JPH0539395A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition which is excellent in moldability and gives a molding excellent in impact resistance, rigidity, etc., by mixing a polyhydroxyphenylene ether of a specified composition and an acid-modified olefin copolymer at a specified weight ratio. CONSTITUTION:A polyhydroxyphenylene ether is prepared which consists of p X structural units of formula I (wherein (m) is 1 to 4, and (n) is 0 to 3, provided that (m+n)<=4; J is of formula II; (a) is 1 to 6; R<1> is a 1-20C polyvalent hydrocarbon group; R<2> is 2-20C alkylene; (k) is halogen, 1-20C alkyl, etc.) and q X structural units of formula III (wherein Q<1>, Q<2>, Q<3>, and Q<4> are each H, halogen, 1-20C alkyl, etc.), wherein (p) and (q) satisfy relation IV, and which has a number-average degree of polymerization of 25 to 400. Separately, a 2-8C alpha-olefin is copolymerized with a chain nonconjugated diene, and the obtained copolymer is grafted with an unsaturated carboxylic acid (derivative). 90-10wt.% acid-modified olefin compolymer thus obtained is mixed with 10-90wt.% of the polyhydroxyphenylene ether to give the objective composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition comprising polypolyhydroxyphenylene ether and an acid-modified olefin copolymer, which is excellent in moldability and appearance of molded articles, and has solvent resistance, The present invention relates to a thermoplastic resin composition that gives an industrial material excellent in heat resistance rigidity.

[0002]

2. Description of the Related Art Polyphenylene ether (hereinafter referred to as PPE
Is known as an engineering plastic having excellent heat resistance, dimensional stability, non-hygroscopicity and electrical characteristics, but the melt flowability during injection molding or extrusion molding is poor and molding processing is difficult, In addition, the molded product has the drawback of being poor in solvent resistance and impact resistance. As a method for improving such a defect, there is a method for improving molding processability by mixing another resin, for example, styrene resin or high impact styrene resin (HIPS), in US Pat. No. 3,383,43.
The solvent resistance of the composition obtained as disclosed in, for example, Japanese Patent No. 5 has not been improved yet.

On the other hand, various mixed compositions with an olefin resin having excellent solvent resistance have been investigated. Japanese Patent Publication 42-
No. 7069 proposes a composition comprising an olefin resin and PPE, but its mechanical strength does not satisfy the level required in the field of industrial materials due to insufficient compatibility. JP-A-53-71158, JP-A-54-889
No. 60 and No. 59-100159, it is proposed to blend, for example, a styrene-butadiene block copolymer or a hydride thereof for the purpose of improving the compatibility of PPE with an olefin resin. Since the compounding amount of is limited to a small amount, the solvent resistance of the olefin resin is not sufficiently exhibited.

In addition, JP-A-58-103557 and JP-A-6-103557.
Japanese Patent Laid-Open No. 0-76547 discloses a composition in which a large amount of an olefin resin is blended to improve tensile properties and brittleness properties, but the rigidity and heat resistance are not at satisfactory levels.

As a method of modifying PPE, a method of introducing various functional groups using a phenolic hydroxyl group at the terminal as a reaction point is known. JP-A-63-199754 and JP-A-62-500456 disclose maleic anhydride-modified PPE, and U.S. Pat. No. 4,744,708 discloses terminal alcoholic hydroxyl-modified PPE. Is the reaction point, the concentration of the functional group is P
The number of PE molecules per PE molecule is at most one, and the degree of modification is insufficient for a wide range of applications.

For the purpose of introducing a functional group such as carboxylic acid into an olefin resin having poor reactivity, a method of graft-modifying propylene resin with maleic anhydride or the like under radical reaction conditions to obtain an acid-modified propylene resin is widely used. It is known (for example, Japanese Patent Publication No. 45-30945, Polymer Chemistry, Volume 29, page 265 (1972), Japanese Patent Publication Nos. 57-59216 and 57-105448).

However, in general, the radical graft modification method does not have a sufficiently high graft ratio or graft efficiency.
When an attempt is made to improve the degree of modification by using an ordinary olefin resin, there is a problem that undesired reactions such as molecular cutting and crosslinking of the trunk polymer to be grafted are likely to occur, and a highly modified product may be obtained. It was difficult.

In order to improve the compatibility of a composition comprising PPE and an olefin resin, it has been attempted to blend both components each modified with a functional group which can be expected to react with each other (for example, JP-A-63). -105022 and JP-A-63-128056). Compositions having improved compatibility by mixing a modified PPE having an alcoholic hydroxyl group added at the terminal with a maleic anhydride graft modified olefin resin are disclosed in JP-A-63-128021 and 63-130660. It is disclosed.

[0009] However, although the above-mentioned method is recognized to have some effect of improving the compatibility, it has not reached a practically satisfactory level.

[0010]

If a composition having both good properties of PPE and an olefin resin and complementing the undesired properties can be obtained, it becomes possible to provide an excellent resin material having a wide range of fields of application, and its industrial use. The meaning can be said to be very large. In order to provide a molding material that complements the drawbacks while maintaining the advantages of both, the affinity for the two-phase structure interface formed by the two components, which are essentially poor in compatibility, is increased and the adhesion is improved. It is desired to have an excellent affinity improving technique by which the two phases are made into a uniform and fine mixed form to suppress delamination which is likely to occur when shear stress is applied during molding such as injection molding. There is.

The present invention provides a thermoplastic resin composition comprising PPE and an olefin resin, the affinity of which is greatly improved, and the composition is in a state of uniform fine dispersion and is excellent in rigidity and impact strength. The purpose is to

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that chemically
It was discovered that PPE, which has an arbitrary number of alcoholic hydroxyl groups in the side chain, which does not usually have extremely high activity, that is, polyhydroxyphenylene ether, and a specific acid-modified olefin resin exhibit extremely good affinity, Was completed.

That is, the present invention is a thermoplastic resin composition comprising the following components (A) and (B). (A) Polyhydroxy having a number of structural units represented by the following general formula (I) and q structural units represented by the following general formula (II) and having a number average degree of polymerization of 25 to 400. Phenylene ether 10 to 90% by weight Here, p and q satisfy the following formula. 0.2 ≦ 100p / (p + q) ≦ 100

[0014]

[Chemical 3]

[In the formula, m represents an integer of 1 to 4 and n represents an integer of 0 to 3, and m + n≤4. J is (HO) _a -R
¹ -S-R ² - (wherein, a represents an integer of 1 to 6, R
¹ represents an aliphatic polyvalent hydrocarbon group having 1 to 20 carbon atoms, which may be interrupted by an oxygen atom, which may be substituted or unsubstituted by a halogen atom, or an aromatic polyvalent hydrocarbon group, R ² Represents an alkylene group having 2 to 20 carbon atoms), and when m is 2 or more, J may be different from each other. K is a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms,
A phenyl group, an aminoalkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms or a halohydrocarbon oxy group, and when n is 2 or more, K May be different]

[0016]

[Chemical 4]

(Wherein Q ¹ , Q ² , Q ³ and Q ⁴ are each a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1 to 20 carbon atoms). , A phenyl group, an aminoalkyl group having 1 to 20 carbon atoms,
Representing a haloalkyl group having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms or a halohydrocarbonoxy group) (B) at least one α-olefin having 2 to 8 carbon atoms and a chain non-conjugated 90 to 10% by weight of an acid-modified olefin copolymer modified by graft-reacting an unsaturated carboxylic acid or a derivative thereof with a crystalline olefin copolymer copolymerized with at least one diene

The present invention will be described in detail below. <Polyhydroxyphenylene ether (A)> The polyhydroxyphenylene ether (A) used in the present invention is one of phenol derivatives having a hydroxyl group represented by the general formula (III).
1 to 2 or more of 0.2 to 100 mol% and 9 to 1 or 2 or more of phenol derivatives represented by the general formula (IV)
It is a resin having a skeleton of PPE obtained by copolymerization with 9.8 to 0 mol%.

[0019]

[Chemical 5]

(Where m, n, J and K are the same as above)

[0021]

[Chemical 6]

(Wherein Q ¹ , Q ² , Q ³ and Q ⁴ are the same as above)

Specific preferred examples of the phenol derivative (III) having a hydroxyl group include 2- [3- (2-hydroxyethylthio) propyl] -6-methylphenol and 2-
[3- (2,3-dihydroxypropylthio) propyl] -6-methylphenol and the like can be mentioned. Also,
Specific preferred examples of the phenol derivative represented by the formula (IV) include 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-allyl-6-methylphenol and the like, or a mixture thereof.

Further, the production of the polymer can be carried out in the same manner as the usual oxidative polymerization of PPE. For example, US Pat.
No. 22062, No. 3306874, No. 33068
No. 75, No. 3257257 or No. 3257358.
No. The catalyst used for the oxidative polymerization is not particularly limited, but any catalyst capable of obtaining a desired degree of polymerization may be used. Many catalyst systems are known in the art consisting of cuprous salts-amines, cupric salts-amines-alkali metal hydroxides, manganese salts-primary amines and the like. The polyhydroxyphenylene ether (A) may be a homopolymer, a random copolymer or a block copolymer. The degree of polymerization is 25 to 400. If it is less than 25, the mechanical properties of the composition are not good, and if it exceeds 400, it is not easy to handle.

Of these, 2- [3- (2-hydroxyethylthio) propyl] -in formula (III) is preferred.
Using 6-methylphenol in the general formula (IV) 2,
In the case of using 6-dimethylphenol, the ratio of the former is preferably 0.5 to 50 mol%, more preferably 1 to 4
0 mol% is more preferable. The number average molecular weight is 3,
000 to 50,000 is preferable, and 5,000 to
30,000 is more preferable. This polymer consists of the number x of structural units of the formula (V) and the number y of structural units of the formula (VI), and x and y satisfy the following equation.

0.5 ≦ 100x / (x + y) ≦ 50,

[0027]

[Chemical 7]

[0028]

[Chemical 8]

<Acid-modified olefin copolymer (B)> The acid-modified olefin copolymer (B) used in the present invention has the following structure. In the acid modification, the crystalline olefin copolymer to be used is at least one α-olefin having 2 to 8 carbon atoms and the general formula (VI) CH ₂ ═CH-(— CR ⁵ R ⁴ —) _n —C ( R ³ ) = C (R ² ) -R ¹ (VI) (In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms;
² , R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10) with at least one kind of chain non-conjugated diene , A copolymer having a diene content of 0.
1 to 30 mol%, preferably 0.5 to 15 mol%.

The copolymer has crystallinity, and the crystallinity at room temperature measured by X-ray diffraction is preferably 10% or more, more preferably 20% or more, and 40 ° C.
It has the above melting point. The decrease in crystallinity results in a decrease in the elastic modulus of the final composition. Also, this copolymer should have a molecular weight sufficient to maintain mechanical strength at room temperature. For example, when propylene is the main component,
The melt flow rate (MFR) measured according to JIS K6758 has a molecular weight corresponding to 0.01 to 500 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes, and measured according to JIS K7203. Elasticity is 5
It is desirable that it is 00 kg / cm ² or more.

Examples of the above α-olefin which is a constituent of the copolymer include ethylene, propylene and butene-
1, pentene-1, hexene-1, 3-methylbutene-
1,4-methylpentene-1,3,3-dimethylpentene-1,3-methylhexene-1,4-methylhexene-1,4,4-dimethylhexene-1,5-methylhexene-1, allylcyclo Pentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1,
Vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo- [2.2.1] -heptane, heptene-
1 or octene-1. Of these, preferred examples include ethylene, propylene, butene-
1, pentene-1, hexene-1, 3-methylbutene-
1,4-methylpentene-1,3-methylhexene-1
Can be mentioned. In particular, ethylene, propylene, butene-1,3-methylbutene-1,4-methylpentene-1 is more preferable.

One or more of these α-olefins can be used as a copolymer component. Formula (VI)
The chain-like non-conjugated diene represented by is preferably n is 5 or less, R ⁴ and R ⁵ are hydrogen atoms, and R ¹ , R ²
And R ³ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and are not all hydrogen atoms.

Specific examples of preferred diene compounds include 1,4-dienes such as 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; 1,5-heptadiene and 1,5-octadiene. 1, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene and the like 1,
5-dienes; 1,6-octadiene, 6-methyl-
1,6-octadiene, 7-methyl-1,6-octadiene, 2-methyl-1,6-octadiene, 6-methylidene-1-octene, 6-ethyl-1,6-octadiene, 7-dimethyl-1, 1,6-dienes such as 6-octadiene and 1,6-nanodiene; 1,7-nonadiene,
7-methyl-1,7-nonadiene, 8-methyl-1,7
-1,7-dienes such as nonadiene; 8-methyl-1,
Examples include 1,8-dienes such as 8-decadiene and 9-methyl-1,8-decadiene.

A particularly preferred example is 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene, 5
-Methyl-1,5-heptadiene, 6-methyl-1,5
-Heptadiene, 6-methyl-1,6-octadiene,
It is 7-methyl-1,6-octadiene. These dienes may be used alone or in combination of two or more.

The crystalline olefin copolymer to be modified according to the present invention is the same as in the production of an α-olefin polymer using the above α-olefin and a chain non-conjugated diene by using a Ziegler-Natta catalyst for α-olefin polymerization. Can be manufactured by using the method and apparatus.

Specific examples of such a production method are disclosed in JP-A-55-165907, JP-A-56-30414 and JP-A-56.
-36508 and 57-155206 can be mentioned. These chain non-conjugated dienes are
It may be randomly distributed in the copolymer, or may be distributed in blocks. The content of the non-conjugated diene is preferably 0.1 to 30 mol%, more preferably 0.5 to 15 mol%. When the diene content is less than 0.1 mol%, a high degree of modification cannot be obtained in the acid modification reaction. If the diene content exceeds 30 mol%, the reaction rate will decrease during the production of the copolymer, and the production of low crystallinity sub-polymers will increase, leading to production problems such as a decrease in productivity, and the acid content. Even when it is subjected to a modification reaction, side reactions such as crosslinking and molecular cleavage of the copolymer itself are likely to occur and the performance of the final product is deteriorated.

The acid-modified olefin copolymer used in the present invention is obtained by radically graft-polymerizing an unsaturated carboxylic acid or its derivative with the above crystalline olefin copolymer.

The unsaturated carboxylic acid or its derivative used as a modifier is an unsaturated carboxylic acid such as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, or the like. Derivatives such as acid halides, amides, imides, anhydrides, esters and the like can be mentioned. In particular,
Malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like are exemplified. Among these, anhydrides are preferable, and maleic anhydride is particularly preferable. Two or more of these carboxylic acids or their derivatives can be used in combination.

In the present invention, the radical reaction conditions for producing the acid-modified olefin copolymer are as follows: a method of irradiating with radiation such as γ-ray or electron beam in the coexistence of the crystalline olefin copolymer and the modifier. Any method such as irradiating the crystalline olefin copolymer with radiation and then coexisting with the modified preparation, coexisting with the crystalline olefin copolymer and the modifier, and heating in the presence or absence of the radical generator. Any method may be used. Any of a solution state, a molten state and a suspension state may be adopted.

As radical generators, benzoyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxyacetate, diisopropyl peroxydicarbonate,
Organic or inorganic peroxides such as 2,2-bis (t-butylperoxy) octane, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, or α, α '
-Azo compounds such as azobisisobutyronitrile are used. The peroxide can be used as a redox system in combination with a reducing agent. For example, a combination of hydrogen peroxide and a ferrous salt can be mentioned. These radical generators can be appropriately selected in relation to the modifier and the reaction form. Further, two or more kinds can be used in combination.

The amount of the radical generator used is 0 to 100 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the crystalline olefin copolymer.

The temperature during radical graft modification is usually
The temperature is 30 to 350 ° C., preferably 50 to 300 ° C., and the modification reaction time is 50 hours or less, preferably 1 minute to 24 hours.

In the present invention, the acid-modified polyolefin copolymer may contain the unmodified crystalline olefin copolymer. It is also possible to include another olefin polymer having the same main component as the crystalline olefin copolymer.
A typical example of the other olefin polymer is a propylene resin from the viewpoint of moldability, rigidity and economy.

<Composition Ratio of Constituents> The composition ratio of the component (A) polyhydroxyphenylene ether and the component (B) acid-modified olefin copolymer in the thermoplastic resin composition of the present invention is the mechanical strength, From the viewpoint of harmonization of moldability and solvent resistance, the weight ratio of component (A) and component (B) is 10:90.
To 90:10, preferably 20:80 to 80: 2
The range is 0, more preferably 30:70 to 70:30. When the content of the polyhydroxyphenylene ether as the component (A) is less than 10% by weight, the heat resistance and the effect of improving rigidity are small as compared with the olefin resin, and when it exceeds 90% by weight, the moldability and the solvent resistance are better than those of the polyphenylene ether resin. The improvement effect is small.

<Additional Component> The thermoplastic resin composition of the present invention may contain a component other than the above-mentioned components (A) and (B). For example, part of the component (A) may be replaced with unmodified PPE up to 80% by weight in the resin composition. Further, an antioxidant, a weather resistance improver, a nucleating agent, a flame retardant, a plasticizer, a fluidity improver and the like may be contained in the resin composition in an amount of 20% by weight or less. Further, organic and inorganic fillers such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate and silica may be contained in an amount of 50% by weight or less, and a colorant dispersant may be included in an amount of 5% by weight or less. it can. Furthermore, addition of impact strength improver, for example, styrene-butadiene copolymer rubber or its hydride, ethylene-propylene- (diene) copolymer rubber,
Furthermore, those α, β-unsaturated carboxylic acid anhydride modified products or modified products with unsaturated glycidyl esters or unsaturated glycidyl ethers, copolymers composed of unsaturated epoxy compounds and ethylene, or unsaturated epoxy compounds, ethylene and A copolymer or the like composed of an ethylenically unsaturated compound may be contained in an amount of 5 to 30% by weight. These additional components may be used alone or in combination of two or more.

<Preparation of Thermoplastic Resin Composition> As a melt-kneading method for obtaining the thermoplastic resin composition of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, powdery or granular components, if necessary, together with the additives and the like described in the section of additional components,
After uniform mixing with a Henschel mixer, ribbon blender, V-type blender, etc., kneading with a uniaxial or multiaxial kneading extruder, roll, Banbury mixer, etc. can be carried out.

The method for molding the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resins, that is, injection molding,
Hollow molding, extrusion molding, sheet molding, thermoforming, rotational molding,
A molding method such as lamination molding or press molding can be applied.

[0048]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, parts and% are by weight.

Reference Example 1 Synthesis of Phenol Derivative Having Hydroxyl Group Under nitrogen gas atmosphere, 496 parts of 2-allyl-6-methylphenol and 392 parts of 2-mercaptoethanol were dissolved in 785 parts of ethanol. At the reflux temperature, 1600 parts of a 1.9% ethanol solution of 2,2'-azobisisobutyronitrile was added dropwise and reacted for 10 hours. After removing ethanol with an evaporator, the temperature is 110 ° C under vacuum.
The temperature is raised to 2 to remove unreacted 2-mercaptoethanol and the by-product 2-hydroxyethyl disulfide, and to remove the desired 2- [3- (2-hydroxyethylthio) propyl]
-6-Methyl-phenol was obtained. The reaction rate of the allyl group based on ¹ H-NMR analysis was about 100%, and the selectivity of the reaction was about 100%.

Reference Example 2: Synthesis of polyhydroxyphenylene ether (1) 74 parts of the phenol derivative obtained in Reference Example 1, 960 parts of 2,6-xylenol and 20 parts of sodium hydroxide were dissolved in 2890 parts of xylene and 766 parts of methanol. It was Next, 40 parts of diethanolamine, 12.6 parts of dibutylamine,
0.96 parts of manganese chloride tetrahydrate dissolved in 316 parts of methanol was added in this order. The polymerization reaction is divided into two stages,
In the former stage, the temperature was kept at 40 ° C. and oxygen gas was introduced at a flow rate of 0.8 liter / min to carry out the reaction until solids were precipitated. In the latter stage, the temperature was kept at 30 ° C.
The gas was introduced at a rate of 8 liters / minute and nitrogen gas at 8 liters / minute until the precipitation of the polymer stopped. After the polymer was washed with hydrochloric acid-methanol to deactivate the catalyst, the target polyhydroxyphenylene ether was obtained.

The yield of the product was 90%, and the hydroxyl group content was 2.4.
The mol%, the number average molecular weight was 9.950, and the Q value was 1.84. Here, the content of the hydroxyl group in the resin is shown in mol% with respect to the number of repeating main chain phenylene rings, and calculated by ¹ H-NMR from the integrated intensity of the signal derived from the methylene group to which the hydroxyl group is bound at around 3.6 ppm. did. The number average molecular weight and Q value (which is an index of the molecular weight distribution and is the ratio of the weight average molecular weight and the number average molecular weight) are polystyrene conversion values measured by the GPC method.

Reference Example 3: Synthesis of polyhydroxyphenylene ether (2) 55.5 parts of the phenol derivative obtained in Reference Example 1, 2,6
-970 parts xylenol, 9.1 parts sodium hydroxide
Parts, diethanolamine 20.5 parts, and manganese chloride tetrahydrate 0.48 parts were used under the same conditions as in Reference Example 2. The yield was 91%, the hydroxyl group content was 1.5 mol%, the number average molecular weight was 10,300, and the Q value was 1.81.

Reference Example 4: Synthesis of polyhydroxyphenylene ether (3) 148.3 parts of the phenol derivative obtained in Reference Example 1, 2,
Reference Example 3 except that 921 parts of 6-xylenol was used.
It carried out on the same conditions as. Yield 87%, hydroxyl group content 4.
9 mol%, number average molecular weight 5,620 and Q value 1.84.
Met.

Reference Example 5: Synthesis of acid-modified olefin copolymer (1) Random copolymer of propylene and 7-methyl-1,6-octadiene (Mitsubishi Yuka Co., Ltd., trial product, 7-methyl-
1,6-octadiene content 2 mol%, crystallinity by X-ray diffraction method 46.5%, MFR: 2g / 10 min) 250
Parts and 250 parts of maleic anhydride were charged in advance into a 10-liter glass flask equipped with a stirrer, which had been sufficiently replaced with nitrogen, and 5 liters of chlorobenzene were added,
The mixture was heated and stirred at ℃ and dissolved. To this solution, 0.6 part of benzoyl peroxide dissolved in 500 ml of chlorobenzene was added dropwise over 2 hours.
Reacted for hours. The obtained reaction product was poured into 15 liters of acetone to precipitate the product, which was filtered and washed twice, and then dried under reduced pressure to obtain an acid-modified olefin copolymer. It was The maleic anhydride content of this acid-modified olefin copolymer was 4.8% by weight by infrared spectroscopic analysis. The MFR is 3.1g / 1
It was 0 minutes.

Reference Example 6: Synthesis of Acid-Modified Olefin Copolymer (2) Propylene and 7-methyl-1,6-as used in Reference Example 5
100 parts by weight of a random copolymer with octadiene and 10 parts by weight of maleic anhydride were used with a TEX30 twin screw extruder manufactured by Japan Steel Works at a temperature of 220 ° C. and a screw rotation speed of 30.
Granulation was carried out under the condition of 0 rpm. The maleic anhydride content of the obtained pellets was 4.1% by weight by infrared spectroscopic analysis. The MFR was 3.8 g / 10 minutes.

Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1 using the polyhydroxyphenylene ethers obtained in Reference Examples 2, 3 and 4 and the acid-modified olefin copolymers obtained in Reference Examples 5 and 6. Each dried component was melt-kneaded at 260 ° C. and 180 rpm for 10 minutes using a Labo Plastomill kneader manufactured by Toyo Seiki Seisakusho according to the composition ratio, and then pulverized to obtain a granular resin composition. The characteristics of the obtained resin composition were measured and evaluated by the following methods, and the results are shown in Table 2.

(1) Bending elastic modulus: Using a hydraulic press molding machine manufactured by Toyo Seiki Seisakusho, pressure molding was performed at 280 ° C. to obtain a sheet having a thickness of 2 mm, and then a test piece having a width of 15 mm and a length of 80 mm was prepared. Cut out, in accordance with JIS K 7106, 23
The cantilever bending elastic modulus was measured at a temperature of ℃ and a bending deformation angle of 10 °.

(2) Impact strength: CS-183M manufactured by Custom Scientific
Using an MX Minimax injection molding machine at a temperature of 280 ° C,
Test pieces with a length of 31.5 mm, a width of 6.2 mm, and a thickness of 3.2 mm are injection-molded, and using a custom scientific Minimax Izod impact tester model CS-138TI, there is no notch at 23 ° C. And, the Izod impact strength with notch (notch R = 0.25 mm, depth 0.32 mm) was measured.

(3) Evaluation of mixed state: A part of the test piece of (2) above was cut out and subjected to ion etching, and then the dispersed particle size was observed with a scanning electron microscope (Hitachi, S-2400). did.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

The thermoplastic resin composition of the present invention comprising the polyhydroxyphenylene ether as the component (A) and the acid-modified olefin copolymer as the component (B) is, as shown in Examples and Comparative Examples, In addition to the mechanical performance expected from the composition of component (A) and component (B), good impact strength can be obtained, and therefore it can be used in a wide range of application fields such as automobile parts and electric parts.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Yamauchi 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising the following components (A) and (B). (A) Polyhydroxy having a number of structural units represented by the following general formula (I) and q structural units represented by the following general formula (II) and having a number average degree of polymerization of 25 to 400. Phenylene ether 10 to 90% by weight Here, p and q satisfy the following formula. 0.2 ≦ 100p / (p + q) ≦ 100 [In the formula, m represents an integer of 1 to 4 and n represents an integer of 0 to 3, and m + n ≦ 4. J is ^{_{(HO) a -R 1 -S-}} R
^2- (wherein, a represents an integer of 1 to 6, R ¹ is a halogen atom-substituted or unsubstituted aliphatic polyvalent group having 1 to 20 carbon atoms, which may be interrupted by an oxygen atom. It represents a hydrocarbon group or an aromatic polyvalent hydrocarbon group, R ² represents an alkylene group having 2 to 20 carbon atoms), and when m is 2 or more, J may be different from each other. K is a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a phenyl group, an aminoalkyl group having 1 to 20 carbon atoms, or a haloalkyl having 1 to 20 carbon atoms. Group, a hydrocarbon oxy group having 1 to 20 carbon atoms or a halohydrocarbon oxy group, and when n is 2 or more, K
May be different from each other] (In the formula, Q ¹ , Q ² , Q ³ and Q ⁴ are each a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a phenyl group. , An aminoalkyl group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms
0 represents a haloalkyl group, a hydrocarbon oxy group having 1 to 20 carbon atoms or a halohydrocarbon oxy group) (B) at least one α-olefin having 2 to 8 carbon atoms and at least one chain non-conjugated diene 90 to 10% by weight of an acid-modified olefin copolymer modified by graft-reacting an unsaturated carboxylic acid or a derivative thereof to a crystalline olefin copolymer copolymerized with a seed