thermoplastic elastomer, or may be added subsequent to the production of the thermoplastic elastomer or separately. However, in the case of the partially crosslinked thermoplastic elastomer, it is preferable to add and knead the inorganic compound after the production of the thermoplastic elastomer or separately.

The olefinic thermoplastic elastomer composition according to the present invention may optionally contain a flame retardant (III) and / or an olefinic resin (IV).

The flame retardant (III) is a known compound such as a halogen type (eg decabromodiphenyl ether), an antimony type (eg antimony trioxide), an inorganic type (eg magnesium hydroxide) or a phosphorus type. Can be raised.

Examples of the olefin resin (IV) include a polypropylene resin and a polyethylene resin used for producing an olefin thermoplastic elastomer, and a polybutene resin and a poly-4-methyl-1-pentene resin.

In the olefinic thermoplastic elastomer composition containing such a component (III), 0.05 parts of the inorganic or organic compound (II) is added to 100 parts by weight of the olefinic thermoplastic elastomer (I). It is preferable that the flame retardant (III) is contained in an amount of ˜5 parts by weight and the flame retardant (III) is contained in an amount of 1 to 50 parts by weight.

In the olefinic thermoplastic elastomer composition containing the component (IV), 30 to 99 parts by weight of the above olefinic thermoplastic elastomer (I) and 70 to 1 parts by weight of the olefinic resin (IV) are used. It is preferable that the inorganic or organic compound (II) is contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight in total.

In the olefinic thermoplastic elastomer composition containing the components (III) and (IV), the above-mentioned olefinic thermoplastic elastomers (I) 30 to 9 are used.
With respect to 100 parts by weight of 9 parts by weight and 70 to 1 parts by weight of the olefin resin (IV), an inorganic or organic compound
It is preferred that I) is contained in an amount of 0.05 to 5 parts by weight, and the flame retardant (III) is contained in an amount of 1 to 50 parts by weight.

As described above, in order to prepare a partially cross-linked thermoplastic elastomer type olefin-based thermoplastic elastomer composition containing the flame retardant (III) and / or the olefin-based resin (IV), an inorganic filler is used. May be added simultaneously with or after the preparation of the partially crosslinked thermoplastic elastomer, but the flame retardant (III) and the olefin resin (IV) may be added separately after the preparation of the partially crosslinked thermoplastic elastomer or separately. do it.

In order to prepare a non-crosslinking type thermoplastic elastomer type olefin-based thermoplastic elastomer composition containing the flame retardant (III) and / or the olefin resin (IV), an inorganic filler and a flame retardant are used. And olefin resin may be blended together and melt-kneaded to prepare in a single step. Alternatively, after the non-crosslinking type thermoplastic elastomer is prepared,
An inorganic filler, a flame retardant and an olefin resin may be mixed and melt-kneaded.

In the olefinic thermoplastic elastomer composition according to the present invention thus obtained, bleed-out of the additives contained therein is extremely unlikely to occur. In the olefinic thermoplastic elastomer composition according to the present invention, a filler other than the above, for example, calcium carbonate, clay, kaolin, talc, diatomaceous earth, mica powder, asbestos, alumina, within a range not deviating from the object of the present invention. , Barium sulphate, aluminum sulphate, calcium sulphate, magnesium carbonate, molybdenum disulfide, graphite, glass fibers, glass spheres, shirasu balloons, carbon fibers, etc. or coloring agents such as carbon black, titanium oxide,
Zinc white, red iron oxide, ultramarine blue, dark blue, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, and softeners other than the above mineral oils such as animal oil, vegetable oil, synthetic oil or silicone oil. Good.

In the present invention, known heat-resistant stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, antiaging agents,
Additives such as a weather resistance stabilizer, a processing aid (lubricant), or an antistatic agent may be blended. Additives such as the above-mentioned fillers and colorants are usually used in an amount of 0.1 to 40 parts by weight with respect to 100 parts by weight of the olefinic thermoplastic elastomer (I).

The timing of addition of such various additives is not particularly limited, and may be used, for example, when preparing the olefinic thermoplastic elastomer (I). Organic compound (I
It may be used when kneading with I).

[0073]

EFFECTS OF THE INVENTION According to the present invention, an olefinic thermoplastic elastomer composition can be obtained in which bleeding out of the additives contained therein hardly occurs.

[0074]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples.

[0075]

Example 1 58 parts by weight of ethylene / propylene / dicyclopentadiene copolymer rubber (ethylene content 77 mol%, iodine value 6, Mooney viscosity ML _{1 + 4} (100 ° C.) 65), polypropylene (density 0.91 g / cm 3 ³ , melt flow rate 25) 26 parts by weight, polyethylene resin (density 0.92 g / cm ³ , melt flow rate 18) 6 parts by weight,
And mineral oil-based softener (Idemitsu Kosan Co., Ltd., PW-380,
VI: 130) To 100 parts by weight of a kneaded product of 10 parts by weight, 0.3 part by weight of organic peroxide (1,3-bis (tert-butylperoxyisopropyl) benzene) and 1 part by weight of carbon black are added, and biaxial Extruder (cylinder set temperature 20
Dynamic heat treatment was performed at 0 ° C. and a residence time in the extruder of about 3 minutes) to obtain a partially crosslinked thermoplastic elastomer.

100 parts by weight of the above-mentioned thermoplastic elastomer, 0.2 parts by weight of a phenolic heat stabilizer (Irganox 1010, manufactured by Ciba Geigy), a hindered amine type weathering stabilizer (Sanol LS770, manufactured by Sankyo Co., Ltd.)
0.2 parts by weight, 0.3 parts by weight of magnesium behenate, and 0.2 parts by weight of silicon dioxide (Carplex 80 manufactured by Shionogi Pharmaceutical Co., Ltd.) were added to the twin-screw extruder (cylinder set temperature 200 ° C., Kneading is performed for a residence time in the extruder of about 3 minutes), and then press molding is performed at 190 ° C. to obtain 30 cm × 3.
A 0 cm x 1 mm sheet was obtained.

Further, the sheet was allowed to stand in an air oven kept at 60 ° C. for 240 hours and then taken out, and a substance spouting on one side of the sheet was washed off with methyl alcohol and acetone. Further, methyl alcohol and acetone were evaporated from the washed-out liquid, and the weight of the remaining substance was measured to obtain the amount of bleed-out substance.

The results are shown in Table 1.

[0079]

Examples 2 to 5 and Comparative Examples 1 to 3 To the thermoplastic elastomer obtained in Example 1, the same stabilizer as in Example 1 and the inorganic (organic) compound shown in Table 1 were added, and Example 1 was added.
A press sheet was obtained in the same manner as in, and the amount of the bleed-out product was measured by the same method as in Example 1.

The results are shown in Table 1.

[0081]

Examples 6 to 10 and Comparative Examples 4 to 6 Ethylene / propylene / dicyclopentadiene copolymer rubber (ethylene content 66 mol%, iodine value 13, Mooney viscosity ML)
_{1 + 4} (100 ° C) 30) 40 parts by weight, butyl rubber (mu-
D-viscosity ML _{1 + 4} (100 ° C.) 45, unsaturation degree 1.0 mol% 25 parts by weight, polypropylene (density 0.91 g / c
m ^3, a melt flow rate 0.2) 15 parts by weight of polyethylene resin (density 0.92 g / cm ^3, a melt flow rate 1
0) 5 parts by weight, and a mineral oil-based softener (made by Idemitsu Kosan Co., Ltd., P
W-380, VI: 130) 15 parts by weight of kneaded material 100
0.2 parts by weight of an organic peroxide (1,3-bis (tert-butylperoxyisopropyl) benzene) and 1 part by weight of carbon black were added to parts by weight, and a dynamic heat treatment was performed in the same manner as in Example 1, A partially crosslinked thermoplastic elastomer was obtained.

Kneaded material 100 containing 70 parts by weight of the above thermoplastic elastomer, 30 parts by weight of polyethylene resin (density 0.91 g / cm ³ , melt flow rate 0.5 g / 10 minutes)
In parts by weight, the same amount of heat stabilizer and weather stabilizer as in Example 1 and decabromodiphenyl ether 6 as a flame retardant were used.
Parts by weight, 2 parts by weight of antimony trioxide, and further inorganic (organic) compounds shown in Table 2 were added. A sheet was obtained in the same manner as in Example 1, and the amount of the bleed-out product was measured in the same manner as in Example 1.

The results are shown in Table 2. The above results are summarized in Tables 1 and 2.

[0084]

[Table 1]

[0085]

[Table 2]

Inorganic compound 1: Silicon dioxide (Shinogi Pharmaceutical Co., Ltd., Carplex 80) Organic compound 2: Magnesium behenate (Eishin Kasei Co., Ltd.)
EM-700) Inorganic compound 3: Magnesium oxide Inorganic compound 4: Hydrocalumite (Eishin Kasei Co., Ltd.)
Manufactured by E-13) Inorganic compound 5: basic zeolite (manufactured by Eishin Kasei Co., Ltd.,
E-47) Organic compound 6: Calcium stearate (CS-1 manufactured by Eishin Kasei Co., Ltd.) Inorganic compound 7: Calcium oxide

[0087]

Example 11 and Comparative Example 7 Ethylene / Propylene /
Ethylidene norbornene copolymer rubber (ethylene content 82
Mol%, iodine value 10, Mooney viscosity ML _{1 + 4} (100
90) 40 parts by weight, polypropylene (density 0.91)
g / cm ³ , melt flow rate 2.5) 60 parts by weight of kneaded material 100 parts by weight of organic peroxide (1,3-bis (tert-
Butyl peroxyisopropyl) benzene) (0.2 parts by weight) and carbon black (1 part by weight) were added, and a dynamic heat treatment was performed in the same manner as in Example 1 to obtain a partially crosslinked thermoplastic elastomer.

To 100 parts by weight of the above thermoplastic elastomer, the same amount of heat stabilizer and weather stabilizer as in Example 1 and the inorganic (organic) compound shown in Table 2 were added. Example 1
A sheet was obtained in the same manner as in, and the amount of the bleed-out product was measured in the same manner as in Example 1.

The results are shown in Table 3.

[0090]

Example 12 and Comparative Example 8 Ethylene / propylene copolymer rubber (ethylene content 80 mol%, Mooney viscosity ML
_{1 + 4} (100 ° C.) 62) 32 parts by weight, polypropylene (density 0.91 g / cm ³ , melt flow rate 2.5) 6
8 parts by weight and 1 part by weight of carbon black were subjected to dynamic heat treatment in the same manner as in Example 1 to obtain a substantially non-crosslinked thermoplastic elastomer.

To 100 parts by weight of the above-mentioned thermoplastic elastomer, the same amounts of heat stabilizer and weather stabilizer as in Example 1 and the inorganic (organic) compounds shown in Table 2 were added. Example 1
A sheet was obtained in the same manner as in, and the amount of the bleed-out product was measured in the same manner as in Example 1.

The results are shown in Table 3.

[0093]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area C08L 23/04 LCD 7107-4J 23/10 LCD 7107-4J (72) Inventor Keigo Umemoto Kanagawa Kanagawa 3-56-6 Hirado, Totsuka-ku, Yokohama-shi, Japan

Claims (6)

[Claims] 1. An olefinic rubber 30 to 90 parts by weight, a polypropylene resin 10 to 70 parts by weight, a polyethylene resin 0 to 40 parts by weight, and a mineral oil softener 0. 40 parts by weight (however, the total of (a), (b), (c) and (d) is 100 parts by weight), and (e) dioxide is added to 100 parts by weight of the olefinic thermoplastic elastomer (I). An inorganic or organic compound comprising silicon, (f) a fatty acid salt of an alkaline earth metal and / or an oxide of an alkaline earth metal, and optionally (g) a basic zeolite and / or hydrocalumite ( II) is 0.05 ~
An olefin-based thermoplastic elastomer composition, which is contained in an amount of 5 parts by weight. 2. (a) 30 to 90 parts by weight of olefinic rubber, (b) 10 to 70 parts by weight of polypropylene resin, (c) 0 to 40 parts by weight of polyethylene resin, and (d) 0 to softening agent of mineral oil 40 parts by weight (however, the total of (a), (b), (c) and (d) is 100 parts by weight), and (e) dioxide is added to 100 parts by weight of the olefinic thermoplastic elastomer (I). An inorganic or organic compound comprising silicon, (f) a fatty acid salt of an alkaline earth metal and / or an oxide of an alkaline earth metal, and optionally (g) a basic zeolite and / or hydrocalumite ( II) is 0.05 ~
An olefinic thermoplastic elastomer composition, characterized in that the flame retardant (III) is contained in an amount of 5 parts by weight and an amount of 1 to 50 parts by weight. 3. (a) 30 to 90 parts by weight of olefin rubber, (b) 10 to 70 parts by weight of polypropylene resin, (c) 0 to 40 parts by weight of polyethylene resin, and (d) 0 to softening agent of mineral oil. 30 to 99 parts by weight of an olefinic thermoplastic elastomer (I) consisting of 40 parts by weight (however, the total of (a), (b), (c) and (d) is 100 parts by weight) and an olefinic resin (IV) 70 to 1 parts by weight based on 100 parts by weight in total, (e) silicon dioxide, (f) an alkaline earth metal fatty acid salt and / or an alkaline earth metal oxide, and if necessary, (G) an inorganic or organic compound (II) consisting of basic zeolite and / or hydrocalumite in an amount of 0.05 to
An olefin-based thermoplastic elastomer composition, which is contained in an amount of 5 parts by weight. 4. (a) 30-90 parts by weight of olefin rubber, (b) 10-70 parts by weight of polypropylene resin, (c) 0-40 parts by weight of polyethylene resin, and (d) 0-mineral oil-based softening agent. 30 to 99 parts by weight of an olefinic thermoplastic elastomer (I) consisting of 40 parts by weight (however, the total of (a), (b), (c) and (d) is 100 parts by weight) and an olefinic resin ( IV) 70 to 1 part by weight per 100 parts by weight in total, (e) silicon dioxide, (f) fatty acid salt of alkaline earth metal and / or oxide of alkaline earth metal, and optionally contained (G) the inorganic or organic compound (II) consisting of basic zeolite and / or hydrocalumite is from 0.05 to
The flame retardant (III) is contained in an amount of 5 parts by weight.
An olefin-based thermoplastic elastomer composition, which is contained in an amount of 50 parts by weight. 5. The olefin resin (IV) is polyethylene, polypropylene, polybutene or poly-4.
-Methyl-1-pentene, The olefinic thermoplastic elastomer composition according to claim 3 or 4, wherein 6. The olefin according to claim 1, wherein the olefin rubber (a) is ethylene / α-olefin copolymer rubber, polyisobutylene or butyl rubber. -Based thermoplastic elastomer composition.