JPH06306177A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To produce the composition being improved in mechanism strengths by reacting an epoxy-modified polyphenylene ether with an olefin resin modified with an alpha, beta-unsaturated carboxylic acid or its derivative in the presence of a catalyst and a good solvent. CONSTITUTION:An epoxy-modified polyphenylene ether (A) such as modified poly(2,6-dimethyl-1,4-phenylene ether) and an olefin resin (B) modified with an alpha, beta-unsaturated carboxylic acid or its derivative such as a modified PP or a mixture thereof with an unmodified olefin resin in amounts corresponding to a weight ratio of 90/10-10-90 are dissolved in 1-100 pts.wt., per 100 pts.wt. total of components A and B, good solvent such as dichlorobenzene. A 0.01-10 pts.wt. catalyst (e.g. benzylmethylamine) which catalyzes the reaction of the epoxy group with the alpha, beta-unsaturated carboxylic acid is added to the above solution to effect a reaction at 100-350 deg.C for 1-180min, and the solvent is removed in a vacuum to obtain the thermoplastic resin composition containing a graft copolymer of good mechanical strengths.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides the heat resistance, mechanical strength and dimensional accuracy of polyphenylene ether (hereinafter referred to as "PPE"), and the moldability and organic solvent resistance of olefin resins. TECHNICAL FIELD The present invention relates to a method for producing a high-performance thermoplastic resin composition having the dual function. The resin composition is an engineering plastic useful as an industrial material for automobile parts such as ignition coils, gears, ignition manifolds, switch sealing materials, electrical parts, mechanical parts and the like.

[0002]

2. Description of the Related Art PPE has excellent heat resistance, dimensional stability,
It is used as an engineering plastic having electrical properties and other properties for electrical components. However, melt flowability and solvent resistance are poor, molding processes such as injection molding are difficult, and the range of use of the molded body is limited. For the purpose of improving these drawbacks, olefin resins represented by polypropylene and polyethylene are blended with PPE because they are excellent in moldability and solvent resistance.

However, the composition of PPE and the olefin resin is brittle and poor in mechanical strength and impact resistance because the polymers of both are essentially incompatible with each other. In order to solve this problem, a composition (JP-A-63-105022) in which PPE modified with an epoxy group and an olefin resin modified with an unsaturated carboxylic acid or a derivative thereof are melt-kneaded is disclosed. There is. However, although the composition obtained by this technique certainly has a significant effect of improving the compatibility between PPE and the olefin resin, it cannot be said to be sufficient to satisfy the high performance. Then, as a result of detailed analysis of this composition, it was found that there is a problem that the production amount of the graft copolymer of PPE and the olefin resin, which contributes most importantly to the improvement of the compatibility, is as small as several%. In practical use, it is desired to increase the yield of graft copolymer production and further improve compatibility and affinity.

[0004]

DISCLOSURE OF THE INVENTION The present invention has a fine structure in which the production yield of a graft copolymer composed of PPE and an olefin resin is increased and the compatibility and affinity between both resins are remarkably improved. In addition, it is an object of the present invention to provide a method for producing a thermoplastic resin composition having excellent mechanical strength, heat resistance, moldability and organic solvent resistance.

[0005]

Means for Solving the Problems As a result of intensive studies to improve the above-mentioned problems of the prior art, the present inventors have found that an epoxy group-modified PPE and a specific modified olefin resin are
The present inventors have found that the resin composition obtained by reacting under specific conditions can achieve the above objects, and have reached the present invention.

That is, according to the present invention, an epoxy group-modified polyphenylene ether (A) and a modified olefin resin (B) modified by introducing an α, β-unsaturated carboxylic acid or a derivative thereof into an epoxy group and an α, Catalyst (C) for promoting reaction with β-unsaturated carboxylic acid or its derivative
Is reacted in the presence of 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B) and a good solvent (D) common to the components (A) and (B). A method for producing a thermoplastic resin composition containing a graft copolymer characterized by the above.

The structure of the present invention will be described in detail below. <Epoxy Group-Modified PPE (A)> The epoxy group-modified PPE used in the present invention is a PPE in which an epoxy group is added to the skeleton of a PPE molecule, and can be produced, for example, by the following method.

(1) PPE PPE used in the production of epoxy group-modified PPE has the general formula (I)

[0009]

[Chemical 1]

(Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and Q ² represents a hydrogen atom. Represents a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and m represents an integer of 10 or more).

A homopolymer or a copolymer thereof having a structure represented by Suitable examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-.
Hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, Q ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q ² is a hydrogen atom.

Suitable homopolymers of PPE are, for example, those composed of 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patents and literature. Also suitable are PPE containing molecular moieties that improve properties such as molecular weight, melt viscosity and / or impact strength. The molecular weight of PPE is usually 0.2-
This corresponds to about 0.8 dl / g. PPE is usually produced by oxidative coupling of the above-mentioned monomers. P
Numerous catalyst systems are known for the oxidative coupling polymerization of PE. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example,
For example, those containing at least one kind of heavy metal compound such as copper, manganese and cobalt, usually in combination with various other substances.

(2) Epoxy group modification The method for producing a modified PPE by introducing an epoxy group into the above PPE is not particularly limited, and for example, it can be produced by the methods shown in the following and.

Terminal epoxy group-modified PPE A PPE in which an epoxy group is added to the terminal phenolic hydroxyl group of PPE by a modifier, for example, JP-A-63-
It is manufactured by the method described in Japanese Patent No. 125525. Specifically, the addition reaction of epicudorhydrin, 2,2-bis (4-glycidylphenylene ether) propane or epoxy resin can be used.

An epoxy group-modified PPE PPE modified with an organic compound having both an ethylenic double bond and an epoxy group in the molecule is an organic compound having both an ethylenic double bond and an epoxy group in the same molecule. An epoxy group-modified PPE obtained by modification, for example, JP-A-63-1280
No. 56 publication. Specifically, glycidyl methacrylate, glycidyl acrylate, monoglycidyl malate, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, etc. are used in the presence or absence of a radical initiator. It can be obtained by denaturation in the presence.

<Modified Olefin Resin (B)> The modified olefin resin used in the present invention is a olefin resin modified by introducing α, β-unsaturated carboxylic acid or its derivative.

(1) Olefin-based resin The olefin-based resin used as the base of the modified olefin-based resin used in the present invention is an α-olefin homopolymer such as ethylene, propylene, butene or hexene, or their α-olefins. And a copolymer of Specific examples of these include low-density polyethylene,
Medium density polyethylene, high density polyethylene, ethylene-
Ethylene resins such as vinyl acetate copolymers; propylene resins; butene-1 resins; 4-methylpentene-1 resins; ethylene-propylene copolymers and the like. Further, as these copolymerization components, dialkenylbenzene compounds such as divinylbenzene, non-conjugated diene compounds such as methyloctadiene, methylhexadiene, 1,9-decadiene and 1,13-tetradecadiene, norbornene,
Tetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] -3-Dodecene and other olefin resins containing a polyunsaturated compound such as a cyclic olefin as a copolymerization component.

(2) α, β-Unsaturated Carboxylic Acid or Derivatives Thereof (i) Type Specific examples of α, β-unsaturated carboxylic acids or derivatives thereof used for modifying an olefin resin include acrylic acid, Methacrylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, mesaconic acid, sorbic acid or their esters, acid anhydrides, metal salts, amides, imides, etc. Acids, methacrylic acid, and maleic anhydride are preferable, and two or more of these can be used in combination.

(Ii) Amount of α, β-unsaturated carboxylic acid or derivative thereof The amount of α, β-unsaturated carboxylic acid or derivative thereof used is 0.1 to 3 with respect to 100 parts by weight of the olefin resin.
The amount is 00 parts by weight, preferably 1 to 200 parts by weight. α,
If the amount of β-unsaturated carboxylic acid or its derivative is less than 0.1 parts by weight, there is almost no effect of improving the compatibility of the resin composition, and if it exceeds 300 parts by weight, the mechanical properties of the resin composition are difficult to be exhibited.

(Iii) Modification of Olefin Resin by α, β-Unsaturated Carboxylic Acid or its Derivative The modified olefin resin used in the present invention contains α, β-unsaturated carboxylic acid or its derivative in the olefin resin. It is produced by radical graft polymerization by a conventionally known method. For example, in the presence of the olefin resin and the monomer, γ
Ray, a method of irradiating radiation such as an electron beam, a method of irradiating an olefin resin with radiation and then allowing the monomer to coexist,
Any method such as coexistence of the olefin resin and the monomer in a solution state, a molten state or a dispersed state, and graft polymerization in the presence or absence of a radical polymerization catalyst can be employed in the present invention. Examples of radical polymerization catalysts include benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, t-butyl hydroperoxide, t-butyl peroxyacetate, diisopropyl peroxydicarbonate, 2,2-bis ( Organic peroxides such as t-butylperoxy) octane and methyl ethyl ketone peroxide; inorganic peroxides such as potassium persulfide; azo compounds such as α, α′-azobisisobutyronitrile; or hydrogen peroxide Examples thereof include redox catalysts such as ferrous salts. These radical polymerization catalysts are appropriately selected in relation to the polymerization method,
One kind or two or more kinds may be used in combination. The temperature of the radical graft polymerization reaction is usually 30 to 350 ° C., preferably 50 to 300 ° C., and the polymerization time is 30 seconds to
It is in the range of 50 hours, preferably 1 minute to 24 hours. The amount of the radical polymerization catalyst used is 0 to 1 with respect to 100 parts by weight of the α, β-unsaturated carboxylic acid or its derivative.
It is appropriately selected from the range of 00 parts by weight, preferably 0 to 30 parts by weight.

<Catalyst (C)> As a catalyst for promoting the reaction between the epoxy group in the modified PPE (A) and the α, β-unsaturated carboxylic acid or derivative thereof in the modified olefin resin (B). The catalyst used in the curing reaction of the epoxy resin can be used. In particular,

Tertiary amines such as benzyldimethylamine, tributylamine, tris (dimethylamino) methylphenol, 4- (dimethylamino) pyridine, triphenylamine and the like;

Quaternary ammonium compounds, eg,
Tetra-n-butylammonium fluoride, tetraethylammonium fluoride, alkyl (having 8 to 1 carbon atoms
8) dimethylbenzylammonium chloride, benzyltri-n-butylammonium bromide, phenyltrimethylammonium iodide and the like;

Phosphonium compounds such as allyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, methyltriphenylphosphonium iodide;

Pyridinium compounds such as 1-acetonylpyridinium chloride, 4-bromopyridine hydrochloride, 1-ethyl-4-methoxycarbonylpyridinium iodide, 2,4,6-trimethylpyridinium-p-toluenesulfonate and the like;

Imidazoles such as imidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-aminoethyl-
2-methylimidazole and the like;

Examples of phosphines include triphenylphosphine, tricyclophosphine, tributylphosphine, allyldiphenylphosphine and the like.

<Solvent (D)> The production of the resin composition of the present invention requires addition of a solvent. The solvent to be added is common to the modified PPE (A) and the modified olefin resin (B). It is a good solvent. Specific examples thereof include aromatic hydrocarbons such as toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene.

<Thermoplastic Resin Composition> (1) Blending Ratio In the thermoplastic resin composition produced by the present invention, the blending ratio of the component (A) and the component (B) is determined by the required performance of the molded product. . Properties such as moldability, mechanical strength, solvent resistance, dimensional accuracy, and high temperature rigidity can often be adjusted by the characteristics of each component and its blending ratio. In many cases, the conflicting properties of the expression mechanism are difficult to achieve at the same time. For practical purposes, it is usually carried out from the viewpoint of appropriate harmonization of various properties such as moldability, mechanical strength and high temperature rigidity.

The modified PPE (A) and the modified olefin resin (B) in the present invention are well mixed in any proportion, but when PPE is the main component, molding processability and appearance are improved. When the olefin resin is the main component, the heat resistance and dimensional accuracy of the olefin resin are improved. The modified PPE (A) and the modified olefin-based resin (B) are blended in a ratio of 90:10 to 10:90 by weight, preferably 70.
The range is 30 to 30 to 70. The component (A) used in the present invention may be a single compound or a mixture of modified PPE and unmodified PPE.

The component (B) used in the present invention may be a mixture of a modified olefin resin and an unmodified olefin resin. The mixing ratio of the modified PPE and the unmodified PPE or the modified olefin resin and the unmodified olefin resin can be set arbitrarily. Usually, the mixing ratio of modified PPE and unmodified PPE or modified olefin resin and unmodified olefin resin is 100: 0 to 20:80.
A weight% range is preferred. When the mixing ratio of the modified PPE or the modified olefin resin is less than 20% by weight, the effect of improving the compatibility becomes small, which is not preferable.

(2) Additional component The thermoplastic resin composition of the present invention may contain other additional components. That is, various elastomer components can be blended for the purpose of improving impact resistance. In this case, the addition amount of the elastomer component is preferably 0 to 40 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). When the amount of the elastomer component exceeds 40 parts by weight, the high temperature elastic modulus of the composition is lowered and the characteristics of the PPE composition are lost. Specific examples of the elastomer include olefin elastomers such as ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, and ethylene-butene copolymer; polybutadiene, polyisoprene,
Diene elastomer such as natural rubber; styrene-butadiene rubber, styrene-butadiene block copolymer,
70% of diene copolymer elastomer such as styrene-isoprene block copolymer or its diene component
The hydrogenated diene-based copolymer elastomers hydrogenated as described above can be mentioned.

These elastomer components can be modified by known methods such as acid modification, hydroxy modification and epoxy modification in order to improve the affinity with the constituents. In addition, an antioxidant, a weather resistance improver, a nucleating agent, a flame retardant, a slip agent, a plasticizer, a styrene resin, a fluidity improver, a release agent, a pigment, a dispersant, etc. in a resin composition of 20% by weight. It can be blended at a ratio of less than%. Furthermore, organic and inorganic fillers, for example, glass fiber, mica, talc, wollastonite, potassium titanate, silica and the like 50% by weight or less,
Alternatively, the colorant dispersant may be contained in an amount of 5% by weight or less.

<Method for Producing Thermoplastic Resin Composition> (1) Reaction Device The reaction device used in the present invention is a so-called high-viscosity reaction device or high-viscosity mixing device, and specifically, a single-screw or biaxial kneading device. Examples thereof include an extruder such as an extruder, a horizontal twin-screw agitator such as a horizontal twin-screw multi-disk device and a horizontal twin-screw surface renewer, and a vertical agitator such as a double helical ribbon agitator. When the reaction is performed using these reactors, the inside of the reactor may be in an open state with the outside, but the components in the reaction vessel are isolated from the outside during the reaction, and It is preferable that the reaction container is kept in a so-called hermetically sealed state in which oxygen does not enter from the outside of the container during the reaction.

(2) Production Method In the thermoplastic resin composition of the present invention, the modified PPE (A) having the epoxy group bonded thereto and the modified olefin resin (B) are present in the presence of the catalyst (C). It can be produced by adding a common good solvent (D) to the modified PPE and the modified olefin resin under the following conditions and reacting them in the reactor. The amount of solvent (D) added to the reaction is
Total amount of PE (A) and modified olefin resin (B) 10
1 to 100 parts by weight, preferably 5 to 7 parts by weight, relative to 0 parts by weight
0 parts by weight. If the amount is less than 1 part by weight, the amount of the graft copolymer formed is decreased, which is not preferable. From the relationship between the boiling point of the solvent used and the vapor pressure, if the amount exceeds 100 parts by weight, it is difficult to maintain the upper limit of the reaction temperature, 350 ° C. Become. In the reactor, the melt viscosity is usually about 5 × 10 ³ to 10 × 10 ⁴ P, preferably about 1 × 10 ⁴ to 10 × 10 ⁴ P.

The amount of catalyst (C) added to the reaction depends on the amount of modified P
Total amount of PE (A) and modified olefin resin (B) 10
It is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 0 parts by weight. If it is less than 0.01 parts by weight, the amount of the graft copolymer produced is reduced, and if it exceeds 10 parts by weight, the amount of the crosslinking component produced is increased, which is not preferable. The reaction temperature is 100 to 350 ° C, preferably 160 to 280.
It is in the range of ° C. The time required for the reaction is 1 to 180 minutes, preferably 5 to 120 minutes, particularly preferably 5 to 60 minutes. If it is less than 1 minute, the amount of graft copolymer produced is small,
If it exceeds 180 minutes, the amount of the cross-linking component produced increases, which is not preferable. The progress of the reaction can be confirmed by the infrared absorption spectrum or the like of the reaction rate of the modified PPE from the residual substance by selectively extracting and removing the unreacted modified PPE from the product with a good solvent for PPE.

After completion of these reactions, the inside of the reaction vessel can be decompressed by a decompression device such as a vacuum pump to remove the component (D).

[0038]

Although not restricted by any theoretical basis, the excellent effect of the present invention can be explained by the following reaction scheme. That is, in the system in which the epoxy group-modified PPE (A) and the α, β-unsaturated carboxylic acid-modified olefin resin (B) react, the PPE and the olefin resin are essentially incompatible, and therefore,
It is considered that the reaction rate is largely controlled by the existence of the interface between the two resins. The presence of (D), which is a good solvent for both resins, eliminates the interface or forms a partially compatible state, and further, the reaction between the functional groups is promoted by the catalyst present in the system.

[0039]

The present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited thereby.

Reference Example 1 Production of Modified PPE (1) 5 liters of epichlorohydrin was placed in a glass flask equipped with a stirrer and having an internal volume of 10 liters, which had been sufficiently purged with nitrogen, and then poly (2,6-dimethyl-1, 4-phenylene ether) (Nippon Polyether, intrinsic viscosity measured in chloroform at 30 ° C .: 0.3 dl / g)
350 g was added. Next, while heating and heating and stirring, 1
After keeping the polymer at 00 ° C. for about 30 minutes to completely dissolve the polymer, a solution of 70 g of sodium ethoxide in 300 ml of ethanol was added dropwise over 30 minutes,
The mixture was further reacted at 100 ° C. for 4 hours under a nitrogen atmosphere.
The reaction mixture was poured into 10 liters of methanol and after stirring, the epoxy group-modified PPE of the product was deposited. This was separated by filtration, washed once more with the same amount of methanol and filtered. The product obtained was poured into 10 liters of water, stirred and then precipitated. This was filtered off and washed once more with the same amount of water. Finally, it was poured again into 10 liters of methanol, washed with stirring, separated, and dried under reduced pressure at 80 ° C. As a result of analyzing the epoxy group-modified PPE by ultraviolet absorption spectrum, it was found that 98% of the terminal phenolic hydroxyl groups were reacted. The modified resin thus obtained is referred to as modified PPE (1).

Reference Example 2: Preparation of modified PPE (2) Poly (2,6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., Ltd., intrinsic viscosity measured in chloroform at 30 ° C .: 0.3 dl / g) 100 parts by weight of N- [4- (2,3-epoxypropoxy) -3,5
6 parts by weight of dimethylbenzyl] acrylamide was added and dry blended, and melt-kneaded with a 30 mm diameter twin-screw extruder (manufactured by Japan Steel Works, trade name: TEX-30) set at 260 ° C. to form a strand. Pelletized. Part of the obtained pellets was dissolved in toluene, poured into methanol to cause precipitation, and filtered and dried. The graft ratio of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide was measured by a nuclear magnetic resonance analyzer (NM
As a result of analysis by R), it was 1.2% by weight. The modified resin thus obtained is referred to as modified PPE (2).

Reference Example 3: Production of Modified Olefin Resin (1) Homopolymer powder of propylene resin (ASTM D12
In accordance with No. 38, melt flow rate (MFR) measured at 230 ° C. (1 g / 10 minutes) 2500 g was added with maleic anhydride 125 g and t-butyl cumyl peroxide 12.5 g and blended, and nitrogen was sufficiently added beforehand. In the closed closed reaction vessel, the reaction temperature was 240 ° C and the rotor speed was 2
After kneading at 0 rpm for 5 minutes, rotate the rotor at 40 rpm.
Then, the mixture was kneaded for another 30 minutes to continue the reaction. As the reaction device, a horizontal twin-screw kneading device (manufactured by Sumitomo Heavy Industries, Ltd.) having an internal volume of 8 liters was used in a sealed state. After completion of the reaction, a vacuum pump attached to this apparatus was used to dry under reduced pressure at a temperature of 240 ° C. and a rotor rotation speed of 80 rpm to remove unreacted monomers, and then the modified olefin resin (1) was taken out.
The amount of added maleic anhydride in the modified olefin resin (1) was 1.1% by weight as a result of using a calibration curve prepared from the absorbance of the carboxyl group of the infrared absorption spectrum.
As a result of gel permeation chromatography, the molecular weight was 43,700 in terms of polystyrene equivalent number average molecular weight.

Example 1 1400 g of homopolymer powder of propylene resin, 70 g of maleic anhydride and 7 g of t-butylcumyl peroxide
A modified olefin resin was obtained in the same manner as in Reference Example 3 except that was used. 1 as a sample from the obtained resin
00 g was taken out, 1300 g of the modified PPE obtained in Production Example 2 and 552 g of 1,2,4-trichlorobenzene were added to the rest of the resin, and the mixture was stirred for 5 minutes in a sealed state, and then 13 g of dimethylaminopyridine and 1,2,2,2. A solution of 72 g of 4-trichlorobenzene was added, and the rotor speed was 80 rp.
The reaction was carried out at an internal temperature of 240 ° C. for 60 minutes. After completion of the reaction, a vacuum pump attached to this apparatus was used to dry under reduced pressure at a temperature of 240 ° C. and a rotor rotation speed of 40 rpm to remove 1,2,4-trichlorobenzene, and then the resin composition was taken out.
The amount of maleic anhydride added to the modified olefin resin taken out earlier was 1.24% by weight as determined by the same method as in Reference Example 3, and the number average molecular weight was 3
It was 0,300. A part of the obtained resin composition was taken out and analyzed and evaluated as follows. The results are shown in Table 1.

[0044]

[Table 1]

Graft Copolymer Production Yield The resin composition was dissolved in a large amount of xylene, stirred at 120 ° C., precipitated with methanol and separated by filtration, and the obtained polymer was vacuum dried and subjected to analysis. The production yield of the graft copolymer was obtained from the following formula. U (wt%) = 100− (V + W) U: Graft copolymer production yield (wt%) in 100 g of the resin composition V: Weight (g) of unreacted modified PPE in 100 g of the resin composition (above) The dried polymer was subjected to Soxhlet extraction with chloroform under refluxing for 8 hours to remove unreacted modified PPE, and the difference between the weight charged during extraction and the weight of the remaining extract was determined and converted to 100 g).

W: Weight (g) of unreacted modified olefinic resin in the resin composition 100 (Soxhlet extraction of the above dried polymer with octane under boiling point reflux for 8 hours was performed to remove unreacted modified olefinic resin. Excluding the difference, the difference between the weight charged at the time of extraction and the weight of the remaining extract was calculated and converted to 100 g)

Dispersion form In order to examine the dispersion state between both resins, a scanning electron microscope (manufactured by Hitachi Ltd., trade name: S-2400 type) was used.
The cross section of the composition was observed.

Impact resistance strength Impact resistance strength is 31.5 mm in length, 6.2 mm in width, and 3.
A 2 mm test piece was injection molded, and an Izod impact tester (Mini Scientific CS manufactured by Custom Scientific) was used.
(-138TI type), Izod impact strength without notch at 23 ° C. was measured.

Example 2 A modified olefin resin was produced in the same manner as in Example 1, and 100 g of a sample was taken out from the obtained modified olefin resin. Subsequently, the modified PPE obtained in Reference Example 2
(2) 1300 g and 1,266 g of 1,2,4-trichlorobenzene were charged, and after stirring for 5 minutes in a sealed state, a solution of 13 g of dimethylaminopyridine and 72 g of 1,2,4-trichlorobenzene was added, and the rotation speed of the rotor was changed. 80rp
The reaction was carried out at m 2 and a temperature of 205 ° C. for 60 minutes. After completion of the reaction, a vacuum pump attached to this apparatus was used to dry under reduced pressure at a temperature of 240 ° C. and a rotor rotation speed of 40 rpm to remove 1,2,4-trichlorobenzene, and then the resin composition was taken out.
The amount of added maleic anhydride in the modified olefin resin taken out earlier was 0.90% by weight as determined by the same method as in Reference Example 1, and the number average molecular weight was 3
It was 7,500. Part of the obtained resin composition and Example 1 were subjected to the same analysis and evaluation. The results are shown in Table 1.

Comparative Example 1 A modified olefin resin was produced in the same manner as in Example 1, and 100 g of a sample was taken out from the obtained modified olefin resin. Subsequently, the modified PPE obtained in Reference Example 2
(2) After adding 1300 g and stirring for 5 minutes in an open state, the mixture was reacted for 60 minutes at a rotor rotation speed of 80 rpm and a temperature of 205 ° C., and then the resin composition was taken out. The amount of maleic anhydride added to the modified olefin resin taken out earlier was 0.91% by weight as determined by the same method as in Production Example 1, and the number average molecular weight was 37,600. Met. One part of the obtained resin composition was subjected to the same analysis and evaluation as in Example 1. The results are shown in Table 1.

Example 3 A cylinder hopper (VHCN type, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was attached to a plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd., model 20C200 type) having an internal volume of 60 ml, and nitrogen replacement was carried out sufficiently. Modified PPE (1) 9.2 obtained in
g, modified olefin resin (1) 3 obtained in Reference Example 3
6.8 g, 1,2,4-trichlorobenzene 9.2 g and dimethylaminopyridine 0.23 g were charged, and after kneading in a closed state at a kneading temperature of 240 ° C. and a rotor rotation speed of 30 rpm for 1 minute, the rotor rotation speed was 180 rpm. And kneaded for another 10 minutes. After completion of the reaction, a vacuum pump was used to dry under reduced pressure at a temperature of 240 ° C. and a rotor rotation speed of 180 rpm to remove 1,2,4-trichlorobenzene, and then the resin composition was taken out. 1 of the obtained resin composition
Parts were subjected to the same analysis and evaluation as in Example 1. The results are shown in Table 1.

Example 4 Kneading and evaluation were carried out in the same manner as in Example 3 except that 23 g of modified PPE (1) and 23 g of modified olefin resin (1) were used in Example 3. The results are shown in Table 1.

Example 5 Kneading and evaluation were carried out in the same manner as in Example 3 except that 36.8 g of modified PPE (1) and 9.2 g of modified olefin resin (1) were used in Example 3. . The results are shown in Table 1.

Example 6 The same as Example 3 except that 23 g of modified PPE (1), 23 g of modified olefin resin (1) and 2.3 g of 1,2,4-trichlorobenzene were used in Example 3. Then, kneading and evaluation were performed. The results are shown in Table 1.

Example 7 Kneading and evaluation were carried out in the same manner as in Example 3 except that 23 g of modified PPE (1), 23 g of modified olefin resin (1) and dichlorobenzene were used. . The results are shown in Table 1.

Comparative Example 2 Modified PPE without installing a cylinder hopper (Toyo Seiki Seisakusho Co., Ltd., VHCN type) to a plastomill (Toyo Seiki Seisakusho Co., Ltd. model 20C200 type) having an internal volume of 60 ml.
(1) 9.2 g and modified olefin resin (1) 36.
After 8 g was charged and kneaded at a kneading temperature of 240 ° C. and a rotor rotation speed of 30 rpm for 1 minute in an open state, the rotor rotation speed was increased to 180 rpm and kneading was continued for 10 minutes. After the reaction was completed, the resin composition was taken out. 1 of the obtained resin composition
Parts were subjected to the same analysis and evaluation as in Example 1. The results are shown in Table 1.

Comparative Example 3 Kneading and evaluation were carried out in the same manner as in Comparative Example 2 except that 23 g of modified PPE (1) and 23 g of modified olefin resin (1) were used in Comparative Example 2. The results are shown in Table 1.

[0058]

As is clear from the results of the above embodiments,
The thermoplastic resin composition produced in the present invention has an extremely high reaction yield of the graft copolymer, and thus the compatibility between the two resins,
The affinity is remarkably improved, and it has excellent mechanical strength.

Claims (1)

[Claims] 1. An epoxy group-modified polyphenylene ether (A) and a modified olefin resin (B) modified by introducing an α, β-unsaturated carboxylic acid or derivative thereof,
0.01 to 10 parts by weight of a catalyst (C) that accelerates the reaction between an epoxy group and an α, β-unsaturated carboxylic acid or a derivative thereof is added to 100 parts by weight of the total amount of the components (A) and (B). A method for producing a thermoplastic resin composition containing a graft copolymer, which comprises reacting in the presence of a good solvent (D) common to both component (A) and component (B).