JPH05320445A - Thermoplastic elastomer composition - Google Patents

Abstract

(57) [Summary] [Structure] A thermoplastic elastomer composition in which the component (B) is present as dispersed particles, which is obtained by kneading a composition containing the components A to C under heating conditions. A: 0.05 to 20 mol% of a specific non-conjugated diene monomer
Reaction product of propylene copolymer contained therein or mixture thereof with specific functional group-containing alkene or alkyne 20 to 70 parts by weight B: acrylic rubber 80
.About.30 parts by weight C: crosslinking agent A + B, based on 100 parts by weight in total,
1 to 10 parts by weight [Effect] It has a high level and an excellent balance in moldability, hardness, mechanical strength, and oil resistance.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition comprising polypropylene, particularly a propylene polymer containing a specific diene monomer, and acrylic rubber, which has an excellent balance between mechanical strength and moldability. ..

[0002]

2. Description of the Related Art Thermoplastic elastomer compositions (hereinafter referred to as T
PE) does not require a vulcanization step and can process and recycle a thermoplastic resin in a molding machine, and thus has been developed for use in industrial parts and automobile parts.

Propylene-based TPE is disclosed in JP-A-48-26.
It is known from Japanese Patent No. 838. However, as far as the present inventors know, this composition is naturally limited in its use because of poor oil resistance or heat resistance. Therefore, in order to improve this performance, it has been attempted to use a nitrile rubber, an acrylic acid ester copolymer rubber, and a compatibility-imparting polymer (JP-A-56-143233 and JP-A-60).
No. 156738, etc.).

[0004]

However, in the above polypropylene-based TPE, the method disclosed in JP-A-60-156738 is used.
Tensile rupture strength, tensile rupture elongation, compression set,
Although there are improvements in oil resistance, there is still room for improvement in order to use them as substitutes for vulcanized rubber. The problem to be solved by the present invention is to provide a polypropylene-based TPE excellent in moldability, hardness, mechanical strength (for example, tensile breaking strength, tensile breaking elongation, compression set) and oil resistance level and their balance. It is to be.

[0005]

Means for Solving the Problems [Outline of the Invention] <Outline> The present inventors have studied various compounding materials for TPE, and as a result, have found that a propylene-based copolymer containing a specific diene monomer is used. The inventors have found that TPE, which is selected by kneading a coalescent component and an acrylic rubber component under heating conditions, is excellent in moldability, hardness, mechanical strength, oil resistance level and balance, leading to the present invention.

That is, the thermoplastic elastomer composition according to the present invention is a component (B) obtained by kneading a composition containing the following components (A), (B) and (C) under heating conditions. Are present as dispersed particles.

Component (A): a copolymer of propylene containing 0.05 to 20 mol% of at least one non-conjugated diene monomer selected from the following formula (I) and the diene monomer,
Or a mixture of the copolymer and another crystalline propylene polymer, wherein the diene monomer is 0.05% or less in the mixture.
A reaction product of an ethylenic or acetylenically unsaturated compound having at least one group selected from an acid anhydride group, a carboxyl group, an epoxy group and an amino group (provided that The content of the ethylenically or acetylenically unsaturated compound in the component (A) is 15
Up to wt%). 20 to 70 parts by weight Component (B): Acrylic rubber having functional group for crosslinking 80 to 30 parts by weight Component (C): Crosslinking agent for crosslinking acrylic rubber by reacting with functional group for crosslinking acrylic rubber To 100 parts by weight of the total amount of the components (A) and (B),
0.1-10 parts by weight of formula (I) In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, R ² and R ³ are not both hydrogen atoms. n represents a number from 1 to 10.

<Effect> The TPE according to the present invention has a high level and an excellent balance in moldability, hardness, mechanical strength (for example, tensile breaking strength, tensile breaking elongation, compression set), and oil resistance. Is. Therefore, the TPE according to the present invention is suitable for various parts in an engine room, various parts for machinery, etc., for automobiles and industrial fields.

[Detailed Description of the Invention] (1) Constituent Component <Component (A)> The component (A) used in the present invention comprises at least one non-conjugated diene monomer selected from the following formula (I): A copolymer of propylene containing 0.05 to 20 mol% of a polymer with the diene monomer, or a mixture of the propylene copolymer with another crystalline propylene polymer, wherein the diene is contained in the mixture. A mixture containing 0.05 to 20 mol% of monomers and an ethylenic or acetylenically unsaturated group having at least one functional group selected from an acid anhydride group, a carboxyl group, an epoxy group and an amino group. A reaction product with a compound (however, the content of the ethylenically or acetylenically unsaturated compound in the component (A) is up to 15% by weight).

[0010] (In the formula, ^{R 1} represents an alkyl group having 1 to 8 hydrogen atoms or carbon atoms, an alkyl group of ^{R 2} and ^{R 3} are each independently a hydrogen atom or 1 to 8 carbon atoms. However, ^{R 2} and ^{R 3}
Are not both hydrogen atoms. n represents a number from 1 to 10. )

Examples of the non-conjugated diene monomer of the above formula (I) include (i) 1,4-dienes (that is, n = 1),
For example, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-
Hexadiene, 4-ethyl-1,4-hexadiene, 5
-Ethyl-1,4-hexadiene, 4,5-diethyl-
1,4-hexadiene, 4-methyl-1,4-heptadiene, 5-methyl-1,4-heptadiene, 4,5-dimethyl-1,4-heptadiene, 4-ethyl-1,4-
Heptadiene, 5-ethyl-1,4-heptadiene,
4,5-diethyl-1,4-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4,5-dimethyl-1,4-octadiene, 4
-Ethyl-1,4-octadiene, 5-ethyl-1,4
-Octadiene, 4,5-diethyl-1,4-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-
1,4-nonadiene, 4,5-dimethyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 4,5-diethyl-1,4-nonadiene, etc. ,

(B) 1,5-dienes (that is, n =
2), for example 5-methyl-1,5-heptadiene, 6-
Methyl-1,5-heptadiene, 5,6-dimethyl-
1,5-heptadiene, 5-ethyl-1,5-heptadiene, 6-ethyl-1,5-heptadiene, 5,6-diethyl-1,5-heptadiene, 5-methyl-1,5-
Octadiene, 6-methyl-1,5-octadiene,
5,6-dimethyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 5,6-diethyl-octadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5,6-dimethyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 5,6-diethyl-1, 5-nonadien, etc.

(C) 1,6-dienes (that is, n =
3), for example 6-methyl-1,6-octadiene, 7-
Methyl-1,6-octadiene, 6,7-dimethyl-
1,6-octadiene, 6-ethyl-1,6-octadiene, 7-ethyl-1,6-octadiene, 6,7-diethyl-1,6-octadiene, 6-methyl-1,6-
Nonadiene, 7-methyl-1,6-nonadiene, 6,7
-Diethyl-1,6-nonadiene, 6-ethyl-1,6
-Nonadiene, 7-ethyl-1,6-nonadiene, 6,
7-diethyl-1,6-nonadiene, etc.,

(D) 1,7-dienes (that is, n =
4), for example 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7,8-dimethyl-1,7
-Nonadiene, 7-ethyl-1,7-nonadiene, 8-
Ethyl-1,7-nonadiene, 7,8-diethyl-1,
Mention may be made of 7-nonadiene and the like.

Among these, 6-methyl-1,5-heptadiene, 6-methyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 8-methyl- Branched non-conjugated dienes such as 1,7-nonadiene, especially 6-methyl-1,6-octadiene and 7-methyl-1,6-octadiene, especially 7-methyl-1,6-octadiene, are preferred. These dienes may be a mixture of two or more.

The copolymer containing a diene monomer can be produced by any known method, for example, JP-A-56-30414.
The method described in the publication can be used. Such a copolymer of a non-conjugated diene monomer and propylene contains other α-olefins as long as the main component is propylene and the diene monomer of the above (I) is contained in a predetermined amount (details described later). Alternatively, an unsaturated monomer may be contained as a subsidiary component (for example, up to 20 mol% based on the total of propylene). Other α-olefins or unsaturated monomers include ethylene, butene-1, vinyl acetate,
There are styrene, vinyl silane, etc., these are random,
It may be contained in any type of copolymer such as block or graft. The diene-containing propylene copolymer may be a mixture of plural kinds of the same copolymer.

Furthermore, the diene-containing propylene copolymer may be a mixture with the diene-free copolymer which is miscible therewith, as long as the diene monomer is contained in a predetermined amount (details described later). Such a polymer may be of any type as long as it is miscible with the diene-propylene-containing copolymer, but for the purpose of the present invention, an acid anhydride group or the like to be reacted with the diene-propylene-containing copolymer. Should be non-polymeric. A preferable polymer corresponds to a composition obtained by removing the diene from a diene-containing propylene copolymer. The preferred polymer is a crystalline propylene polymer.

The content of the non-conjugated diene monomer represented by the above formula (I) in the diene-containing propylene copolymer or the diene-containing propylene copolymer mixture is 0.05 to 2
The range is 0 mol%, preferably 0.15 to 12 mol%, and particularly preferably 0.2 to 6 mol%. If this content is too small, the compatibilizing effect or the effect of improving the physical properties is insufficient,
If it is too large, it is not preferable because the occurrence of local gelation and the control of the dispersed particle size become difficult.

The component (A) in the present invention is an alkene having an acid anhydride group or the like in the above-mentioned diene propylene copolymer (in addition to a single product, it may be a mixture as described above). Alternatively, it is obtained by reacting an alkyne monomer. The reaction between the functional unsaturated compound and the diene-propylene-containing copolymer is mainly carried out by reacting the ethylenically unsaturated bond in the functional unsaturated compound and the residual ethylenically-unsaturated bond in the diene-propylene-containing copolymer. Addition reaction or polyaddition or polymerization. In addition, it is possible that the functional alkene or alkyne is graft-bonded by abstraction or addition of hydrogen on the tertiary carbon of the diene-containing propylene copolymer. When the functional unsaturated compound contains active hydrogen as an unsaturated bond, for example, when the functional group is a carboxyl group or an amino group (having at least one unsubstituted hydrogen atom), The possibility of a Michael-type addition reaction of the ethylenically unsaturated bond in the diene-containing propylene copolymer may be considered.

The unsaturated compound to be reacted with the above-mentioned diene-propylene copolymer or diene-propylene-containing copolymer mixture is at least one kind selected from an acid anhydride group, a carboxyl group, an epoxy group and an amino group. It has a group and has a double bond or a triple bond as an unsaturated bond in the molecule. Both an aliphatic unsaturated hydrocarbon compound and an aromatic unsaturated hydrocarbon compound can be used, and those having an α, β-unsaturated double bond are preferably used.

(A) Examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, citraconic anhydride, chloromaleic anhydride and the like, preferably maleic anhydride. (B) Examples of the unsaturated compound containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and the like, with acrylic acid and methacrylic acid being preferred. (C) Epoxy group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3- There are methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, p-glycidylstyrene and the like, and glycidyl acrylate and glycidyl methacrylate are preferable.

(D) As amino group-containing unsaturated compounds, alkyl ester derivatives of acrylic acid and methacrylic acid such as aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, N -Vinyldiethylamine, N-methylallylamine, and other vinylamine derivatives, allylamine, methacrylamine, and other allylamine derivatives, and p-aminostyrene, acrylamide, and the like. As is clear from these examples, the “amino group” in the present invention includes a mono- or di-substituted amino group in addition to the typical N-unsubstituted amino group.

Of these unsaturated compounds, preferred are:
It is an unsaturated compound having an acid anhydride group and an epoxy group, and maleic anhydride and glycidyl methacrylate are particularly preferable.

The amount of the functional group-containing unsaturated compound contained in the component (A) is 0.01 to 15% by weight, preferably 0.01 to 10% by weight, particularly preferably 0.05 to 8%.
% By weight. If it is less than 0.01% by weight, the compatibility with acrylic rubber is poor and it is difficult to achieve the dispersion state of the acrylic rubber of the present invention.
When it exceeds 0% by weight, a crosslinking reaction occurs in the component (A), and it becomes difficult to form the component (B) as dispersed particles, which is not preferable.

The diene monomer of the above formula (I) is added in an amount of 0.05 to
The reaction of a propylene polymer containing 20 mol% or a mixture thereof with a crystalline propylene polymer and an unsaturated compound having at least one kind of functional group can be carried out by either a melting method or a solution method. Is. The melt-kneading method is preferable from the viewpoint of production cost and reactivity of unsaturated compounds. The temperature at the time of melt-kneading is generally 150 to 250 ° C., preferably 1
70-230 degreeC.

Since the reactivity of the unsaturated compound is improved, it is preferable that the peroxide be present during the melt kneading. As the peroxide used at this time, a known organic peroxide can be used. Examples of such organic peroxides include t-butyl-hydroperoxide, di-
t-butyl-peroxide, 2,2-bis-t-butyl-peroxy-octane, t-butyl-peroxybenzoate, bis-t-butyl-peroxy-isopropyl-benzene, benzoyl peroxide, etc.,
Bis-t-butyl-peroxy-isopropyl-benzene is preferred.

Melt flow rate (MF) of component (A)
R, 230 ° C, load 2.16 kg) is 0.05 to 100
g / 10 minutes, preferably 0.05 to 70 g / 10 minutes, particularly preferably 0.1 to 50 g / 10 minutes.
When the MFR value is less than 0.05 g / 10 minutes, the moldability is poor, and when it is more than 100 g / 10 minutes, the mechanical strength level of the TPE obtained is low, which is not preferable.

<Component (B)> The component (B) of the thermoplastic elastomer composition according to the present invention is an acrylic rubber.

The term "acrylic rubber" as used in the present invention means a rubber-like polymer having rubber elasticity mainly in the acrylate unit. In addition, the acrylic rubber needs to be crosslinkable, as is customary for rubbers, and the rubbery copolymer has functional groups such as ethylenic or acetylenically unsaturated groups which should be utilized for crosslinking. It is a copolymer of a group and an unsaturated monomer having a functional group such as a carboxyl group, an epoxy group and an active chlorine-containing group.

Therefore, a group of such acrylic rubbers is obtained by copolymerizing a necessary amount of a monomer having a functional group capable of forming a crosslinked structure with an acrylic acid ester.

Another group of acrylic rubbers for use in the present invention is acrylates and "elastic" monomers other than acrylates, eg alpha-olefins such as ethylene, propylene and isobutene and / or butadiene. , A copolymer with a conjugated diene such as isoprene and chloroprene.

As the acrylic acid ester mainly responsible for rubber elasticity, an ester with a monohydric alcohol having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, such as methyl acrylate,
The same ethyl, the same butyl and the same ethylhexyl, and an ethylene glycol or polyalkylene glycol having 2 to 3, preferably 2, which is etherified at one end with an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms ( Representative examples thereof include esters with a polymerized alkylene ether and a degree of polymerization of about 2 to 4), such as methoxyethyl acrylate and ethoxyethyl acrylate, methoxyethoxyethyl acrylate, and others. Of these, the former is preferable. These can be used in combination within each group and between each group.

The monomers which are to play a part in the rubber elasticity together with the acrylic ester are, as mentioned above, α-olefins such as ethylene, propylene or isobutene and conjugated dienes such as butadiene, isoprene or chloroprene. ..

The functional monomer for providing the crosslinked structure is
For example, non-conjugated dienes, such as those of formula (I) described above for component (A), such as 4-methyl-1,4-hexadiene, alkylidene, merbornene, such as ethylidene, norbornene, carboxyl group containing monomers such as ( (Meth) acrylic acid, an epoxy group-containing monomer such as glycidyl (meth) acrylate (herein, "(meth) acrylic" means acryl and methacryl), allyl glycidyl ether, and other active hydrogen atoms There are monomers included, such as 2-chloroethyl vinyl ether, vinyl benzyl chloride, vinyl chloroacetate, and others.

"Non-elastomeric" monomers (which may include those having crosslinkable functional groups) that may be copolymerized include nucleus and / or side chain-substituted or unsubstituted styrene (substituent Is lower alkyl, lower alkoxy, halogen, vinyl, etc.), for example, unsubstituted styrene, ethylenically unsaturated nitrile, such as acrylonitrile, carbon number 1-8.
Methacrylic acid esters of monohydric alcohols, such as methyl methacrylate, tetrahydrobenzyl methacrylate, divinylbenzene, and the like.

A preferred acrylic rubber is a copolymer of acrylic acid C _1-8 alkyl ester and an epoxy group- or carboxyl group-containing monomer (the ester: molar composition of the monomer = 99.95: 0. 05-90: 10),
Copolymer of acrylic acid C _1-8 alkyl ester, ethylene and a carboxyl group-containing monomer (molar composition of the ester: ethylene: monomer = 89.95: 10: 0.0
5 to 10:80:10) and the like.

The viscosity of the component (B) is such that the melt flow rate of the component (A) is 0.05 to 100 and the composition of the component (A) / component (B) is 20/80 to 70/30 (weight ratio). This is the range in which the component (B) is the continuous phase. Specifically, the Mooney viscosity ML _{1 + 4} (100
C.) is 10 to 150, preferably 10 to 120, particularly preferably 15 to 80.

When ML _{1 + 4} (100 ° C.) is less than 10,
It is sufficient to make the component (B) a continuous phase, but the subsequent crosslinking by dynamic heat treatment with the component (C) of the component (B) increases the viscosity of the component (B), and further the target component (B). ) Is difficult to be dispersed particles.

When ML _{1 + 4} (100 ° C.) exceeds 150, the composition of component (A) / component (B) is 20/80 to 70 /
In 30, it is difficult to form the component (B) as a continuous phase, and the target dispersed particle diameter of the component (B) can be obtained even if the component (C) is subjected to the dynamic heat treatment. No
Not preferable.

<Component (C)> The component (C) which gives the thermoplastic elastomer composition according to the present invention has at least two functional groups capable of reacting with the crosslinking functional group of the acrylic rubber of the component (B). Is.

The functional groups of the cross-linking agent depend on the given acrylic rubber, so that specific examples of cross-linking agents where the cross-linking site of the acrylic rubber is an epoxy group or a carboxyl group can react with this functional group. It is a compound containing two or more functional groups in one molecule, such as an amino group, an acid anhydride group, a carboxyl group, an isocyanate group, and an epoxy group. It is preferable to use a known cross-linking accelerator together with these cross-linking agents.

As the compound containing an amino group,
(A) Aliphatic diamines such as trimethylhexamethylenediamine, ethylenediamine, and 1,4-diaminobutane, (b) aliphatic polyamines such as triethylenetetramine, pentaethylenehexamine, aminoethylethanolamine, and (c) phenylenediamine , 4,4′-methylenedianiline, toluenediamine, diaminoditolylsulfone, and other aromatic amines.

Examples of the acid anhydride group- or carboxyl group-containing compound include trimellitic anhydride, pyromellitic anhydride, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, cyanuric acid and the like. Examples of the isocyanate group-containing compound include toluene diisocyanate and isocyanates of a prepolymer having an isocyanate terminal group. Examples of the epoxy group-containing compound include epoxides such as bisphenol A, resorcinol and diglycidyl ether such as hydroquinone.

A specific example of a preferred crosslinking agent system for an acrylic rubber in which the crosslinking site is an epoxy group is 4,4 'as the crosslinking agent.
-Methylenedianiline, 4,4 '-(α, α'-dimethylbenzyl) diphenylamine, ammonium benzoate as a promoter, zinc dimethyl-dithiocarbamate, ferric dimethyl-dithiocarbamate. In particular, the combination of 4,4 '-(α, α'-dimethylbenzyl) diphenylamine and ferric dimethyl-dithiocarbamate is preferred.

Specific examples of preferred crosslinking agent systems for acrylic rubbers having a carboxyl group at the crosslinking site are hexamethylenediamine, 4,4'-methylenedianiline as a crosslinking agent and 1,3-diphenylguanidine as an accelerator. A combination of 4,4'-methylenedianiline and 1,3-diphenylguanidine is particularly preferred.

It has been described above that the acrylic rubber may have a functional group other than an epoxy group and a carboxyl group as a functional group which provides a crosslinking point. When the functional group is, for example, an amino group, a bifunctional compound having a functionality to react with such a functional group is easily known to those skilled in the art, and as the crosslinking agent in that case, for example, bisglycidyl is used. There is no difficulty in selecting an appropriate compound such as a compound.

<Other Components> The thermoplastic elastomer composition according to the present invention is obtained by kneading the above-mentioned three essential components (A) to (C) under heating conditions. If necessary, the elastomer composition may contain the component (A)
Other components besides (C) can be added. Therefore, the thermoplastic elastomer according to the present invention includes those containing such other components.
This is the reason why the composition to be heated and kneaded is defined as "comprising components (A), (B) and (C)".

Other components used as required include, for example, phthalic acid esters such as dimethyl phthalate and dioctyl phthalate, tributyl phosphate,
Phosphoric acid esters such as triphenyl phosphate, trimellitic acid esters, plasticizers such as sulfonamides, fillers such as talc, silica and glass fiber, known flame retardants, stabilizers such as antioxidants, colorants , Lubricants, etc.

(2) Composition Ratio of Constituents The composition of the components (A) and (B) is important because the TPE of the present invention is preferably produced by using the phase inversion method. The composition of components (A) and (B) is 20
70 to 80 to 30 parts by weight, preferably 20 to 60/8
0-40 parts by weight, more preferably 25-50 / 75-
50 parts by weight. The amount of the cross-linking agent (C) used for the purpose of cross-linking the acrylic rubber depends on the components (A) and (B).
0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of
Parts by weight.

The content of the functional alkene or alkyne in the component (A) is up to 15% by weight, preferably 0.0
As described above, it is 1 to 10% by weight, more preferably 0.05 to 8% by weight.

(3) Production The TPE according to the present invention has a structure in which the dispersed phase of the component (B) is uniformly dispersed in the matrix derived from the component (A). Although such a structure can be formed by any purposeful method, a typical or preferable method is a so-called phase inversion method. By using such a phase inversion method,
It becomes easy to improve the compatibility by forming a cross-linked product of the acrylic rubber and the diene-propylene-containing copolymer, to achieve cross-linking within the acrylic rubber, and to realize a fine dispersion TPE of the cross-linked acrylic rubber. In the phase inversion method here, first, a mixed state or mixture of the component (A) and the component (B) having the component (B) as a continuous phase is formed, and then the component (C) is formed.
Component (B) in the presence of a cross-linking agent of
The crosslinking reaction of the phase is allowed to proceed, that is, the heat treatment is dynamically performed to increase the viscosity of the phase (B) and to perform the phase inversion.
Although the component (B) was initially a continuous phase as the viscosity of the (B) phase increased, the component (A) / (B) passed through the continuous phase state, and finally the component (A). Is the continuous phase / component (B)
Becomes a mixture of discontinuous phases. The obtained mixture is a thermoplastic elastomer composition having a structure in which a crosslinked acrylic rubber and a diene-propylene-containing copolymer are appropriately contained and the crosslinked acrylic rubber is finely dispersed.

As the manufacturing apparatus for obtaining the TPE of the present invention, various apparatuses for blending resins with each other or resins with stabilizers and colorants can be generally applied. For example, a powder or granular component is first uniformly dispersed by a Henschel mixer, super mixer, ribbon blender, V blender, etc., and then a uniaxial kneading extruder, a biaxial kneading extruder, a roll. Melt kneading with a Banbury mixer, plastomill, Brabender plastograph, etc. In the present invention, it is particularly preferable to carry out kneading in an atmosphere of an inert gas such as nitrogen gas.
The melt-kneading temperature is usually 150 to 250 ° C., preferably 1
The range is 70 to 230 ° C.

(4) Objective Thermoplastic Elastomer Composition The thermoplastic elastomer composition according to the present invention is provided by the method as described above, and the dispersed phase derived from the component (B) is contained in the matrix derived from the component (A). Has a so-called "sea-island" structure in which are uniformly and finely dispersed. The particle size of the dispersed phase is about 0.1 to 10 μm, preferably 0.3 to 6 μm.
It is about m.

Regarding the dispersed particle size of acrylic rubber in the thermoplastic elastomer composition, an ultrathin section was prepared by dyeing by a known method, and then observed using a transmission electron microscope, and an image analyzer (Nippon Mavionics Spica II was used. ) Was used to measure the area-equivalent circle equivalent diameter: Di for each dispersed particle of the component (B). The average dispersed particle diameter was calculated by the following formula. still,
ni is the number of particles having a circle equivalent diameter Di.

[0055]

EXAMPLES The following experimental examples concretely show the present invention. These are merely examples, and the examples do not limit the scope of the present invention. The polymer components used are as follows.

<Component (A)> A-1 Polypropylene resin manufactured by Mitsubishi Petrochemical Co., Ltd. Grade name MA4 A-2 Propylene copolymer containing 7-methyl-1,6-octadiene synthesized by the following method and maleic anhydride Melt kneading reaction product of acid.

[Preparation of Supported Catalyst] 1 liter of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, and then 1.0 mol of MgCl ₂ and Ti were added.
2.0 mol of (O.nC ₄ H ₉ ) ₄ was introduced and reacted at 100 ° C. for 2 hours. After the reaction was completed, the temperature was lowered to 40 ° C., and then methyl hydrogen polysiloxane was added to 15
0 ml was introduced and the reaction was carried out for 3 hours. After completion of the reaction, the produced solid component was washed with n-heptane, and a part thereof was taken out and analyzed for composition. Ti = 15.2
% By weight and Mg = 4.2% by weight.

1 liter of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, and 0.3 mol of the above-synthesized component was introduced in terms of Mg atom. Si
Introduce 0.5 mol of Cl ₄ at 30 ° C for 15 minutes and
And reacted for 2 hours. After completion of the reaction, it was washed with purified n-heptane. Then, 250 ml of n-heptane was mixed with 0.04 mol of ortho-C ₆ H ₄ (COOl) ₂ and introduced at 50 ° C., and then 0.5 mol of SiCl ₄ was introduced and reacted at 90 ° C. for 2 hours. After completion of the reaction, it was washed with n-heptane to obtain a catalyst component. Ti content is 2.0
It was 3% by weight.

[Manufacture of Copolymer] After replacing the autoclave having a capacity of 100 liters with propylene, 30 liters of n-heptane was charged and triethylaluminum was used.
0 g, 4.0 g of diphenyldimethoxysilane and 10.0 g of the carrier-supported catalyst prepared by the above method were added. Next, after adding 12.5 liters of hydrogen, propylene was injected under pressure and stirred at 50 ° C. and 0.5 kg / cm ² G. After this, 7
-Methyl-1,6-octadiene (12 liters) was added, and the temperature was raised while pressurizing propylene at 70 ° C and 7 kg / cm.
Polymerization was carried out while holding at ² G. Then, after deactivating the catalyst with n-butanol, the catalyst residue was extracted with water, the copolymer was recovered by centrifugation and dried. 19.3 kg of dry powder was obtained. The melting peak of this copolymer by DSC was 152.3 ° C. In addition, the content of 7-methyl-1,6-octadiene was 4.0 mol% as analyzed by H ¹ -NMR.

[Production of Melt-Kneaded Reaction Product] 7-Methyl-1,6-octadiene-containing propylene copolymer 10 described above
0 parts by weight, 4 parts by weight of maleic anhydride and 0.1 part by weight of bis-t-butyl-peroxy-isopropyl-benzene were mixed. These are sealed with nitrogen gas 20
The mixture was melt-kneaded with a twin-screw kneading extruder set at 0 ° C. to obtain a granular melt-kneading reaction product. The physical properties are as follows. MFR: 2.1 (g / 10 minutes) Maleic anhydride content: 2.8% by weight

A-3 In A-2, 4 parts by weight of maleic anhydride was changed to 5 parts by weight of glycidyl methacrylate and 0.2 part by weight of organic peroxide was used, and the same operation as in A-2 was performed. The physical properties of the obtained melt-kneading reaction product are as follows. MFR: 2.5 (g / 10 minutes) Glycidyl methacrylate content: 3.9% by weight

A-4 In A-2, the same operation as in A-2 was carried out by changing the amount of maleic anhydride to 2.4 parts by weight and the amount of organic peroxide to 0.1 parts by weight. The obtained physical properties are as follows. MFR: 2.3 (g / 10 minutes) Maleic anhydride content: 1.2% by weight

Using an A-5 Brabender plastograph, 100 parts by weight of A-1, 3 parts by weight of maleic anhydride, and 0.3 parts by weight of an organic peroxide similar to A-2 were added at 180 ° C., 120 rpm, The mixture was melt-kneaded for 5 minutes, 5 parts by weight of 4,4'-methylene dianiline was further added, and the mixture was kneaded for 5 minutes. The melt-kneaded product was dissolved in hot xylene, and a small amount of insoluble matter was present, but 3
The lysate was precipitated with twice the amount of acetone, filtered and dried. By infrared analysis of the dried product, the content of 4,4'-methylenedianiline having a terminal amino group calculated from the amino group was 0.5% by weight. Next, 40 parts by weight of the powdery dried material and 60 parts by weight of B-2 (described later) were melt-kneaded with a Gravender Plastograph at 130 rpm for 6 minutes to obtain a reaction product.

A-6 The same operation as in A-2 was carried out by changing 7-methyl-1,6-octadiene to 6,7-dimethyl-1,6-octadiene. The content of 6,7-dimethyl-1.6-octadiene was 3.6 mol%. The physical properties of the resulting granular melt-kneading reaction product are as follows. MFR: 2.3 (g / 10 minutes) Maleic anhydride content: 2.6% by weight

A-7 7-methyl-1,6-octadiene was replaced with 8-methyl-1,
The same operation as in A-2 was performed by changing to 7-nonadiene. The content of 8-methyl-1,7-nonadiene is 3.7
It is mol%, and the physical properties of the melt-kneading reaction product are as follows. MFR: 2.5 (g / 10 minutes) Maleic anhydride content: 2.5% by weight

[0066] <Component (B)> B-1 Nippon Mektron Ltd. acrylate rubber: "Knox tight PA303" crosslinking sites: epoxy group Mooney viscosity _{ML 1 + 4 (100 ℃)} : 36 B-2 Showa Denko - DuPont (Ltd. ) Ethylene-methyl acrylate copolymer rubber: Mooney viscosity ML _{1 + 4} (100 ° C.): 16 “Baymac G” Crosslinking site: carboxyl group

<Evaluation Method> The TPEs obtained in Examples 1 to 10 and Comparative Examples 1 to 8 were press molded under the following conditions,
A test piece was cut from the sheet. It was measured for the following items. Molding condition Temperature 220 ° C. Pressure 50/100 kgf / cm ² Hour 1 min / 1 min Melt flow rate (MFR) Measured at 230 ° C. under a load of 5 kg (unit: g / 10 min) according to JIS K-7210. Tensile rupture strength, tensile rupture elongation Dumbbell-shaped was formed by a small injection molding machine (Minimax) and measured at 23 ° C. according to JIS K-7113 (unit: kgf / cm ² ,%). Compression set According to JIS K-6301, after compression at 100 ° C. for 22 hours at a compression ratio of 25%, measurement was performed (unit:%). Hardness: Measured with A type according to JIS K-6301. Oil resistance ASTM No. After immersing in 3 oils at 125 ° C. for 72 hours, the degree of swelling was calculated by the following formula (unit:%).

Examples 1 to 3 According to the composition of Table 1, the components A-1, A-2, B-1 and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethyl) Benzyl) cyanuric acid and tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4-
Hydroxyphenyl) propionate) methane was added to each.
It was added so as to be 05 parts by weight, and using a Brapender Plastograph under a nitrogen atmosphere at 190 ° C., 160 rpm,
Was kneaded for 4 minutes, a predetermined amount of the cross-linking agent was added according to the composition of Table 1, and kneaded for 8 minutes under the same conditions as above. The completion of the reaction was confirmed from the transition of the kneading torque, and the obtained kneaded product was pulverized to obtain TPE.

Examples 4 to 6 The components (A) and (B) and the type of the cross-linking agent were changed, and Table 1
The same operation as in Examples 1 to 3 was repeated according to the composition of
PE was obtained.

Experimental Example 7 A TPE was obtained by repeating the same procedure as in Example 2 except that the component (A) was changed according to the composition shown in Table 1.

Comparative Examples 1-2 According to the composition shown in Table 1, the same antioxidant as in Example 1 was added, and the mixture was kneaded at 190 ° C. and 160 rpm for 12 minutes.

Comparative Examples 3 to 5 According to the compositions shown in Table 1, the same operations as in Examples 1 to 7 were performed. The evaluation results of the obtained TPE are shown in Table 2.

Comparative Example 6 In Example 5, except that A-3 was changed to A-5,
The same operation as in Example 5 was carried out to obtain TPE. The evaluation results are shown in Table 2. From the results in Table 2, it can be seen that the levels of tensile properties and compression set are inferior to those of Example 5.

Examples 8 to 10 The components (A) were changed according to the compositions shown in Table 3, and the same operation as in Example 2 was performed. The evaluation results are shown in Table 4.

Comparative Examples 7 to 8 According to the compositions shown in Table 3, the same operations as in Examples 8 to 10 were performed. The evaluation results are shown in Table 4.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

EFFECTS OF THE INVENTION The TPE according to the present invention has excellent moldability, hardness,
As described above in the "Summary of the Invention", it has a high level and an excellent balance in mechanical strength and oil resistance.

Claims (1)

[Claims] 1. A thermoplastic elastomer composition obtained by kneading a composition comprising the following components (A), (B) and (C) under heating conditions, in which the component (B) exists as dispersed particles. object. Component (A): a copolymer of propylene containing at least one non-conjugated diene monomer selected from the following formula (I) in an amount of 0.05 to 20 mol% and the diene monomer, or the copolymer: A mixture of a polymer and another crystalline propylene polymer, wherein the diene monomer is 0.05 to 20 mol% in the mixture.
A reaction product of the mixture contained with an ethylenic or acetylenically unsaturated compound having at least one group selected from an acid anhydride group, a carboxyl group, an epoxy group and an amino group (provided that the ethylenic Alternatively, the content of the acetylenically unsaturated compound in the component (A) is up to 15% by weight). 20 to 70 parts by weight Component (B): Acrylic rubber having functional group for crosslinking 80 to 30 parts by weight Component (C): Crosslinking agent that crosslinks acrylic rubber by reacting with functional group for crosslinking acrylic rubber To 100 parts by weight of the total amount of the components (A) and (B),
0.1-10 parts by weight of formula (I) In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, R ² and R ³ are not both hydrogen atoms. n represents a number from 1 to 10.