JPH07188507A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer composition containing respective specific thermoplastic graft copolymer and styrene resin, exhibiting high tensile strength without deteriorating rubber elasticity, having high hardness and excellent heat resistance and useful as a material for hose, etc. CONSTITUTION:This thermoplastic elastomer composition contains (A) 100 pts.wt. of a thermoplastic graft copolymer obtained by reacting (i) a polymer having a glass transition temperature of <=10 deg.C for forming main chain with (ii) an aromatic oligomer having a flow temperature of >=100 deg.C for forming side chain and (B) 1-40 pts.wt. of a styrene resin. Preferably, the component (ii) is e.g. an oligomer having benzene ring in the main skeleton and especially containing 50-60wt.% of a structural unit of formula I [X is O or S; Ar is group of formula II (R<1> is a 1-3C alkyl; p is 0-2), etc.] and the component B is a copolyme containing >=50wt.% of a styrenic monomer of formula III (R3 to R7 each is H, a halogen or a 1-6C hydrocarbon group; R8 is H or a 1-4C alkyl).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic elastomer composition having excellent heat resistance.

[0002]

2. Description of the Related Art A thermoplastic graft copolymer obtained by reacting a main chain polymer having a glass transition temperature of 10 ° C. or lower with an aromatic oligomer whose side chain has a flow temperature of 100 ° C. or higher (hereinafter simply referred to as a graft copolymer). Sometimes called a polymer.)
Is a thermoplastic elastomer having excellent heat resistance, but further improvements in tensile strength and fluidity during molding have been desired. Further, although this thermoplastic graft copolymer is characterized by being extremely soft, it has been required to have higher hardness depending on its use.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a thermoplastic elastomer composition having higher hardness and improved tensile strength and fluidity during molding while maintaining the heat resistance of the thermoplastic elastomer. Especially.

[0004]

[Means for Solving the Problems] In view of such circumstances,
As a result of intensive studies, the present inventors have found that a resin composition comprising 100 parts by weight of the thermoplastic graft copolymer and 1 to 40 parts by weight of a styrene-based resin becomes a thermoplastic elastomer having excellent tensile strength. The inventors have found that it is possible to further increase hardness by adjusting the amount of resin added, and have completed the present invention. That is, the present invention comprises the inventions described below. [1] 100 parts by weight of a thermoplastic graft copolymer obtained by reacting a polymer having a glass transition temperature of 10 ° C. or lower, which is a main chain, with an aromatic oligomer whose side chain has a flow temperature of 100 ° C. or higher defined below. A thermoplastic elastomer composition containing 1 to 40 parts by weight of a styrene resin. Flow temperature: 100 kg by heating and melting at a temperature rising rate of 4 ° C / min
A temperature at which the apparent melt viscosity measured by a method of extruding from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of / cm ² is 48,000 poise.

The glass transition temperature (hereinafter sometimes abbreviated as Tg) of the main chain (trunk polymer) constituting the graft copolymer used in the present invention is 10 ° C. or lower, preferably 0 ° C. or lower, and particularly It is preferably -10 ° C or lower.
The glass transition temperature is a second-order transition point at which an endotherm is observed in a differential scanning calorimeter (DSC) at a temperature rising rate of 10 ° C./min. The glass transition temperature of the main chain (trunk polymer) is 1
When the temperature exceeds 0 ° C, the thermoplastic elastomer composition of the present invention does not exhibit rubber elasticity in a use temperature range of room temperature or higher, which is not preferable.

The main chain (stem polymer) having a Tg of 10 ° C. or less, which constitutes the graft copolymer used in the present invention, is an acrylic acid ester polymer, polybutadiene, polyisoprene, polychloroprene, chlorosulfonated polyethylene, etc. Homopolymer of styrene / butadiene copolymer and hydrogenated product thereof, styrene / isoprene copolymer and hydrogenated product thereof, ethylene / propylene copolymer,
Examples thereof include ethylene / propylene / diene copolymers, acrylonitrile / butadiene copolymers and hydrogenated products thereof, random copolymers such as ethylene / acrylic acid ester copolymers; and polyorganosiloxane and polyphosphazene. Further, a copolymer of a monomer that forms the homopolymer or the random copolymer described above and a monomer having a copolymerizable unsaturated double bond can also be used. However, in any copolymer, T
The copolymer composition must be controlled so that g is 10 ° C. or less.

The side chain aromatic oligomer constituting the graft copolymer used in the present invention has a flow temperature of 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 170 ° C.
It is an aromatic oligomer of ℃ or more. Further, the flow temperature of the aromatic oligomer is 400 ° C. or lower, preferably 350 ° C.
Hereafter, it is more preferably 300 ° C. or lower.

The flow temperature of the aromatic oligomer is 100 ° C.
When it is lower, the temperature range showing rubber elasticity in the obtained thermoplastic elastomer composition becomes narrow, that is, the heat resistance of the thermoplastic elastomer composition becomes insufficient, which is not preferable.

The aromatic oligomer having a flow temperature of 100 ° C. or higher, which constitutes the graft copolymer used in the present invention, is an oligomer having a benzene ring in the main skeleton, and preferably has a structure represented by the general formula 1. It is an oligomer containing a unit of 50% by weight or more, preferably 60% by weight or more.

[Chemical 1] (In the formula, X is selected from O and S, and one oligomer may simultaneously contain a structural unit containing O and a structural unit containing S.

Ar is selected from the general formulas 2, 3, and 4.

[Chemical 2]

[Chemical 3]

[Chemical 4]

Here, R ¹ and R ² are selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group, and R ¹ and R ² may be the same or different. Different groups may be attached to one benzene ring. p and q are integers of 0-2. )

The number average molecular weight of the oligomer is 300 to 1
It is preferably in the range of 500, and more preferably in the range of 400 to 1000. Number average molecular weight is 300
If it is less than 1, the polycondensate is likely to be thermally decomposed, the flow temperature is remarkably lowered, and the heat resistance of the obtained graft copolymer is lowered, which is not preferable, and if the number average molecular weight is more than 1500, the flow is deteriorated. The temperature is close to the thermal decomposition temperature of the oligomer, and the moldability of the thermoplastic elastomer composition obtained is unfavorable.

In order to control the properties such as the melting point of the oligomer mainly composed of hydroxyarylcarboxylic acid polymer, monomers such as hydroxyalkylcarboxylic acid, aminoalkylcarboxylic acid and aminoarylcarboxylic acid are polycondensed. And a structure in which a monofunctional carboxylic acid compound, a phenol compound, and an amino compound are condensed.

The reason why the thermoplastic elastomer composition of the present invention exhibits rubber elasticity is that the aromatic oligomer of the side chain of the graft copolymer constituting the composition functions as a hard segment in the graft copolymer. It is presumed that it forms a microdomain structure and serves as a physical crosslinking point. However, this estimation does not limit the invention in any way.

The glass transition temperature of the graft copolymer constituting the thermoplastic elastomer composition of the present invention is 10
The ratio of the polymer having a temperature of not more than 0 ° C. to the aromatic oligomer having a flow temperature of not less than 100 ° C. is 99/1 to 50/50 (weight ratio), preferably 97/3 to 65/35 (weight ratio).

When the amount of the polymer having a glass transition temperature of 10 ° C. or lower exceeds 99% by weight, the thermoplastic elastomer composition obtained is not preferable in the temperature range of room temperature or higher because it remarkably causes plastic deformation. Is difficult to show, which is not preferable.

The graft copolymer can be used alone as a thermoplastic elastomer, but by blending a styrene resin with the graft copolymer, tensile strength can be obtained without impairing the properties as a thermoplastic elastomer. It has become possible to improve the hardness and freely increase the hardness.

The styrene resin used in the present invention is
It means a copolymer or polystyrene containing 50% by weight or more of a styrene-based monomer unit. Here, the styrene-based monomer is a compound represented by the general formula 5.

[Chemical 5] (In the formula, R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms and a substituted hydrocarbon group having 1 to 8 carbon atoms, Carbon number 1
It is selected from the group consisting of a hydrocarbon oxy group having 6 to 6 and a substituted hydrocarbon oxy group having 1 to 8 carbon atoms. R ₈
Is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. )

Examples of the copolymer containing 50% by weight or more of the styrene-based monomer unit include a copolymer of the styrene-based monomer unit and the above-mentioned monomer unit. Examples of the monomer unit other than the styrene-based monomer unit include a monomer unit copolymerizable with the styrene-based monomer, and specifically, dienes such as butadiene and isoprene;
Vinyl compounds such as acrylonitrile and vinyl acetate; styrene derivatives such as α-methylstyrene and p-chloro-α-styrene copolymers; acrylic acid esters and their derivatives; maleic anhydride and its derivatives;
Methacrylic acid ester and its derivative are mentioned. Furthermore, a styrene-butadiene-acrylonitrile copolymer, a styrene-acrylonitrile-α-methylstyrene copolymer, a styrene-acrylonitrile-vinylcarbazole copolymer, and a multi-component copolymer with several types of comonomers copolymerizable with styrene, such as Can be mentioned. The styrene content of the styrene resin is 50% by weight or more,
It is preferably 70% by weight or more, more preferably 80% by weight or more. If the styrene content is less than 50% by weight, the resulting thermoplastic elastomer composition may not exhibit sufficient strength, which is not preferable.

The method for producing the styrene resin in the present invention includes radical polymerization, ionic polymerization and coordination polymerization, but is not particularly limited. Further, the copolymer containing a styrene unit is not particularly required to be the above-mentioned random copolymer or alternating copolymer, and may be a block copolymer or a graft copolymer.

Further, the ratio of the styrene resin to 100 parts by weight of the thermoplastic graft copolymer constituting the thermoplastic elastomer composition of the present invention is 1 to 40 parts by weight,
It is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the proportion of the styrene resin is more than 40 parts by weight, the obtained thermoplastic elastomer composition does not show good rubber elasticity, which is not preferable. When the proportion of styrene resin is less than 1% by weight, the thermoplastic elastomer has insufficient tensile strength and hardness.

Further, in the thermoplastic elastomer of the present invention, carbon black, silica, calcium carbonate, mica, diatomaceous earth, zinc white, basic magnesium carbonate, and
Fillers such as aluminum silicate, titanium dioxide, talc, glass fibers, silica-alumina fibers, plasticizers, antioxidants, colorants, ultraviolet absorbers, flame retardants, oil resistance improvers, scorch inhibitors and tackifiers, etc. Can be arbitrarily mixed and used.

As a method for producing the thermoplastic graft copolymer constituting the thermoplastic elastomer composition of the present invention, a polymer having a glass transition temperature of 10 ° C. or lower and having a functional group capable of reacting with a carboxyl group and flowing Temperature is 100
Examples include a method of reacting with an aromatic oligomer having a carboxyl group at one end at a temperature of not less than ° C. The functional group capable of reacting with the carboxyl group is preferably an epoxy group, an isocyanate group, a hydroxyl group or an acetoxy group. An epoxy group is particularly preferable.

The epoxy group-containing polymer includes methyl acrylate / glycidyl methacrylate copolymer, ethyl acrylate / glycidyl methacrylate copolymer, propyl acrylate / glycidyl methacrylate copolymer, butyl acrylate / glycidyl methacrylate copolymer, Hexyl acrylate / glycidyl methacrylate copolymer, dodecyl acrylate /
Examples thereof include glycidyl methacrylate copolymer.

Further, methyl acrylate / glycidyl styrene copolymer, ethyl acrylate / glycidyl styrene copolymer, propyl acrylate / glycidyl styrene copolymer, butyl acrylate / glycidyl styrene copolymer, hexyl acrylate / glycidyl styrene copolymer, Examples thereof include dodecyl acrylate / glycidyl styrene copolymer.

Further, methyl acrylate.N- [4-
(2,3-Epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethyl acrylate
N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, propyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer Polymer, butyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, hexyl acrylate / N- [4-
(2,3-Epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, dodecyl acrylate.N- [4- (2,3-epoxypropoxy) -3,5
Dimethylbenzyl] acrylamide copolymer and the like.

Further, acrylonitrile-butadiene-
Examples thereof include a glycidyl methacrylate copolymer, an acrylonitrile / butadiene / glycidyl styrene copolymer, and an acrylonitrile / butadiene / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer.

Further, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl styrene copolymer, ethylene / vinyl acetate / N
-[4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer and the like.

Further, ethylene / methyl acrylate /
Glycidyl methacrylate copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer, ethylene / propyl acrylate / glycidyl methacrylate copolymer, ethylene / butyl acrylate / glycidyl methacrylate copolymer, ethylene / hexyl acrylate / glycidyl methacrylate copolymer, Examples thereof include ethylene / dodecyl acrylate / glycidyl methacrylate copolymers.

Further, ethylene methyl acrylate
Glycidyl styrene copolymer, ethylene / ethyl acrylate / glycidyl styrene copolymer, ethylene / propyl acrylate / glycidyl styrene copolymer, ethylene / butyl acrylate / glycidyl styrene copolymer, ethylene / hexyl acrylate / glycidyl styrene copolymer, Examples thereof include ethylene / dodecyl acrylate / glycidyl styrene copolymers.

Further, ethylene methyl acrylate
N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene.
Ethyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene / propyl acrylate / N- [4
-(2,3-Epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene / butyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer , Ethylene hexyl acrylate N- [4-
(2,3-Epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene dodecyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, etc. Is mentioned.

Further, styrene / butadiene / glycidyl methacrylate copolymer, styrene / butadiene / glycidyl styrene copolymer, styrene / butadiene / N
Examples thereof include various copolymers such as-[4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer. These various copolymers can be usually obtained by well-known radical polymerization.

The aromatic oligomer used in the present invention having a flow temperature of 100 ° C. or higher, preferably 150 ° C. or higher and having a carboxyl group at one end is preferably represented by the following general formula 6.

[Chemical 6]

(In the formula, X is selected from O and S, and a structural unit containing O and a structural unit containing S may be simultaneously contained in one oligomer. N is a number average of 2 to 10.

R ¹⁰ is an alkyl group having 5 or more carbon atoms, or an aryl group or aralkyl group having 6 or more carbon atoms.
Ar is selected from general formulas 7, 8, and 9.

[Chemical 7]

[Chemical 8]

[Chemical 9]

Here, R ¹ and R ² are selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group, and R ¹ and R ² may be the same or different. Different substituents may be attached to the same benzene ring. p and q are integers of 0-2. )

It is also possible to copolymerize and use a hydroxycarboxylic acid having 2 to 6 carbon atoms in the above oligomer. The number average molecular weight of the aromatic oligomer having a carboxyl group at one end shown above is preferably in the range of 300 to 1500, and the number average degree of polymerization depends on the selected species of R ¹⁰ , R ¹ , R ² and Ar. 2-10, preferably 3-8,
More preferably, it is 4-7.

Predominantly hydroxyarylcarboxylic acid polymers are hydroxyarylcarboxylic acids, and optionally small amounts of copolymerizable monomers, such as hydroxyalkylcarboxylic acids having 2 to 6 carbon atoms, aminoalkylcarboxylic acids, aminoarylcarboxylic acids. Although any method may be used as long as it is a method of producing a polycondensate from an acid, a monofunctional phenol compound, a carboxylic acid compound, an amino compound or the like as a raw material, the following method is preferable.

That is, an acetylating agent such as acetic anhydride or acetyl chloride is added to hydroxyarylcarboxylic acid,
Acetoxyarylcarboxylic acid is obtained by heating and stirring. When acetylating a hydroxyarylcarboxylic acid or the like with acetic anhydride in the above reaction, the reaction is
Acetylation is achieved by performing the reaction at 00 ° C. or higher for 15 minutes or more, and in the reaction with acetyl chloride at room temperature or higher for 30 minutes or more. In any reaction, it is preferable to add acetic anhydride and acetyl chloride in excess, preferably about 1.1 times, the number of moles of hydroxyl groups to be reacted. After the acetylation is finished,
The polycondensation reaction proceeds by deacetic acid while heating the system and stirring. The temperature in the system should preferably be 200 ° C. or higher. The number average molecular weight can be controlled by the amount of acetic acid to be distilled off.To control the desired degree of polymerization, calculate the amount of charged monomers such as hydroxyarylcarboxylic acid and the amount of acetic acid to be distilled off. is necessary. An aromatic oligomer containing a mercaptoarylcarboxylic acid can also be produced according to the above.

The obtained aromatic oligomer is used for the purpose of improving the thermal stability thereof, such as methanol, ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone,
Wash with a solvent such as chloroform or pyridine to remove the monomer,
It is desirable to remove dimers.

The aromatic oligomer having a carboxyl group at one end is a monocarboxylic acid or hydroxyaryl having an alkyl group having 5 or more carbon atoms, preferably 5 to 20 or an aryl group having 6 or more carbon atoms, preferably 6 to 15 carbon atoms. After acetylating a mixture of a carboxylic acid and optionally a hydroxycarboxylic acid having 2 to 6 carbon atoms with acetic anhydride or acetyl chloride in the same manner as in the above-mentioned method for producing a hydroxyarylcarboxylic acid polymer, A polycondensate can be obtained by deacetic acid. In this reaction, the number average molecular weight is determined by the molar ratio of monocarboxylic acid and hydroxycarboxylic acid.

The obtained oligomer having a carboxyl group at one end is methanol, ethanol, acetone, tetrahydrofuran, N-, as described above.
It is preferable to wash with a solvent such as methylpyrrolidone, chloroform or pyridine.

The thermoplastic elastomer composition of the present invention comprises
A graft copolymer is obtained by reacting a polymer having Tg of 10 ° C. or less and a functional group capable of reacting with a carboxyl group with an aromatic oligomer having a flowing temperature of 100 ° C. or more and a carboxyl group at one end. After that, by mixing the graft copolymer and a styrene resin,
Alternatively, a polymer having a functional group capable of reacting with a carboxyl group and having a Tg of 10 ° C. or lower is mixed with a styrene resin, and then the mixture and the aromatic oligomer having a flow temperature of 100 ° C. or higher and a carboxyl group at one end are mixed. A polymer having a functional group capable of reacting with a carboxyl group and having a Tg of 10 ° C. or less, and an aromatic oligomer having a carboxyl group at one end and having a carboxyl group at one end, and a styrene resin are packaged together by reaction. It can be obtained by mixing and reacting with. The reaction and / or mixing is not particularly limited, but a method of reacting and / or mixing by melt kneading is preferable.

This melt-kneading is carried out by the melting temperature of the polymer existing in the system at the time of kneading (flowing temperature of an aromatic oligomer,
If it is a styrene-based resin, it can be carried out using a usual kneader at a melting temperature higher than the glass transition temperature). As the kneading machine, any device such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a roll or a kneader can be used as long as it can apply a high shearing force at a high temperature.

The reaction or mixing temperature is not lower than the temperature showing the highest melting temperature among the polymer species present in the system at the time of kneading and lower than the temperature showing the lowest thermal decomposition temperature among the polymer species present in the system. Preferably there is. When the reaction or mixing temperature is lower than the temperature showing the highest melting temperature among the polymer species existing in the system during kneading, for example, the carboxyl group of the aromatic oligomer does not react with the polymer having Tg of 10 ° C. or less, or the styrene resin is sufficient. It is not preferable because it is not mixed, and when the reaction or mixing temperature exceeds the temperature showing the lowest thermal decomposition temperature among the polymer species existing in the system at the time of kneading, the decomposition of the polymer progresses during kneading and it is not preferable. .

A polymer having a functional group capable of reacting with a carboxyl group and having a Tg of 10 ° C. or lower and a flowing temperature of 100 ° C.
Above, and to react an aromatic oligomer having a carboxyl group at one end, that is, in order to promote grafting, it is preferable that the temperature is higher within the above temperature range, and that the reaction time is longer, and the shearing force is higher. Is preferably larger.

Further, in promoting the grafting, a phosphine-based catalyst such as triphenylphosphine, triparatolylphosphine, trimetaltolylphosphine, triorthotolylphosphine, tri-2,6-dimethoxyphenylphosphine, or 2-phenylimidazole. , 2-undecylimidazole, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]
It is preferable to use an amine-based catalyst such as -ethyl-S-triazine and 1,8-diazabicyclo (5,4,0) undecene-7.

[0048]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The measurement conditions for each physical property are as follows.

Compression set test: Using a constant strain compression tester manufactured by Toyo Seiki Seisakusho, in accordance with JIS K-6301, 10
The measurement was performed at 0 ° C. for 22 hours.

Flowing temperature: Using a high-performance flow tester CFT-500 manufactured by Shimadzu Corporation, heating and melting at a temperature rising rate of 4 ° C./min and a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 100 kg / cm ^2. The temperature at which the melt viscosity was 48,000 poise when extruded was taken as the flow temperature. Melt index (hereinafter sometimes abbreviated as MI):
It was measured with a melt indexer manufactured by Toyo Seiki Seisakusho Ltd.

Tensile test: Using a tensile tester Tensilon EM-500 manufactured by Toyo Baldwin Co., Ltd., JIS K-6
The measurement was performed according to 301.

Shore A hardness: A Shore hardness tester manufactured by Toyo Seiki Seisaku-sho, Ltd. was used to measure the hardness according to ASTM D-2240. The thickness of the sample was 4.2 mm and the interval was 15 seconds.

Example 1 An ethylene / methyl acrylate / glycidyl methacrylate terpolymer (ethylene / methyl acrylate / glycidyl methacrylate = 35/63) was used according to the method described in Example 5 of JP-A-61-127709. / 2
(Weight ratio), MI = 190 ° C., 2.16 kg load
8.7 g / 10 minutes) was obtained.

The glass transition temperature of this polymer was measured by a stand-alone type differential scanning calorimeter DSC-50 type manufactured by Shimadzu Corporation in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. From the obtained figure, the endothermic onset temperature was determined by the tangential method according to the conventional method and used as the glass transition temperature. Glass transition temperature is -33.
It was 7 ° C. In addition, the heating loss curve of this polymer was measured by Shimadzu's stand-alone thermogravimetric analyzer TGA-5.
It was measured at 0 at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From this measurement, it was found that this polymer was thermally stable up to around 350 ° C.

An aromatic oligomer having a carboxyl group at one end was synthesized as follows. Parahydroxybenzoic acid 1 in a 50 liter reaction vessel that had been washed and replaced with nitrogen
6.56 kg (120 mol), benzoic acid 7.32 kg
(60 mol) Acetic anhydride 13.46 kg (132 mo
l) was charged and stirred at a stirring speed of 130 rpm for 15 minutes,
The system was homogenized. Cooling water was caused to flow through the reflux pipe to raise the jacket temperature to 160 ° C. Jacket temperature 160 ℃
The mixture was kept at room temperature, and acetylation was carried out for 3 hours while refluxing acetic anhydride. After the completion of the acetylation reaction, the cooling water in the reflux pipe was stopped, and the cooling water was flown into the condenser for flowing out acetic acid.
The jacket temperature was raised to 280 ° C, and the reaction was continued at 280 ° C until acetic acid and acetic anhydride were not distilled from the system. After 3 hours from the start of heating to 280 ° C, acetic acid, etc.
5 kg was recovered. At this point, distillation of acetic acid and the like had disappeared, so the oligomer was taken out from the lower portion of the reaction tank. All of the above operations were performed under a nitrogen atmosphere.

The oligomer thus taken out was coarsely pulverized by using a coarse pulverizer and then finely pulverized by a bantam mill (screen having a diameter of 1.50 mm). A 100-liter reaction tank purged with nitrogen was charged with 7.5 kg of the obtained powder and 75 liters of acetone, a jacket temperature of 25 ° C. or lower, and a stirring speed of 13
The mixture was stirred at 0 rpm and washed for 1 hour. After washing, the washed slurry was taken out from the lower part of the reaction tank into a filter and the oligomer was filtered off. The obtained wet cake was put in a tray, and dried at 80 ° C. for 12 hours by using shelf vacuum drying. The oligomer obtained was 5.8 kg and the yield was 77.
%Met. When the flow temperature of this purified oligomer was measured, it was 202 ° C. Next, the heating loss of this purified oligomer was measured using the above-mentioned TGA-50 type apparatus in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. From this, it was found that this purified oligomer was stable up to around 300 ° C.

Next, the number average degree of polymerization of the purified oligomer was measured according to the chemical decomposition method described in the example of JP-A-4-11657. The number average degree of polymerization of the oligomer was n in the general formula 10. = 4.2.

[Chemical 10]

The ethylene / methyl acrylate / glycidyl methacrylate terpolymer described above and an aromatic oligomer having a carboxyl group at one end, triparatolylphosphine (manufactured by Kitako Chemical Industry Co., Ltd.), Naugart 445 (manufactured by Uniroyal Corporation), Styrene / acrylonitrile copolymer obtained by suspension polymerization (styrene / acrylonitrile = 78/22 (weight ratio), MI (200 ° C.,
5 kg load) = 16 g / 10 min) was melt-kneaded using a twin-screw extruder. The details will be described below. As a twin-screw extruder, Japan Steel Works twin-screw extruder TEX30-XSST-
42BW-4V, cylinder temperature 220 ° C., screw rotation number 200 rpm, ethylene / methyl acrylate / glycidyl methacrylate terpolymer 8.5 kg / hr, aromatic oligomer / Naugard 445 / triparatolyl phosphine = 100/10 /
A mixture of 2 in a weight ratio of 2.0 kg / hr and 1.5 kg / h of a styrene-acrylonitrile copolymer.
supplied at r. Following melt-kneading with a twin-screw extruder,
The composition obtained by a PASC-21HS type pellet manufacturing apparatus manufactured by Tanabe Plastic Machinery Co., Ltd. connected to a twin-screw extruder was pelletized. The pellets of the obtained composition were vacuum-dried at 80 ° C. for 12 hours, and then injection molded machine IS-25 EP-1A manufactured by Toshiba Machine Co., Ltd. was used to measure JIS dumbbell No. 3 test piece and 70 mm × 70 mm × 2 mmt.
Was molded into a flat plate.

The MI of the composition at 260 ° C. under a load of 10 kg is shown in Table 1. Also, tensile test, hardness test,
The results of the compression set test are also shown in Table 1. The test pieces for the hardness test and the compression set were cut out from the molded flat plate.

Example 2 3.0 kg / h of styrene / acrylonitrile copolymer
A composition was obtained in the same manner as in Example 1 except that the composition was supplied at r. An injection molded article was obtained in the same manner as in Example 1, and various physical properties were measured from this in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that the styrene / acrylonitrile copolymer was not supplied. An injection molded article was obtained in the same manner as in Example 1, and various physical properties were measured from this in the same manner as in Example 1. The results are shown in Table 1.

[0062]

[Table 1]

[0063]

EFFECT OF THE INVENTION The thermoplastic elastomer composition of the present invention exhibits high tensile strength and high hardness without impairing rubber elasticity. It exhibits excellent behavior as a rubber elastic body even at high temperatures, and is extremely useful as a thermoplastic elastomer having excellent heat resistance.

Therefore, various hose materials such as oil cooler hoses, air duct hoses, power steering hoses, control hoses, oil return hoses, heat-resistant hoses, various oil seals, O-rings, packings, gaskets, and other sealing materials Various diaphragms,
It has a wide range of applications such as rubber plates, belts, oil level gauges, hose masking, and sound insulation materials, and is useful.

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[Procedure amendment]

[Submission date] November 16, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Further, methyl acrylate.N- [4-
(2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, ethyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5
- dimethylbenzyl] acrylamide copolymer, acrylate · N-[4- (2,3-epoxypropoxy) -3,5 - dimethyl benzyl] acrylamide copolymer, butyl acrylate · N-[4- (2,3 -Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, hexyl acrylate / N- [4
-(2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, dodecyl acrylate / N- [4- (2,3-epoxypropoxy)-
3,5 - dimethylbenzyl] acrylamide copolymer and the like.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

Further, acrylonitrile-butadiene-
Examples thereof include a glycidyl methacrylate copolymer, an acrylonitrile / butadiene / glycidyl styrene copolymer, and an acrylonitrile / butadiene / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

Further, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl styrene copolymer, ethylene / vinyl acetate / N
-[4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer and the like can be mentioned.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

Further, ethylene methyl acrylate
N- [4- (2,3-epoxypropoxy) -3,5 -
Dimethylbenzyl] acrylamide copolymer, ethylene / ethyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, ethylene / propyl acrylate / N-
[4- (2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, ethylene / butyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] Acrylamide copolymer, ethylene / hexyl acrylate / N- [4
-(2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, ethylene / dodecyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer Examples thereof include polymers.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

Further, styrene / butadiene / glycidyl methacrylate copolymer, styrene / butadiene / glycidyl styrene copolymer, styrene / butadiene / N
Examples thereof include various copolymers such as-[4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer. These various copolymers can be usually obtained by well-known radical polymerization.

Claims (1)

[Claims] 1. A polymer having a glass transition temperature of 10 ° C. or lower, which is a main chain, has a side chain with a flow temperature defined below of 100 ° C.
100 parts by weight of a thermoplastic graft copolymer obtained by reacting the above aromatic oligomer and styrene resins 1 to 4
A thermoplastic elastomer composition containing 0 part by weight. Flow temperature: 100 kg by heating and melting at a temperature rising rate of 4 ° C / min
A temperature at which the apparent melt viscosity measured by a method of extruding from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of / cm ² is 48,000 poise.