JPH0598146A - Modified polyphenylene ether-based resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in molding processability, thermal stability, impact resistance, etc., comprising a specific polyphenylene ether-based resin, (partially hydrogenated conjugated diene rubber-contg.) styrene- based resin and modified block copolymer resin. CONSTITUTION:The objective composition comprising (A) 10-90 pts.wt. of an unsaturated carboxylic acid (derivative)-modified polyphenylene ether-based resin, (B) 90-10 pts.wt. of an impact-resistant styrene-based resin containing a partially hydrogenated conjugated diene rubber with 5-70wt.% of the whole double bond therein hydrogenated, (C) 0-80 pts.wt. of a styrene-based resin, and (D) 0-20 pts.wt. of a modified block copolymer resin made up of (1) unsaturated carboxylic acid (derivative)-modified styrene-based polymer block and (2) olefin elastomer block. The 1,2- and 1,4-vinyl bond contents of the above partially hydrogenated conjugated diene rubber in the component B are >=3wt.% and >=30wt.%, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether resin composition having excellent impact resistance, heat stability, excellent processability such as moldability, and secondary processability such as coating adhesion. More specifically, a modified polyphenylene ether resin modified with an unsaturated carboxylic acid or a derivative thereof is used as the polyphenylene ether resin, and a partially hydrogenated conjugated diene rubber in which a part of all double bonds of the conjugated diene rubber is hydrogenated. The present invention relates to obtaining a polyphenylene ether-based resin composition excellent in the above-mentioned properties and particularly suitable for a large-sized molding application by reinforcing the impact-resistant styrene-based resin containing

[0002]

2. Description of the Related Art Polyphenylene ether resin has heat resistance,
It is a resin that has excellent properties such as electrical characteristics, acid resistance, alkali resistance, and low specific gravity and low water absorption, but on the other hand, its low fluidity makes it difficult to perform melt molding and has low impact strength. Therefore, it also has a drawback of being slightly brittle. In order to remedy these drawbacks at the same time, a technique of blending high impact polystyrene containing a polybutadiene component has been developed and disclosed in US Pat. No. 3,383,435. However, due to the chemical instability of the double bond, the physical properties change greatly due to oxidative deterioration, etc., and it was very difficult to avoid deterioration of the physical properties due to melt molding, heat exposure or light exposure. On the other hand, a technique of reinforcing with a hydrogenated styrene-butadiene block copolymer containing almost no double bond is disclosed in, for example, JP-A-50-71.
Although disclosed in Japanese Patent Publication No. 742, the thermal stability is excellent even with this technique, but since the dispersed particles of the styrene-based polymer are not included in the rubber particles of the impact-resistant styrene-based resin, the rubber efficiency is low and the impact resistance is low. It was necessary to add a large amount of rubber component in order to improve the properties. Moreover, since the affinity between the hydrogenated styrene-butadiene block copolymer and the polyphenylene ether resin is not always sufficient, the molded product often peels. In addition, the higher the hydrogenation rate of the 1,4-butadiene component in the butadiene block,
Since the glass transition point of the rubber component rises, it is not possible to obtain sufficient low temperature impact resistance only with such a technique. Apart from this, a technique for improving impact strength while maintaining the rigidity of impact-resistant styrene resin is disclosed in Japanese Patent Laid-Open No. 64-9020.
It is disclosed in Japanese Patent Publication No. 8 and in Examples, it is shown that the impact strength is improved even when blended with the polyphenylene ether resin as compared with the conventional impact resistant styrene resin.
However, a resin composition containing a polyphenylene ether-based resin is characterized by high heat resistance, and in the region containing a large amount of 1,2-vinyl residues in the technique disclosed in the publication, molding processing at high temperature or heat exposure is performed. In that case, there is a problem that the physical properties are significantly deteriorated. Further, there is a problem that low temperature impact strength cannot be obtained in a region where the hydrogenation rate is high, and the technical range of the impact-resistant styrene resin required for improving the physical properties of the polyphenylene ether resin is sufficiently satisfactory. It cannot be an indication of. Furthermore, recently, the size of molded products has increased,
Demand for secondary workability such as coating adhesion is increasing, and conventional polyphenylene ether-based resin compositions are insufficient in secondary workability, particularly coating adhesion.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyphenylene ether resin with molding processability and impact resistance by a melt processing step in which the above problems are solved or by heating such as heat exposure. The purpose of the present invention is to obtain a polyphenylene ether-based resin composition which does not cause deterioration in physical properties and has an excellent balance of impact resistance, coating adhesion and the like as compared with conventional resin compositions, and which is particularly suitable for large-scale molding.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that when a polyphenylene ether-based resin is reinforced with an impact-resistant styrene-based resin containing a conjugated diene-based rubber, the amount of the diene-based rubber component It was found that the greater the amount of heavy bonds, the more susceptible to oxidative degradation the greater the deterioration of physical properties. Furthermore, the greater the amount of 1,2-vinyl bonds among the double bonds, the more oxidative deterioration is promoted, resulting in the deterioration of physical properties. It was If the total amount of double bonds is unnecessarily large, the thermal stability and rigidity will decrease, and if it is unnecessarily small, the low temperature impact strength will decrease, so there is an appropriate amount of double bonds for maintaining the physical property balance. I found that
Furthermore, as the polyphenylene ether resin, by using a modified polyphenylene ether resin modified by an unsaturated carboxylic acid or a derivative thereof, it is found that excellent moldability, coating adhesion can be achieved, and further, if necessary. The present invention has been completed by finding that the effect is further improved by adding a modified block copolymer resin composed of a styrene-based polymer block modified with an unsaturated carboxylic acid or a derivative thereof and an olefin-based elastomer block. ..

That is, the present invention comprises (A) 10 to 90 parts by weight of a modified polyphenylene ether resin modified with an unsaturated carboxylic acid or a derivative thereof, and (B) 5 out of all double bonds of a conjugated diene rubber. 90 to 10 parts by weight of a high-impact styrene-based resin containing a partially hydrogenated conjugated diene rubber in which 70 to 70% by weight is hydrogenated, (C) styrene-based resin 0 to 80
(B) parts by weight, (D) 0 to 20 parts by weight of a modified block copolymer resin comprising a styrene-based polymer block modified with an unsaturated carboxylic acid or a derivative thereof, and an olefin-based elastomer block; )component,
The component (C) and the component (D), and the 1,2-vinyl bond content and the 1,4-bond content in the partially hydrogenated conjugated diene rubber in the component (B) are 3% by weight or less, respectively. A polyphenylene ether resin composition excellent in molding processability, thermal stability, impact resistance, and coating adhesion, which is characterized by being 30% by weight or more.

The modified polyphenylene ether resin which is the component (A) of the composition of the present invention is a modified polyphenylene ether resin obtained by modifying the following polyphenylene ether resin with an unsaturated carboxylic acid or a derivative thereof. The polyphenylene ether resin used in the present invention is represented by the general formulas (1) and (2)

[0007]

[Chemical 1]

[0008]

[Chemical 2]

(Wherein R1, R2, R3, R4, R5
R6 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen and hydrogen, and R5 and R6 are not hydrogen at the same time) and the structural unit is represented by the formula (1).
A homopolymer or a copolymer represented by the formula (2) can be used. As a typical example of a homopolymer of a polyphenylene ether resin, poly (2,6-dimethyl-1,4) is used.
-Phenylene ether, poly (2-methyl-6-ethyl 1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1) , 4-phenylene) ether,
Poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-)
1,4-phenylene) ether, poly (2-ethyl-6)
-Isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly ( Homopolymers such as 2-methyl-6-chloroethyl-1,4-phenylene) ether are mentioned.

The polyphenylene ether copolymer is 2,
Polyphenylene ether structure such as copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol, copolymer of o-cresol, copolymer of 2,3,6-trimethylphenol and o-cresol, etc. A polyphenylene ether copolymer mainly composed of

The partially hydrogenated conjugated diene rubber used in the present invention is obtained by partially hydrogenating the conjugated diene rubber obtained by a known method. The conjugated diene rubber obtained by a known method generally includes all rubbers used in the production of impact-resistant styrene resins. For example, polybutadiene (low-cis polybutadiene and high-cis polybutadiene) styrene-butadiene copolymer,
Polyisoprene, butadiene-isoprene copolymer, natural rubber and the like are preferred, and polybutadiene is most preferred.

The preferred amount of 1,2-vinyl bonds in the total double bonds of the conjugated diene rubber varies depending on the hydrogenation rate of the total double bonds and is not particularly limited, but generally 5 It is desirable that the content is at least wt%. This is because when the hydrogenation rate is increased to improve the thermal stability, the rubber elasticity is lost, but the degree of decrease in rubber elasticity decreases as the 1,2-vinyl bond content increases.

Examples of the styrene resin used in the present invention include styrene compounds, compounds copolymerizable with styrene compounds, and rubbery polymers. The styrene compound is represented by the general formula (3)

[0014]

[Chemical 3]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5) Means Specific examples of these include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene and ethylstyrene. Further, as the compound copolymerizable with the styrene compound, methacrylic acid esters; methyl methacrylate, ethyl methacrylate, etc., unsaturated nitrile compounds; acrylonitrile, methacrylonitrile, etc.,
Examples thereof include acid anhydrides such as maleic anhydride, which are used together with styrene compounds. Examples of the rubbery polymer include conjugated diene rubbers and ethylene-propylene copolymer rubbers. All of them are combined with the partially hydrogenated conjugated diene rubbers, and the 1,2-vinyl bond contained in the rubbers. And the amount of 1,4-bonding is 3% by weight or less and 30 respectively.
It is necessary that the content is at least wt%.

In the present invention, in the partially hydrogenated conjugated diene rubber, 5 to 70% by weight of all double bonds are hydrogenated, and the 1,2-vinyl bond content is 3% by weight or less, preferably 2% by weight. % Or less, and the amount of 1,4-bonds is preferably 30% by weight or more. When the hydrogenation rate of all double bonds is less than 5% by weight, the effect of partial hydrogenation cannot be sufficiently exhibited. For example, hydrogenation of a conjugated diene rubber having a 1,2-vinyl content before hydrogenation of 8% by weight to 5% by weight cannot reduce the 1,2-vinyl content to 3% by weight or less, and the total double bond Even if 5% by weight of the amount is hydrogenated, impact resistance and environmental crack resistance can hardly be improved. When the hydrogenation rate exceeds 70% by weight, impact resistance, particularly low temperature impact resistance, cannot be sufficiently obtained, which is not preferable. When the 1,2-vinyl bond content in the partially hydrogenated conjugated diene rubber exceeds 3% by weight, the rubber component is oxidized and further the main chain splitting of the styrene resin is easily induced, resulting in thermal stability. Is not preferable because it cannot be sufficiently improved. Furthermore, the 1,4-bond content is 30% by weight
If it is less than the above range, the effect of improving impact resistance becomes poor, which is not preferable.

In the present invention, the content of the impact resistant styrene resin containing the partially hydrogenated conjugated diene rubber is 90 to 10.
It is preferably selected from the range of parts by weight. Content is 9
When it exceeds 0 parts by weight, the necessary amount of polyphenylene ether resin cannot be added, and when it is less than 10 parts by weight, the partially hydrogenated conjugated diene rubber cannot be sufficiently contained. It is not preferable because the environmental crackability cannot be sufficiently improved.

In the present invention, the styrene resin is used for controlling the heat distortion temperature and the molding processability, and is added if the purpose is achieved by the impact resistant styrene resin containing the partially hydrogenated conjugated diene rubber. It may be omitted, but if necessary, up to 80 parts by weight can be added. If it exceeds 80 parts by weight, the impact-resistant styrene-based resin including the polyphenylene ether-based resin and the partially hydrogenated conjugated diene-based rubber cannot be added in a required amount, which is not preferable.

The partially hydrogenated conjugated diene rubber used in the present invention is obtained by partially hydrogenating the above-mentioned conjugated diene rubber. As the hydrogenation method, any conventionally known method may be used. L. Ramp. et
al, J .; Amer. Chem. Soc. , 83, 46
72 (1961), hydrogenation method using triisobutylborane catalyst, Hung Yu Chen,
J. Polym. Sci. Polym. Letter
Ed. , 15, 271 (1977). A method of hydrogenating using the toluenesulfonyl hydrazide described above, a method of hydrogenating using an organic cobalt-organoaluminum catalyst or an organic nickel-organoaluminum catalyst described in JP-B-42-8704, and the like can be mentioned. it can. A particularly preferable method of hydrogenation in the practice of the present invention is to use a catalyst capable of selectively hydrogenating a 1,2-vinyl bond prior to a 1,4-bond.
No. 71890, or the use of a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure.
33203 and JP-A-60-220147.

The method for producing the impact resistant styrene resin of the present invention is not limited, and any of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization well known to those skilled in the art may be used. .. The modified block copolymer resin, which is the component (D) of the composition of the present invention, is a modified block copolymer resin obtained by modifying the block copolymer with an unsaturated carboxylic acid or a derivative thereof.

The block copolymer as the raw material of the component (D) referred to in the present invention is a block copolymer comprising at least one styrene polymer block and at least one olefin elastomer block. The styrene-based polymer block referred to in the present invention is specifically represented by the general formula (3)

[0022]

[Chemical 4]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5) Is a polymer or copolymer block derived from The olefin elastomer block referred to in the present invention includes monoolefins such as ethylene, propylene, 1-butene and isobutylene, conjugated diolefins such as butadiene, isoprene and 1,3-pentadiene, 1,4-hexadiene and norbornene derivatives. A polymer block having a form in which one or more olefin compounds selected from non-conjugated diolefins are polymerized or copolymerized, and the unsaturation degree of the block is 20% or less. Therefore, when the above diolefins are used as the constituent monomers of the olefin elastomer block, the degree of unsaturation of the block portion is 2
Measures to reduce the degree of unsaturation, such as hydrogenation, must be taken to the extent that it does not exceed 0%. Further, a styrene compound may be randomly copolymerized with the olefin elastomer block. The method for obtaining the modified compound of the component (A) and the component (D) is not limited, but the most useful method is to melt in the presence of the original polymer and the unsaturated carboxylic acid or its derivative and, if necessary, an organic peroxide. It is a method of kneading. It is also useful to separately prepare the components (A) and (D), but simultaneous modification treatment in the coexistence of the polyphenylene ether resin and the block copolymer is also a useful means. Furthermore, in order to control the amount of modification, an unmodified original polymer may be added to the final composition within a range that does not impair the effects of the present invention.

Examples of the unsaturated carboxylic acid or its derivative used in the present invention include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis. -Bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid and acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., and esters of these monocarboxylic acids, Examples thereof include amide.
These can be used not only as one type but also as a mixture of two or more types. Of these, unsaturated dicarboxylic acids or derivatives thereof are preferable, and maleic anhydride is particularly preferable.

The radical initiator used in the present invention is an organic or inorganic radical generator usually used as a polymerization catalyst for vinyl compounds. Of these, organic peroxides are preferable. Specific examples include tertiary butyl hydroperoxide, cumene hydroperoxide,
Ditertiary butyl peroxide, dicumyl peroxide,
2,5-dimethyl-2,5-di (tertiary butyl peroxy) hexane, isobutyl peroxide, benzoyl peroxide, diisopropyl peroxy carbonate,
Examples thereof include tertiary butyl peroxybenzoate, α, α′-azobisisobutyl nitrile, tertiary butyl peroxylaurate and the like.

The amount of the molecular unit containing a carboxylic acid group or its derivative group contained in the modified polyphenylene ether resin, that is, the addition amount of the unsaturated carboxylic acid or its derivative is the whole modified polyphenylene ether resin used in the present invention. The average value is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polyphenylene ether resin. When the molecular unit containing the carboxylic acid group or its derivative group is less than 0.05 parts by weight, almost no improvement effect is recognized as compared with the unmodified polyphenylene ether, and even if it exceeds 10 parts by weight, it is The improvement effect is not so remarkable.

The amount of molecular units containing carboxylic acid groups or their derivative groups contained in the modified block copolymer resin,
That is, the amount of addition of the unsaturated carboxylic acid or its derivative is 0.05 to 10 parts by weight, preferably 0. 0, based on 100 parts by weight of the block copolymer, as an average value of the entire modified block copolymer resin used in the present invention. 2 to 5 parts by weight. When the molecular unit containing the carboxylic acid group or its derivative group is less than 0.05 parts by weight, almost no improvement effect is recognized as compared with the unmodified block copolymer resin.
Even if it exceeds the weight part, the improvement effect is not remarkable as compared with the case of less than that. When the amount of the molecular unit containing a carboxylic acid group or its derivative group exceeds 0.05 parts by weight,
The unmodified block copolymer can be used in combination, and the amount that can be used in combination is 0. with respect to the total amount of the modified and unmodified block copolymer resins in which the amount of the molecular unit containing the carboxylic acid group or its derivative group is 0. It is preferable that the amount is not less than 05 parts by weight, and the amount of the unmodified block copolymer does not exceed the amount of the modified block copolymer resin.

In the present invention, the content of the modified polyphenylene ether resin as the component (A) is preferably in the range of 10 to 90 parts by weight. When the content is less than 10 parts by weight,
The modified polyphenylene ether resin is not preferable because the improvement effect is not sufficiently exhibited, and when it exceeds 90 parts by weight, it is not preferable because the moldability or impact resistant styrene resin cannot be added.

The component (C) is mainly used for controlling the processability of the composition and the heat distortion temperature. When the amount of the component exceeds 80 parts by weight, the properties of the polyphenylene ether resin are significantly impaired, which is not preferable. The component (D) is useful for further improving impact resistance and oil resistance. However, if the amount of the component exceeds 20 parts by weight, the rigidity is extremely lowered, which is not preferable. In the composition of the present invention, other additives such as a plasticizer, a stabilizer, an ultraviolet absorber, a flame retardant, a colorant, a release agent and a fibrous reinforcing agent such as glass fiber and carbon fiber, and further glass beads. Fillers such as calcium carbonate and talc can be added.

As the stabilizer, phosphite esters, hindered phenols, alkanolamines, acid amides, metal salts of dithiocarbamic acid, inorganic sulfides and metal oxides may be used alone or in combination. be able to. As the flame retardant, aromatic phosphate ester,
Red phosphorus, aromatic halogen compounds, antimony trioxide, etc. are particularly effective.

Any method may be used for mixing the respective components constituting the present invention. For example, an extruder, a heating roll, a Banbury mixer, a kneader or the like may be used.

[0032]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples. Less than,
% And part represent% by weight and part by weight, respectively. The impact-resistant styrene-based resin used in the following examples and comparative examples was prepared by the manufacturing method described below. The impact-resistant styrene resins used in Examples and Comparative Examples, and the conjugated diene rubber and the partially hydrogenated conjugated diene rubber used in the preparation thereof are as shown in Table 2.

Production Example 1 Production of Partially Hydrogenated Conjugated Diene Rubber (corresponding to Table 1), Partially Hydrogenated Conjugated Diene Rubber used in Examples is typically produced by the following method. .. Using a jacketed autoclave with an internal volume of 10 liters as a reactor, a butadiene / n-hexane mixture solution (butadiene concentration 20%) was added with an n-butyllithium / n-hexane solution (concentration 5%) at 20 l / hr. It was introduced at 70 ml / hr, and continuous polymerization of butadiene was carried out at a polymerization temperature of 110 ° C. The active polymer obtained was deactivated with methanol, and another internal volume of 10
l of the polymer solution in a reactor with a stirrer and jacket
At a temperature of 60 ° C. and 250 ml of a di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1.2 mmol / l) as a hydrogenation catalyst.
And n-butyllithium solution (concentration 6 mmol / l) 5
A mixture of 0 ml and 0 ° C. under a hydrogen pressure of 2.0 kg / cm ² was added, and a hydrogen partial pressure of 3.0 kg / cm ² was added to 60.
Let react for minutes. To the obtained partially hydrogenated polymer solution, 0.5 part of 2,6-di-tert-butylhydroxytoluene was added as an antioxidant per polymer, and the solvent was removed.

The analytical values of the polybutadiene before partial hydrogenation and the partially hydrogenated polybutadiene obtained by sampling after deactivation of methanol are shown in Table 1. Production Example 2; Production of Impact-Resistant Styrenic Resin {(B) Component: Corresponding to Table 2} The impact-resistant styrene-based resin used in the examples was produced by a bulk polymerization method. A typical example will be described below.

10 parts of partially hydrogenated polybutadiene shown in Table 1 was dissolved in 90 parts of styrene and 8 parts of ethylbenzene, and 0.05 part of benzoyl peroxide and 0.01 part of α-methylstyrene dimer were added to styrene. And add 80
Polymerization was carried out with stirring at 4 ° C. for 4 hours, 110 ° C. for 4 hours, and 150 ° C. for 4 hours. Further, heat treatment was performed at about 230 ° C. for 30 minutes, and then unreacted styrene and ethylbenzene were vacuum removed to obtain an impact-resistant styrene-based resin.

The content of partially hydrogenated polybutadiene in the obtained impact-resistant styrene-based resin was 11%, and the average particle diameter of partially hydrogenated polybutadiene in the state of containing dispersed polystyrene particles was 2.7 μm. there were. Production Example 3; Preparation of modified polyphenylene ether resin {component (A)}, intrinsic viscosity 0.50 (measured in chloroform at 30 ° C)
Of poly (2,6-dimethyl-1,4-phenylene) ether (PPE) of 100 parts by weight of polystyrene 50
Parts, maleic anhydride 2 parts, and perbutyl D 0.5 parts uniformly mixed, and then, using an extruder, under a nitrogen atmosphere at 300 ° C.
Was melt-kneaded and a maleinization reaction was performed to obtain a modified polyphenylene ether resin mixture. Polyphenylene ether resin 1 determined by titration with sodium methylate
The amount of maleic anhydride added to 00 parts was 0.8 parts.

In the examples, the amount of maleic anhydride added to the components in the composition was measured as follows. The composition was dissolved in dichloromethane at 38 ° C. and then filtered to separate the modified block copolymer. Then, the solution portion was left at -5 ° C for 24 hours to precipitate a modified polyphenylene ether resin, which was filtered to separate the resin. Next, the filtrate was added dropwise to methanol to reprecipitate polystyrene, which was then filtered and separated. The amount of maleic anhydride added to each component was measured by titration with sodium methylate.

No addition of maleic anhydride to polystyrene was observed. Production Example 4; Preparation of modified block copolymer {(D) component}, 2 parts of maleic anhydride, perbutyl D (Japan) to 100 parts of a block copolymer consisting of a styrene polymer block and an olefin elastomer block 260 parts by an extruder after uniformly mixing 0.5 parts
The mixture was melt-kneaded at 0 ° C. to carry out a maleation reaction to obtain a modified block copolymer mixture. The addition amount of maleic anhydride to the block copolymer of the modified block copolymer determined by titration with sodium methylate is 1.0 to 1.2.
It was a department.

Preparation Example 5: Preparation of Simultaneous Modification of Polyphenylene Ether and Block Copolymer {Component (A) and (D)
Ingredient}, Intrinsic viscosity 0.50 (measured in chloroform at 30 ° C)
To 50 parts of poly (2,6-dimethyl-1,4-phenylene) ether (PPE), 17 parts of a block copolymer consisting of a styrene polymer block and an olefin elastomer block, 33 parts of polystyrene, maleic anhydride After uniformly mixing 0.5 parts of acid and 0.25 part of perbutyl D, the mixture was melt-kneaded at 300 ° C. in a nitrogen atmosphere using an extruder to carry out a maleation reaction. The addition amount of maleic anhydride to 100 parts of the polyphenylene ether resin determined by titration with sodium methylate was 0.
It was 2 parts.

In the examples, the amount of maleic anhydride added to the components in the composition was measured as follows. The composition was dissolved in chloroform, reprecipitated with methanol to remove unreacted maleic anhydride, dissolved in dichloromethane at 38 ° C., filtered, and then the solution portion was -5
The modified polyphenylene ether-based resin was precipitated by leaving it at 24 ° C. for 24 hours and filtered to separate the resin. Next, the filtrate was added dropwise to methanol to reprecipitate the modified block copolymer and polystyrene, and the precipitate was filtered and separated.
The amount of maleic anhydride added to each component was measured by titration with sodium methylate.

No addition of maleic anhydride to polystyrene was observed. The amount of maleic anhydride added to the block copolymer resin was 0.8 to 1.2 parts. Next, a method for measuring and evaluating physical properties of the resin composition will be described. (1) Melting index According to JIS K 7210.

Temperature: 250 ° C. Load: 10 Kg An injection molding machine (manufactured by Toshiba Machine Co., IS80C, cylinder temperature 280 ° C. or 290 ° C.) was used to prepare a test piece,
The following (2) to (5) were measured. (2) Heat distortion temperature ASTM D648 Load: 18.6 Kg / cm ² (3) Izod impact strength ASTM D256, with notch Temperature: 23 ° C (4) Molding stability Molded at injection molding temperature of 280 ° C (or 290 ° C) 310 ℃ (or 3 for the Izod impact strength of the molded product
It was judged from the retention rate of the Izod impact strength of the molded product which was molded after being retained in the cylinder at 20 ° C. for 10 minutes (or 15 minutes).

Injection molding machine (manufactured by Toshiba Machine Co., IS8
75 × 75 × 3mm at 0C, cylinder temperature 290 ℃)
A test piece was prepared and the following (7) to (8) were measured. (5) Coating adhesion After coating with a commercially available urethane-based paint, conduct a cross-cut test,
The following ranks were given according to the number of peeled squares in all squares (100 pieces).

◎: Peeling number is 0 ◯: Peeling number is 1 to 10 Δ: Peeling number is 11 to 20 ×: Peeling number is 21 to 100

[0045]

Example 1 35 parts of the modified polyphenylene ether resin prepared in Production Example 3, No. 1 in Table 2. 54 parts of high impact polystyrene (hereinafter abbreviated as HIPS) of No. 1, 11 parts of the modified block copolymer resin (addition amount of maleic anhydride of 1.0 part) prepared in Production Example 4 and Sumilizer BHT (Sumitomo Chemical Hinder 1 part of dephenol) was melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition.
Table 3 shows the results of physical property tests of the resin composition.

[0046]

Example 2 7 parts of the modified polyphenylene ether resin prepared in Production Example 3 and poly (2,6-dimethyl-1,2) with an intrinsic viscosity of 0.50 (measured in chloroform at 30 ° C.)
4-phenylene) ether (hereinafter abbreviated as PPE) 2
No. 8 of Table 2, No. Impact-resistant polystyrene of 1 (hereinafter H
Abbreviated as IPS) 54 parts, modified block copolymer resin prepared in Production Example 4 (addition amount of maleic anhydride 1.0 part)
11 parts and Sumilyzer BHT (Sumitomo Chemical's hindered phenol) 1 part were melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition. Table 3 shows the results of physical property tests of the resin composition.

[0047]

Example 3 46 parts of the co-modified resin of the polyphenylene ether and the block copolymer prepared in Production Example 5, No. 2 in Table 2. 280 by using an extruder with 54 parts of high impact polystyrene (hereinafter abbreviated as HIPS) and 1 part of Sumilizer BHT (hindered phenol manufactured by Sumitomo Chemical Co., Ltd.)
A resin composition was obtained by melt-kneading at a temperature of ° C. Table 3 shows the results of physical property tests of the resin composition.

[0048]

Comparative Example 1 Intrinsic viscosity 0.50 (in chloroform, 30
Poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter abbreviated as PPE) (measured at C) was used in Example 1.
The same operation as in Example 1 was carried out except that the modified polyphenylene ether resin was used instead of the modified polyphenylene ether resin. The results are shown in Table 3.

[0049]

[Comparative Example 2] No. 2 in Table 2 Table 2 instead of HIPS 1
No. Comparative Example 1 was repeated except that HIPS of No. 2 was used to obtain a resin composition. The results are shown in Table 3.

[0050]

Example 4 45 parts of the modified polyphenylene ether resin prepared in Production Example 3, No. 2 in Table 2. 55 parts of HIPS 1 and 1 part of Sumilizer BHT (hindered phenol manufactured by Sumitomo Chemical Co., Ltd.) were melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition. Table 4 shows the results of physical property tests of the resin composition.

[0051]

Example 5 9 parts of the modified polyphenylene ether resin prepared in Production Example 3 and poly (2,6-dimethyl-1,2) with an intrinsic viscosity of 0.50 (measured in chloroform at 30 ° C.)
4-phenylene) ether (hereinafter abbreviated as PPE) 3
No. 6 in Table 2, No. 6 55 parts of HIPS 1 and 1 part of Sumilizer BHT (hindered phenol manufactured by Sumitomo Chemical Co., Ltd.) were melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition. Table 4 shows the results of physical property tests of the resin composition.

[0052]

Sixth Embodiment No. 2 in Table 2 Table 2 instead of HIPS 1
No. Example 3 was repeated except that HIPS of 3 was used to obtain a resin composition. The results are shown in Table 4.

[0053]

Comparative Example 3 Instead of the modified polyphenylene ether used in Example 3, an intrinsic viscosity of 0.50 (in chloroform,
Example 3 was repeated except that PPE (measured at 30 ° C.) was used to obtain a resin composition. Table 4 shows the results of physical property tests of the resin composition.

[0054]

[Comparative Example 4] No. 2 in Table 2 Table 2 instead of HIPS 1
No. Comparative Example 3 was repeated except that HIPS of 2 was used to obtain a resin composition. The results are shown in Table 4.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

EFFECTS OF THE INVENTION The composition of the present invention does not deteriorate in physical properties due to heating such as a melt processing step or heat exposure, and has a better balance of fluidity, impact resistance, coating adhesion and the like than conventional resin compositions. It is excellent and is industrially useful especially for large-scale molding.

Claims (1)

[Claims] 1. (A) 10 to 90 parts by weight of a modified polyphenylene ether resin modified with an unsaturated carboxylic acid or a derivative thereof, and (B) 5 to 70% by weight of all double bonds of a conjugated diene rubber. 90 to 10 parts by weight of a high-impact styrene resin containing a partially hydrogenated conjugated diene rubber that is hydrogenated, (C) 0 to 80 parts by weight of a styrene resin, (D) modified with an unsaturated carboxylic acid or a derivative thereof. Modified block copolymer resin comprising treated styrene polymer block and olefin elastomer block 0
To 20 parts by weight of (A) component, (B) component, (C) component, (D) component, and 1,2-vinyl contained in the partially hydrogenated conjugated diene rubber in the component (B). Polyphenylene ether resin composition excellent in molding processability, thermal stability, impact resistance, and coating adhesion, characterized in that the bonding amount and the 1,4-bonding amount are 3% by weight or less and 30% by weight or more, respectively. object.