JPH1036457A - Modifier and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modifier which can give engineering plastics excellent in impact resistance, moldability, etc., by using a modified ethylene/propylene copolymer rubber having a specified composition. SOLUTION: An ethylene/propylene copolymer rubber (A), an aromatic vinyl monomer (B) (e.g. styrene) and a polar-group-containing vinyl monomer (C) are subjected to a polymerization reaction under melt kneading to obtain a modified ethylene/propylene copolymer rubber. The obtained modified rubber is used as a modifier for engineering plastics. Component C is suitably a vinyl monomer having a polar functional group selected among hydroxyl, carboxyl and epoxy. Desirable examples include 2-hydroxyethyl methacrylate, maleic anhydride and glycidyl methacrylate. Components B and C are suitably used in such a mixing ratio that component C is used in an amount at most equimolar to that of component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a modifier useful for improving the impact resistance of engineering plastics and a composition containing the same. More specifically, the present invention provides
Melt-kneading polymerization of aromatic vinyl monomer and polar functional group-containing vinyl monomer in the presence of ethylene propylene copolymer rubber.Excellent in impact resistance, mechanical strength and moldability. , Especially polyamides,
The present invention relates to a modifier for engineering plastics such as polyester resin and polyphenylene sulfide, and a composition containing the modifier.

[0002]

2. Description of the Related Art Engineering plastics such as polyamide resin, polycarbonate resin and polyester resin have excellent heat resistance and chemical resistance.
BACKGROUND ART Molding materials reinforced with reinforcing materials such as non-reinforced resins and glass fibers have been used in various fields such as automobile parts and electronics-related parts, and the demand has been greatly increased in recent years. However, it has been widely recognized that these engineering plastics do not always have sufficient impact resistance and have a particularly low notched Izod impact value.

[0003] Therefore, in order to improve the brittleness of engineering plastics with such a notch, it has been attempted to improve the brittleness by blending a rubber-like substance. In particular, ethylene propylene copolymer rubber has good heat resistance and weather resistance, and also has good rubber properties, so that it is suitable as an impact resistance improver for engineering plastics. It has been applied to various uses as an impact modifier.

However, engineering plastics having a high polarity and ethylene propylene copolymer rubber having a low polarity originally have no affinity. Therefore, when the two components are simply mixed, the adhesion at the interface of the two-phase structure is good. In addition, not only is the effect of improving the impact resistance low, but also the molded product is liable to delaminate. Therefore, it has been proposed to blend a modified ethylene propylene copolymer rubber in which a vinyl monomer such as maleic acid is introduced into the ethylene propylene copolymer rubber (Japanese Patent Publication No. 55-44108, Japanese Patent Application Laid-Open No. 2-160813). .

Further, it has been proposed that such a modified ethylene-propylene copolymer rubber is still insufficient in compatibility with a highly polar polyamide or aromatic polyester resin, and that an epoxy group-containing ethylene copolymer is blended. (JP 6
0-63250).

However, these compositions have insufficient impact resistance improving effects due to lack of compatibility, insufficient moldability, particularly insufficient weld strength, or have insufficient impact resistance and mechanical properties. In order to share the strength, not only the modified ethylene-propylene copolymer rubber but also an expensive third-component compatibilizer is required, resulting in a complicated compounding system, which is industrially disadvantageous.

On the other hand, the inventors of the present invention have proposed a thermoplastic resin obtained by a melt-kneading reaction of a propylene-based polymer or olefin-based rubber and an aromatic vinyl-based monomer in a molten state in the presence of a radical initiator. A resin composition (JP-A-6-313077) has been proposed. However, in order to improve the impact resistance of propylene-based polymers in which olefin-based rubber is easily compatible, olefin-based rubber is added to propylene-based polymer and melt-kneading graft reaction is performed. It was not intended to improve the impact resistance of the sample.

As described above, the engineering plastics blended with the ethylene-propylene copolymer rubber according to the conventional method are not industrially satisfactory in terms of mechanical properties or moldability. This is because it is difficult to microdisperse the ethylene propylene copolymer rubber into resins having different polarities. In order to sufficiently disperse the ethylene propylene copolymer rubber in the resin phase, a chemical bond or a hydrogen bond is formed between the ethylene propylene copolymer rubber and the resin phase in order to improve the affinity with the resin phase. It is desirable to have such as. However, since the ethylene-propylene copolymer rubber has almost no unsaturated bond unlike the butadiene-based polymer, a conventional method introduces a sufficient amount of polar functional groups capable of forming a chemical bond or a hydrogen bond. It seems that it was difficult.

[0009]

However, the problem to be solved by the present invention is to solve all the drawbacks of the engineering plastics in the prior art, and to excel particularly in mechanical properties such as impact resistance. The present invention relates to a modifier for engineering plastics which improves moldability such as weld strength, which has been a problem of the composition, and a composition containing the same.

[0010]

As a result of detailed studies, the present inventors have found that an aromatic vinyl monomer and a polar functional group-containing vinyl monomer are melt-kneaded and polymerized in the presence of an ethylene-propylene copolymer rubber. For the first time, it was found that a high-polymerization reaction rate and a high graft-reaction rate, and a resin composition containing the same with excellent physical properties and moldability were obtained. The present invention has been completed.

That is, the present invention can be obtained by subjecting (A) an ethylene propylene copolymer rubber to a melt kneading polymerization reaction of (B) an aromatic vinyl monomer and (C) a vinyl monomer having a polar functional group. A modifier for engineering plastics, preferably a polar functional group selected from a hydroxyl group, a carboxyl group and an epoxy group, wherein the modifier for engineering plastics comprises a modified ethylene / propylene copolymer rubber; Containing, preferably an aromatic vinyl monomer (B) and a polar functional group-containing vinyl monomer (C)
(C) is a modified ethylene propylene copolymer rubber obtained by using the same molar amount or less of (B), preferably a radical polymerization initiator is blended, the radical initiator Under such conditions of temperature and time that decomposition of the ethylene propylene copolymer rubber (A) does not substantially occur,
Performing the impregnation operation with the aromatic vinyl monomer (B) and the polar functional group-containing vinyl monomer (C) before the melt-kneading polymerization reaction,
6. A modified ethylene propylene copolymer rubber obtained preferably by using a radical polymerization initiator having a decomposition temperature of 1 minute half-life of 180 ° C. or higher as a radical polymerization initiator in combination, and any one of claims 1 to 5. An engineering plastic composition comprising an engineering plastic modifier having a polar functional group and an engineering plastic having a functional group capable of reacting with the functional group, wherein the polar functional group is a carboxyl group and / or an epoxy group The present invention provides an engineering plastic composition characterized by using a modifier for engineering plastics, wherein the engineering plastic is selected from polyamide resins, aromatic polyester resins and polyphenylene sulfide.

Hereinafter, the present invention will be described in detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylene-propylene copolymer rubber (A) of the present invention is a rubbery copolymer containing ethylene and propylene as essential components, and the weight ratio of ethylene to propylene is usually 90:10 to 20. : 80, preferably in the range of 75:25 to 40:60. Mooney viscosity ML1 + of ethylene propylene copolymer rubber used
4 (100 ° C.) is preferably from 10 to 100, more preferably from 20 to 70. A small amount of other monomers other than ethylene and propylene may be copolymerized, for example, butene, pentene, heptene, octene, and the like.
As the diene component, dicyclopentadiene, ethylidene norbornene, 1,4-pentadiene, 1,4-hexadiene, 1,5-cyclooctadiene and the like can be used.

The above-mentioned ethylene propylene copolymer rubber (A)
Is converted into an iodine value,
Preferably, it is in the range of 4 to 50. These ethylene-propylene copolymer rubbers may be commercially available pellets, or may be masses obtained by finely cutting a lump. Other rubbers and thermoplastic resins can be used in combination as long as the properties of the ethylene propylene copolymer rubber are not impaired. In particular, it is preferable that a resin whose impact resistance is to be improved is previously present in the melt-kneading polymerization reaction.

Examples of the aromatic vinyl monomer (B) include styrene, methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, isopropylstyrene, chlorostyrene, dichlorostyrene, and bromostyrene. Is preferred.

Polar functional group-containing vinyl monomer used in combination
(C), copolymerizable epoxy group-containing vinyl monomer, carboxyl group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, oxazoline group-containing vinyl monomer, silyl group-containing vinyl monomer, etc. No.

As the epoxy group-containing vinyl monomer, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, methacryl glycidyl ether and the like can be mentioned, and these can be used alone or in combination. Glycidyl methacrylate is particularly preferred.

The carboxyl group-containing vinyl monomer includes, for example, acrylic acid, methacrylic acid, maleic anhydride, maleic acid and the like, and also includes acid anhydrides, and these are used alone or as a mixture. . Particularly, maleic anhydride is preferred.

Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
-Hydroxybutyl methacrylate and the like can be used alone or as a mixture.

Examples of the silyl group-containing vinyl monomer include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltris ( 2-methoxyethoxy) silane and the like may be used alone or as a mixture.

Examples of the oxazoline group-containing vinyl monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-oxazoline and the like.

Further, a small amount of other monomers which can be copolymerized with the aromatic vinyl monomer, for example, various vinyl cyanides such as acrylonitrile;
Various vinyl esters; alkyl esters of acrylic acid or methacrylic acid or glycidyl esters, and further, maleic esters may be used in combination.

The amount of the aromatic vinyl monomer (B) added is 35% by weight of the graft-modified ethylene propylene copolymer rubber.
Hereinafter, it is preferably 1 to 20% by weight. If it exceeds 35% by weight, the effect of improving the impact resistance of the ethylene-propylene copolymer rubber is impaired, which is not preferred. In addition, the aromatic vinyl monomer (B) not only increases the polarity of the ethylene-propylene copolymer rubber to improve compatibility with a high-polarity resin such as an aromatic polyester resin, but also enhances the ethylene-propylene copolymer rubber. This has the effect of significantly increasing the rate of graft polymerization of the polar functional group-containing vinyl monomer. Therefore, the aromatic vinyl monomer
The amount of (B) added is preferably at least the same molar amount as that of the polar functional group-containing vinyl monomer, and more preferably 1 to 5 times the molar amount.

The amount of the polar functional group-containing vinyl monomer (C) is 10% by weight or less, preferably 0.1 to 5% by weight of the graft-modified ethylene propylene copolymer rubber. If the amount exceeds 10% by weight, not only the molecular weight of the product is reduced, but also adverse effects such as tackiness, water absorption and mechanical properties of the composition may occur, which is not preferable.

From the characteristics of the present invention, the above-mentioned radical polymerization initiator is easily dissolved in a monomer such as aromatic vinyl, and is used for polymerization at a melting and kneading temperature of ethylene propylene copolymer rubber. The decomposition temperature for obtaining a half-life of 1 minute is 150 ° C. or higher, preferably 1
The temperature is preferably within a range of 80 to 250 ° C.

Typical examples of the radical polymerization initiator include tert-butyl perbenzoate, dimethyl-di (tert-butylperoxy) hexane, bis (tert-butylperoxyisopropyl) benzene, dimethyl -Di (tert-butylperoxy) hexine, diisopropylbenzene hydroperoxide or cumene hydroperoxide.

The amount of the radical polymerization initiator used is based on 100 parts by weight of the aromatic vinyl monomer (B).
Preferably within the range of 0.1 to 10 parts by weight, particularly preferably within the range of 1 to 5 parts by weight.

Further, in performing the graft polymerization, it is desirable to add additives such as a stabilizer of fine powder and an anti-adhesive agent for the purpose of preventing heat deterioration and blocking. However, it goes without saying that it is necessary to consider the type and the amount of addition so as not to hinder the polymerization of the aromatic vinyl monomer.

As typical examples of such stabilizers, pentaerythrityl-tetrakis ((di-tert-butyl-hydroxyphenyl) propionate), octdecyl (di-tert-butyl-) are exemplified. Various hindered phenolic stabilizers, such as (hydroxyphenyl) propionate, thiobis (methyl t-butylphenol) or trimethyl-tris (di-tert-butylhydroxybenzyl) benzene;
Various phosphorus stabilizers, such as tetrakis (di-tert-butylphenyl) biphenylene phosphite or tris (di-tert-butylphenyl) phosphite; various metal soaps, such as zinc stearate or calcium stearate; Or various antacid adsorbents, such as magnesium oxide or hydrotalcite,
Anti-adhesives such as talc and silica. In particular, as the anti-adhesive agent, fine calcined silica having an average particle diameter of 3 μm or less is preferable from the viewpoints of anti-blocking ability, transparency of the modified ethylene propylene copolymer rubber, and suppression of fish eyes.

The amount of the additive to be used is usually 100 parts by weight of the ethylene-propylene copolymer rubber.
The range of 0.01 to 5 parts by weight is preferably 0.1 to 5 parts by weight.
A range of from 2 to 2 parts by weight is appropriate.

Further, as additives, a small amount of solvent or water may be added for the purpose of diluting or degassing monomers or radical initiators.

Aromatic vinyl monomer (B) to ethylene propylene copolymer rubber (A), polar functional group-containing vinyl monomer (C)
Impregnating the aromatic vinyl monomer (B) on the ethylene propylene copolymer rubber (A) under conditions of temperature and time such that decomposition of the radical initiator does not substantially occur. That is, as the conditions for such impregnation, specifically, first, the temperature is 80 ° C.
In the following, the temperature is preferably in the range of 50 to 20 ° C., and the time is preferably 5 minutes or more, preferably in the range of 10 to 60 minutes, although it is preferably related to the temperature.

In the impregnation, a closed system or a nitrogen atmosphere is preferable. The melt-kneading polymerization reaction of the ethylene-propylene copolymer rubber (A), the monomer such as aromatic vinyl (B), and the vinyl monomer having a polar functional group (C) can be carried out in various closed containers such as Banbury or by extrusion. It can be performed using various continuous kneaders such as a kneader.

When so-called industrial production, such as granulation of modified rubber, is considered, it is preferable to use an extruder, and furthermore, supply of reactants, removal of volatile components, and control of polymerization time. It is more desirable to use a twin-screw extruder or the like from the viewpoint of simplicity.

Preferred production methods include fine-grain ethylene propylene copolymer rubber (A), aromatic vinyl monomer
(B), a compound with a polar functional group-containing vinyl monomer (C), etc., is supplied to an extruder, and while pressurized, 180 to 250 ° C.
Heat to within the range, ethylene propylene copolymer rubber
(A) is melted, and a monomer such as aromatic vinyl (B) and a polar functional group-containing vinyl monomer (C) are melt-kneaded and polymerized, and then discharged from a die. good.

At this time, the aromatic vinyl monomer (B) and the polar functional group-containing vinyl monomer (C) are mixed with an ethylene propylene copolymer rubber before being supplied to an extruder. When the amount of the monomer is large, a part of the monomer may be supplied to the ethylene-propylene copolymer rubber in a molten state using a liquid feeder in combination.

The radical polymerization initiator is preferably added in a state of being dissolved in an aromatic vinyl monomer in advance. However, the radical polymerization initiator is added to a mixture of the ethylene-propylene copolymer rubber and the monomer using a liquid feeder. You may. For stabilizers,
It is preferable to mix the ethylene propylene copolymer rubber in advance.

In the extruder, the ethylene-propylene copolymer rubber (A) and the aromatic vinyl monomer (B) in a molten state are brought into sufficient contact with each other in the presence of a radical initiator to form a homogeneous melt. As a result, a graft polymer of the ethylene-propylene copolymer rubber (A) and the aromatic vinyl monomer (B) is obtained.

The ethylene-propylene copolymer rubber (A) is likely to form a network when melt-mixed in the presence of a radical initiator, but it can be formed in the presence of an aromatic vinyl monomer (B) and a stabilizer. Conversely, it is considered that a grafting reaction is likely to occur while preventing reticulation.

The product obtained is composed of an ethylene propylene copolymer rubber (A) and an aromatic vinyl polymer. The product itself is microscopically homogeneous,
As it is, it can be taken out as a molded product or as a pellet. Because the modified ethylene propylene copolymer rubber is composed of polar and non-polar polymer parts, the modified ethylene propylene copolymer rubber obtained according to the method of the present invention can be used for various thermoplastic resins, especially for highly polar engineering plastics. As an impact resistance improver, or as a compatibility improver with other polymers and inorganic fillers (inorganic fillers).

Examples of the high-polarity engineering plastic include polyamide resin, aromatic polyester resin, polycarbonate, polyphenylene ether, polyphenylene sulfide, and polyacetal. The types of functional groups possessed by the modified ethylene propylene copolymer rubber compounded depending on the type of these plastics are superior. In the case of a polyamide resin, a carboxyl group, in the case of an aromatic polyester resin, an epoxy group, and in the case of polyphenylene sulfide, a modified ethylene-propylene copolymer rubber containing an epoxy group is preferred.

The composition comprising the modified ethylene propylene copolymer rubber (A) of the present invention is used in an amount of 5 to 60% by weight, preferably 10 to 60% by weight, of the above modified ethylene propylene copolymer rubber (A).
30% by weight, engineering plastic (B) 95
-40% by weight, preferably 90-70% by weight. In the composition, the modified ethylene propylene copolymer rubber contains 5
If the amount is less than 10% by weight, the effect of improving the impact resistance, moldability and the like by the modified ethylene propylene copolymer rubber cannot be obtained.
On the other hand, if the amount of engineering plastic such as polyamide resin or aromatic polyester resin is less than 40% by weight, heat resistance, rigidity, etc. cannot be maintained by the plastic (B).

In addition to these essential components, additional components can be added to the composition of the present invention as long as the effects of the present invention are not impaired. Additional components include, for example, other thermoplastic resins, rubbers, inorganic fillers, pigments, various stabilizers (antioxidants, light stabilizers, antistatic agents, antiblocking agents,
Lubricant).

In preparing the composition of the present invention, these components are dry-blended with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, and the like.
This mixture is melt-mixed by a kneader such as a single-screw or twin-screw extruder, a roll, a Banbury mixer, pelletized or ground, and then subjected to molding. Molding is injection molding, hollow molding,
Any method such as extrusion molding can be employed.

Thus, the composition of the present invention
A thermoplastic resin composition having a good balance of impact resistance, heat resistance, rigidity, moldability and the like can be obtained.

[0046]

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, all parts and percentages are by weight unless otherwise specified.

Example 1 <Production of Modified Ethylene Propylene Copolymer Rubber> A unidirectional twin-screw extruder having a screw diameter of 44 mm and an L / D of 42 was heated to a barrel temperature of 200 ° C.
80 ° C.) and a die temperature of 210 ° C. 0.5 part of Irganox 1010 (stabilizer manufactured by Ciba-Gaiky) in 930 parts of pelletized ethylene propylene copolymer rubber (EP-02P [propylene content 26%, Mooney viscosity 24], manufactured by Nippon Synthetic Rubber Co., Ltd.), phosphite 168 (Stabilizer manufactured by Ciba-Gaiky Co., Ltd.) 0.5 part and calcium stearate (stabilizer) 1 part were mixed. Styrene 50 parts, maleic anhydride 20 parts, perhexin 25B
2.1 parts of (radical initiator manufactured by NOF Corporation) and 1.5 parts of Fine Seal E-50 (finely-divided silica manufactured by Tokuyama Corporation) were added to "stabilizer-containing ethylene propylene copolymer rubber" at 40 ° C using a Henschel mixer. Mix for 20 minutes to absorb and impregnate. The obtained impregnated blend is put into an extruder at 20 kg / h.
The mixture was melted and kneaded at 150 rpm to perform a graft reaction, and 970 parts of product pellets were obtained through a pelletizer. Let the obtained pellet be "A-1."

The styrene and maleic anhydride contents of "A-1" were measured by infrared spectroscopy of the product. The styrene content was 4.7% and the maleic anhydride content was 1.
9%. Extraction using an acetone / tetrahydrofuran mixed solution (8/2 weight ratio) that dissolves only the polymer of styrene and maleic anhydride to determine whether styrene or maleic anhydride has grafted onto the ethylene-propylene copolymer rubber. And the graft ratio was measured, and it was 67%, which was a high ratio.

(Example 2) The same as Example 1 except that in the production of the modified ethylene propylene copolymer rubber of Example 1, 40 parts of styrene and 30 parts of glycidyl methacrylate were used instead of 50 parts of styrene and 20 parts of maleic acid. The mixture was subjected to a melt-kneading graft reaction, and 965 parts of product pellets were obtained through a pelletizer. This is referred to as [A
-2]. The styrene content was 3.7% and the glycidyl methacrylate content was 2.8%. When the graft ratio was measured, it was as high as 64%.

Comparative Example 1 The procedure of Example 1 was repeated, except that only 20 parts of maleic anhydride were used instead of 50 parts of styrene and 20 parts of maleic anhydride in the production of the modified ethylene propylene copolymer rubber of Example 1. A melt-kneading graft reaction was performed, and 920 parts of product pellets were obtained through a pelletizer. Hereinafter, this is referred to as [A-3]. The maleic anhydride content was 0.3% using infrared spectroscopy of the product.
And low rates.

(Example 3) 930 parts of "ethylene propylene copolymer rubber containing stabilizer" used in Example 1 was used under the same temperature conditions as in Example 1 and had a screw diameter of 44.
mm / L / D is 42 and fed at a rate of 18.6 kg per hour to a co-rotating twin-screw extruder by a fixed-quantity feeder.
While melting and kneading at a speed of 20 revolutions, perhexin 25B is supplied from the sixth supply port from the far side from the outlet of the extruder.
A mixed solution of 50 parts of styrene and 20 parts of maleic anhydride mixed with 1% of [Nippon Yushi Co., Ltd.] was melted into ethylene-propylene copolymer rubber at a rate of 1.4 kg per hour by a liquid injection pump. Injected. Melt kneading polymerization of the aromatic vinyl monomer was carried out in the same manner as in Example 1 to obtain 970 parts of product pellets. The obtained pellet is referred to as “A-
4 ". "A-4" had a styrene content of 4.6% and a maleic anhydride content of 1.7%. When the graft ratio was measured, it was slightly low at 37%.

Example 4 200 parts by weight of the graft-modified ethylene propylene copolymer rubber (A-1) obtained in Example 1 and a polyamide resin (6 nylon MC112L,
800 parts by weight (manufactured by Kanebo Co., Ltd.) were blended using a tumbler. Then, the mixture was kneaded at a cylinder temperature of 250 ° C. and pelletized using the twin-screw extruder. Test pieces were prepared from the obtained pellets using a Toshiba IS50AM injection molding machine at a resin temperature of 260 ° C., and physical properties such as bending strength and impact strength were evaluated. Using the same injection molding machine, molten resin was introduced from both upper and lower inflow gates of the impact test die, and a test piece in which the molten resin was joined at the center was prepared to evaluate weld impact strength. Table 2 shows the results. As is clear from Table 2, it is superior to Comparative Example 1 in terms of impact resistance, heat resistance, and rigidity, and it can be seen that the physical properties are well balanced.

Example 5 200 parts by weight of the graft-modified ethylene propylene copolymer rubber (A-2) obtained in Example 2 and a PBT resin (Planac 120, aromatic polyester manufactured by Dainippon Ink and Chemicals, Inc.) Resin) 800
Parts by weight were blended using a tumbler. Then, the mixture was kneaded at a cylinder temperature of 250 ° C. and pelletized using the twin-screw extruder. The obtained pellets are manufactured by Toshiba IS5
Specimens were prepared using a 0AM injection molding machine at a resin temperature of 260 ° C., and physical properties such as bending strength and impact strength were evaluated. or,
Using the same injection molding machine, molten resin was introduced from both upper and lower inflow gates of the impact test piece mold, and a test piece in which the molten resin was joined at the center was prepared, and the weld impact strength was evaluated. Table 2 shows the results. As is clear from Table 2, the impact resistance is higher than that of the aromatic polyester resin, and the physical properties are well balanced.

(Embodiment 6) In Embodiment 4, (A-1)
Instead of using 200 parts by weight and 800 parts by weight of (B-1), 250 parts by weight of (A-2) obtained in Example 2 and a polyphenylene sulfide resin (DICPPS)
MB600, manufactured by Dainippon Ink and Chemicals, Inc.) 750
Using the above-mentioned twin screw extruder, the mixture was kneaded at 290 ° C. and pelletized. The obtained pellets were subjected to a resin temperature of 29 using a Toshiba IS50AM injection molding machine.
A specimen was prepared at 0 ° C., and physical properties were evaluated in the same manner as in Example 4 using the obtained specimen. The results of the physical property measurements are shown in Table 2. As is clear from Table 2, it is understood that the balance of physical properties such as higher impact resistance than PPS resin is good.

(Comparative Example 2) In Example 4, (A-1)
The same operation as in Example 4 except that the same amount of ethylene propylene copolymer rubber in pellet form (EP-02P [propylene content 26%, Mooney viscosity 24], manufactured by Nippon Synthetic Rubber Co., Ltd.) was used instead of using 200 parts by weight. And a test piece was obtained.
Thereafter, the physical properties were evaluated in the same manner as in Example 4. The results of the physical property measurements are shown in Table 2. As is clear from Table 2, it can be seen that it is inferior to Example 4 in terms of impact resistance, heat resistance and rigidity.

Comparative Example 3 In Example 4, (A-1)
A test piece was obtained in the same manner as in Example 4 except that the same amount (A-3) obtained in Comparative Example 1 was used instead of using 200 parts by weight. Thereafter, the physical properties were evaluated in the same manner as in Example 4. The results of the physical property measurements are shown in Table 2. As is evident from Table 2, it is inferior to Example 4 in terms of impact resistance, heat resistance, rigidity and especially moldability.

(Reference Example) For comparison of physical properties, a molded article was manufactured using PBT resin (Pranac 120, manufactured by Dainippon Ink and Chemicals, Inc.) alone, and various physical properties were measured in the same manner as in Example 4. evaluated. As is evident from Table 2, it is inferior to Example 5 in terms of impact resistance.

[0058]

[Table 1]

<< Footnotes in Table 1 >> The units of "the ratio of charged monomers" and "the conversion of the polymer" are "% by weight".

(Note) Physical property evaluation method Delamination: The molded surface was wiped with toluene and the presence or absence of delamination was visually determined. Thermal deformability: Measured JIS K7202 (Load 4.6 kg) Flexural strength: Measured ASTM D790 Flexural modulus, 23
℃ Impact strength: ASTM D256 Notched specimen, 2
3 ° C. Moldability: Measured ASTM D256 Impact value at the weld part of the injection specimen, 23 ° C.

[0061]

[Table 2]

[0062]

The present invention is directed to a modified ethylene-propylene copolymer obtained by a melt-kneading polymerization reaction using an aromatic vinyl monomer and a polar functional group-containing vinyl monomer in combination with a molten ethylene-propylene copolymer rubber. By using a modifier for engineering plastics having a functional group made of rubber, a composition comprising an aromatic polyester resin, a polyamide resin, and an engineering plastic such as PPS having a functional group capable of reacting with the functional group can be used in a composition comprising It is possible to provide an engineering plastic material having high impact strength, weld strength, etc., and an excellent balance between physical properties and moldability.

Claims (8)

[Claims] (1) The ethylene-propylene copolymer rubber (A)
Modification for engineering plastics characterized by comprising a modified ethylene-propylene copolymer rubber obtained by melt-kneading and polymerizing (B) an aromatic vinyl monomer and (C) a vinyl monomer having a polar functional group. Agent. 2. The method according to claim 1, wherein the polar functional group-containing vinyl monomer (C) is
2. The modifier for engineering plastics according to claim 1, wherein the modifier contains a polar functional group selected from a hydroxyl group, a carboxyl group, and an epoxy group. 3. The quantitative ratio of the aromatic vinyl monomer (B) and the polar functional group-containing vinyl monomer (C) is obtained by using (C) in an amount equal to or less than the same molar amount of (B). The modifier for engineering plastics according to claim 1, which is a modified ethylene propylene copolymer rubber. 4. An ethylene-propylene copolymer rubber which is compounded with a radical polymerization initiator under conditions of temperature and time such that decomposition of said radical initiator does not substantially occur.
2. The modification for engineering plastics according to claim 1, wherein the impregnating operation with (A), the aromatic vinyl monomer (B) and the polar functional group-containing vinyl monomer (C) is performed before the melt-kneading polymerization reaction. Quality agent. 5. A modified ethylene propylene copolymer rubber obtained by using a radical polymerization initiator having a half-life decomposition temperature of 180 ° C. or more for one minute as a radical polymerization initiator in combination. Impact modifier for thermoplastic resins. 6. An engineering plastic composition comprising an engineering plastic modifier having a polar functional group according to any one of claims 1 to 5 and an engineering plastic having a functional group capable of reacting with the functional group. . 7. The engineering plastic composition according to claim 6, wherein the polar functional group is a carboxyl group and / or an epoxy group. 8. The engineering plastic composition according to claim 6, wherein the engineering plastic is selected from a polyamide resin, an aromatic polyester resin, and polyphenylene sulfide.