JPS6346782B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyphenylene ether resin composition having excellent impact strength, appearance, solvent resistance, and colorability. Polyphenylene ether resin has excellent mechanical properties, electrical properties, and heat resistance, as well as low water absorption and good dimensional stability. However, its drawback is poor moldability. This resin, which has poor impact resistance, has been improved by blending it with high-impact polystyrene and has been widely used in recent years. However, polyphenylene ether resins and resin compositions of polyphenylene ether and high-impact polystyrene tend to degrade when they come into contact with organic solvents such as acetone, hexane, cyclohexane, gasoline, machine oils, and greases, especially under stress. It has the disadvantage of easily causing cracks (stress cracks). For this reason, their applications are severely limited, and improvements are in great demand. Various proposals have been made to improve this stress crack resistance. For example, Unexamined Japanese Patent Publication No. 48-
42047 discloses that high molecular weight polystyrene is used, and JP-A-48-62851 discloses that A-B-
The addition of an A' type elastomer block copolymer and the addition of a hydrogenated block copolymer have been proposed in JP-A-50-71742. However, with these improvement measures, other mechanical properties such as rigidity are significantly impaired, and the effect of improving stress crack resistance itself is insufficient. Additionally, U.S. Patent No. 3383435 describes acrylonitrile-butadiene-styrene copolymer (ABS resin) and poly(2,6-dimethyl-1,4
-phenylene) ether is described. However, although the US patent shows an example of blending ABS resin with 16% acrylonitrile units, 41% styrene units, and 43% butadiene units and polyphenylene ether, the US patent's polystyrene or impact-resistant As shown in the comparison of physical properties between polystyrene and compounded agents,
The ABS resin and polyphenylene ether are
The compatibility is extremely poor, and the resulting composition is extremely brittle and has a very poor appearance, making it unsuitable for practical use. Furthermore, as polyphenylene ether resin compositions are used in a wide range of applications, there is an increasing demand for them to be colored in various hues. However, resin compositions of polyphenylene ether and high-impact polystyrene have poor coloring properties, and are said to be particularly difficult to color to bright hues, and improvements have been desired for some time. However, for example, although JP-A-52-98097 discloses a method for decolorizing polyphenylene ether, there is no improvement in the colorability of a resin composition of polyphenylene ether resin and styrene resin.
Until now, no technique has been shown. The present inventors have disclosed in Japanese Patent Application No. 57-35836 that the solvent resistance and coloring properties of polyphenylene ether resin compositions were improved by adjusting the acrylonitrile content in the graft phase and resin phase of the rubber reinforcing resin. I showed what I could get. However, although the composition disclosed in the patent application has improved dispersibility of the polyphenylene ether resin and rubber reinforcing resin,
However, it was not perfect, and as a result, the appearance of the molded product was poor, and there was still room for improvement in terms of impact strength. The present invention relates to a polyphenylene ether resin composition that has significantly improved appearance, improved impact strength, and excellent solvent resistance and colorability. The present inventors studied in detail the influence of the composition of the rubber-reinforced resin on the mixing performance with the polyphenylene ether in a resin composition of polyphenylene ether and rubber-reinforced resin. As a result, in a rubber reinforcing resin made of a copolymer of a vinyl cyanide compound and a vinyl aromatic compound, the amount of the vinyl cyanide compound in the graft phase grafted to the elastomer rubber phase was determined to be in a certain distribution state. By adjusting to We have discovered the surprising fact that it is possible to obtain a composition that has excellent appearance and impact strength, as well as good solvent resistance and coloring properties,
The present invention has been accomplished. That is, the present invention provides the following components (a) and (b): (a) General formula

【formula】

[Formula] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are the same or different alkyl groups having 1 to 4 carbon atoms excluding tertiary butyl groups, aryl groups, halogens, hydrogen A monovalent substituent such as R ₅ and R ₆ are not hydrogen at the same time) as a repeating unit, and the constituent units are [ ] or [ ] and [ ]. phenylene ether resin 10 to 80% by weight (b) rubber reinforcing resin 90 to 20% by weight; as for component (b), the elastic rubber phase is co-grafted with a vinyl cyanide compound and a vinyl aromatic compound; a grafted rubber phase which is polymerized and has a grafting amount of 20% by weight or more and which contains at least the following two phases (a) and (b) as the grafting phase; and (a) a vinyl cyanide compound amount of 15 to 15%. Copolymer of 40% by weight of vinyl cyanide compound and vinyl aromatic compound 90-10% by weight (b) Vinyl cyanide compound Copolymer of 1-15% by weight of vinyl cyanide compound and vinyl aromatic compound 10 to 90% by weight A copolymer of a vinyl cyanide compound and a vinyl aromatic compound, or this copolymer, in which the average amount of vinyl cyanide compound in the resin phase other than the graft rubber phase is in the range of 1 to 15% by weight. A polyphenylene ether resin composition comprising a blend of a polymer and a polymer of a vinyl aromatic compound. In the present invention, the polyphenylene ether resin (PPE) has the general formula:

【formula】

[Formula] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are the same or different alkyl groups having 1 to 4 carbon atoms excluding tert-butyl groups, aryl groups, halogens, hydrogen, etc. It is a monovalent residue of R ₅ and R ₆ are not hydrogen at the same time) as a repeating unit, and a homopolymer or copolymer consisting of [ ] or [ ] and [ ] can be used. Representative examples of PPE homopolymers include poly(2,6-dimethyl-1,4-phenylene) ether and 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-chloro-1,4-phenylene) ether, poly( 2
Examples include homopolymers such as -methyl-6-hydroxyethyl-1,4-phenylene) ether and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether. Polyphenylene ether copolymer has the general formula (Here, R ₃ , R ₄ , R ₅ , R ₆ have the same meanings as above.) A combination of an alkyl-substituted phenol such as 2,3,6-trimethylphenol and, for example, O-cresol, etc. It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by polymerization. In the present invention, if the added amount of polyphenylene ether, which is a constituent component of the composition, is less than 10% by weight in the resin composition, the heat resistance, which is a characteristic of polyphenylene ether, will be lost, so it will have no practical value.
In addition, if the amount exceeds 80% by weight, the processability will be significantly reduced, so the amount of polyphenylene ether added should be
A range of 10 to 80% by weight is desirable. The vinyl aromatic compound used in the rubber reinforcing resin has the following general formula: (In the formula, R is a hydrogen atom, a halogen atom, or an alkyl group, and Z is a hydrogen atom, a halogen atom,
It is a vinyl group or an alkyl group, and p is an integer of 1 to 5. ), and one or more types of these can be used. Specific examples of the above-mentioned vinyl aromatic compounds include styrene, α-methylstyrene,
Examples include vinyltoluene, vinylethylbenzene, vinylxylene, tert-butylstyrene, and chlorostyrene. Vinyl cyanide compounds have the following general formula: (In the formula, R is a hydrogen atom or an alkyl group.) One or more of these can be used. Specific examples of the vinyl cyanide compounds include acrylonitrile, methacrylonitrile, α-ethyl acrylonitrile, α-
Examples include propyl acrylonitrile and α-butyl acrylonitrile. As a result of intensive studies by the present inventors, in a composition consisting of polyphenylene ether and rubber reinforcing resin, the graft phase of the rubber reinforcing resin consists of at least the following two types of graft phases (a) and (b). (a) 10 to 90% by weight copolymer containing 15 to 40% by weight of a vinyl cyanide compound that has good solvent resistance and coloring properties; (b) Vinyl cyanide that is well compatible with polyphenylene ether. Copolymer with a compound amount of 1 to 15% by weight
90 to 10% by weight On the other hand, it is important to keep the average amount of vinyl cyanide compound in the resin phase other than the graft rubber phase within the range of 1 to 15% by weight. If the amount of vinyl cyanide compound in the graft phase (a) of the rubber reinforcing resin is less than 15% by weight, solvent resistance will not be sufficient, and if it exceeds 40% by weight, the effect of improving solvent resistance will be exceeded. impact strength decreases, thermal discoloration is severe, and colorability becomes insufficient. In addition, the graft phase (B) containing 1 to 15% by weight of vinyl cyanide compound in the graft phase has good compatibility with polyphenylene ether, and the presence of this graft phase (B) increases the It provides very good dispersion in phenylene ether, so that the appearance and impact strength of the resin are maintained at very good levels. In order to obtain such characteristics, it is necessary to maintain the ratio of the graft phases (a) and (b) within the ranges of 10 to 90% by weight and 90 to 10% by weight, respectively. Particularly preferred ranges are 20 to 80% by weight and 80 to 20% by weight, respectively. If the amount of the graft phase (a) in which the amount of vinyl cyanide compound is 15 to 40% by weight is less than 10% by weight, the solvent resistance of the composition will not be improved sufficiently; If the amount of graft phase (b) in the weight percentage is less than 10% by weight, the impact strength and appearance of the composition will decrease. In addition, in order to obtain the quality characteristics shown in the present invention, the amount of grafting of the copolymer consisting of a vinyl cyanide compound and a vinyl aromatic compound to the elastomer rubber phase must be at least 20% by weight and up to about 300% by weight. range is suitable.
If the amount of grafting is less than 20% by weight, the appearance, impact strength,
Solvent resistance and coloring properties are insufficient. On the other hand, if the amount of grafting is too high, the impact strength and appearance will deteriorate, so the amount of grafting is preferably about 300% by weight or less. On the other hand, the average amount of vinyl cyanide compound in the continuous resin phase other than the graft rubber phase is 1 to 1.
It is necessary to maintain the content in the range of 15% by weight, particularly preferably in the range of 1 to 10% by weight. Note that the amount of vinyl cyanide compound as used in the present invention refers to the weight percent of vinyl cyanide compound to the total amount of vinyl cyanide compound and vinyl aromatic compound. The elastic rubber phase used in the above rubber reinforcing resin includes polybutadiene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer,
Styrene-butadiene block copolymer or its hydrogenated product, ethylene-propylene copolymer,
One type from ethylene-propylene-nonconjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene terpolymer, ethylene-propylene-dicyclopentadiene terpolymer, polyacrylic acid alkyl ester, polyisoprene, natural rubber, etc. You can select from the above. The amount of the elastomer rubber phase added may range from 1 to 25% by weight depending on the target strength level of the final composition. As long as the graft state of the elastic rubber phase and the resin composition of the continuous phase are within the above range, the method for manufacturing the rubber reinforced resin as described above can be carried out by emulsion polymerization, bulk polymerization, and solution polymerization, which are well known to those skilled in the art. or suspension polymerization may be used. Emulsion polymerization methods are particularly suitable for producing the rubber-reinforced resin of the present invention, and the following two methods are typical examples thereof. Method 1: In a reactor containing elastic rubber latex,
First, graft polymerization is carried out while adding a monomer composition with a constant concentration within the range of 15 to 40% by weight of vinyl cyanide compound corresponding to the graft phase (a),
After the added monomer completes polymerization, the amount of vinyl cyanide compound corresponding to the graft phase (b) is 1 to 1.
A method of graft polymerization while adding a monomer composition at a constant concentration within the range of 15% by weight. Method 2: The vinyl cyanide compound in the monomer composition to be graft copolymerized into a reactor containing an elastomer rubber latex is continuously added from a high concentration level corresponding to the graft phase (a) to a low concentration level corresponding to the graft phase (b). A method of continuously changing the amount of vinyl cyanide compound in the graft phase by graft copolymerization while changing the amount of vinyl cyanide compound. The distribution state of the vinyl cyanide compound amount in the graft phase obtained by the above methods 1 and 2 is schematically shown in Figures 1 and 2. These manufacturing methods -1 and -2 are just typical examples, and the distribution state of the vinyl cyanide compound in the graft phase of the rubber-reinforced resin of the present invention is shown in Figure-1.
Of course, it is possible to include materials with a distribution state intermediate between the two in addition to those shown in FIG. 2, and a manufacturing method suitable for obtaining such a distribution may also be adopted. Alternatively, the graft rubber phase and the continuous resin phase may be individually polymerized and used in combination. The amount of grafted rubber reinforcing resin can be adjusted by adjusting the amounts of chain transfer agents, polymerization catalysts, and emulsifiers added during graft polymerization, and by adjusting the rate of addition of monomers into the polymerization tank, polymerization temperature, etc. Note that various methods have been reported for analyzing the graft state of rubber-reinforced resin. For example, J.
Polymer Sei A3 3825 1965, Rubber Chem.
& Technol 38 No.3 655 1965 etc. The present inventors separated the grafted rubber phase and the resin phase and analyzed the amount of grafting using the following method.
That is, 1 g of rubber reinforcing resin was added to 25 c.c. of methyl ethyl ketone, shaken thoroughly, and the insoluble matter was removed at 0°C.
It was centrifuged at 20,000 rpm and separated into a supernatant and a precipitate. The supernatant liquid contained a resin phase, which was precipitated and recovered by adding it to methanol. Further, the precipitate obtained by centrifugation was separated and recovered as a graft rubber phase. The amount of grafting referred to in the present invention was determined using the following calculation formula. Graft amount (%) = Graft phase weight - Rubber reinforcing resin 1
Amount of rubber in g/Amount of rubber in 1 g of rubber-reinforced resin x 100 The amount of vinyl cyanide compound in the resin phase was determined by elemental analysis of the recovered sample. In addition, the amount of vinyl cyanide compound in the graft phase was analyzed by decomposing the rubber phase in the graft rubber phase using a combination of osmium tetroxide and hydroperoxide, which is well known as an oxidative decomposition method for rubber. I took it out. Various methods have been reported regarding composition fractionation of this graft phase.
For example, J. Polymer Sci., Polymer Physics
The column fractionation method shown in Edition Vol. 19 1377 (1981) can be used. As a simpler method, the present inventors adjusted the mixing ratio of an acetone/methanol mixed solvent system and used a method of fractionating by centrifugation for the composition separation of the present invention. In particular, acetone/methanol 7/3 mixed solvent contains acrylonitrile content.
Less than 15% is insoluble and can be used for separation. The amount of vinyl cyanide compounds in the fractionated graft phase was determined by elemental analysis. The analysis results obtained by these methods were no different from the results obtained by extracting and analyzing each component from the final composition after blending with polyphenylene ether. Polystyrene, high-impact polystyrene, and styrene within the range that maintains the characteristics of the composition of the present invention.
It is also possible to add various butadiene-based block copolymers. Other additives may be added to the composition of the present invention, such as plasticizers, stabilizers, ultraviolet absorbers, flame retardants, colorants, mold release agents, and fibrous reinforcing agents such as glass fibers and carbon fibers, as well as glass beads and carbon dioxide. Fillers such as calcium, talc, etc. may be added. Particularly effective plasticizers include polybutene, low molecular weight polyethylene, mineral oil, epoxidized soybean oil, polyethylene glycol, and fatty acid esters. As stabilizers, phosphorous esters, hindered phenols, alkanolamines, acid amides, dithiocarbamic acid metal salts, inorganic sulfides, and metal oxides may be used alone or in combination. Can be done. Particularly effective flame retardants include aromatic phosphate esters, red phosphorus, aromatic halogen compounds, and antimony trioxide. Any method may be used to mix the components constituting the present invention, and for example, an extruder, heated roll, Banbury mixer, kneader, etc. can be used. Examples are shown below, but it goes without saying that the present invention is not limited to the following examples. Hereinafter, parts represent parts by weight. Impact strength: 150 x 150 x 2 injection molded at 290℃
A hemispherical missile with a radius of 1/2 inch with an appropriate weight attached to the center of a flat plate (mm) is dropped from a height of 150 cm, the load with a 50% probability of failure of the test piece is determined, and this load is added to the 150 cm The falling weight impact strength was determined and compared by multiplying by the height of . Solvent resistance was determined by immersing a dumbbell test piece of the type shown in ASTM D638, injection molded at 290°C and a mold temperature of 80°C, in cyclohexane for 24 hours at 23°C, then taking it out and measuring its weight 10 minutes later. The amount of cyclohexane absorbed was determined from the weight increase rate of , and the amount was evaluated based on the amount of absorption. The presence or absence of cracks on the surface of the immersion test piece was also evaluated. Regarding the appearance, the 60 degree specular gloss of the center of the dumbbell test piece was the same as that used for the solvent resistance test.
Measured and evaluated according to JISZ8741. Colorability evaluation is based on 100 parts of polyphenylene ether/impact polystyrene 40/60 resin.
TiO ₂ and carbon black were added, respectively, and standard samples for white and black coloring were determined as follows. Samples for evaluation are colored white and black by adding 3 parts of TiO ₂ and 0.5 parts of carbon black to 100 parts of resin, and visually judge which rank the coloring level of this product corresponds to by comparing it with the standard. method was used.

[Table] Typical methods for producing rubber reinforced resins are shown below. 40 parts solids of polybutadiene latex having a weight average particle diameter of 3500 Å and 100 parts water were charged into a reactor, and the temperature was raised to 70° C. in a nitrogen atmosphere while stirring. After reaching 70°C, a first monomer phase containing 9 parts of acrylonitrile, 21 parts of styrene, and 0.1 part of dodecyl mercaptan, and an aqueous solution of 0.1 part of potassium persulfate dissolved in 50 parts of water were each added continuously over 3 hours. After the addition was complete, a second monomer phase containing 30 parts of styrene and 0.1 part of dodecyl mercaptan, and an aqueous solution of 0.1 part of potassium persulfate dissolved in 50 parts of water were each added continuously for 3 hours. The polymerization was completed by keeping the temperature at 70°C for 2 hours. The conversion rate of the added monomers into polymer was 93%. This latex was salted out by adding aluminum sulfate, filtered, washed with water, and dried to recover the polymer. For comparison, a conventionally known ABS resin was manufactured by the method shown below. That is, 40 parts of solid content of the same polybutadiene rubber latex as above and 100 parts of water were charged into a reactor, and the temperature was raised to 70° C. in a nitrogen atmosphere while stirring. 70℃
After reaching , a monomer phase containing 18 parts of acrylonitrile, 42 parts of styrene and 0.2 parts of dodecyl mercaptan, and an aqueous solution of 0.2 parts of potassium persulfate dissolved in 50 parts of water were each added continuously over a period of 5 hours. After the addition was completed, the temperature was kept at 70°C for another 2 hours to complete the polymerization. Conversion rate of added monomers to polymer is 93%
It was hot. The polymer was recovered from this product through the same treatment. Table 1 shows the analysis results of these two types of polymers. In particular, regarding the fractionation of the amount of acrylonitrile in the graft phase, 1 g of the graft phase was added to the rubber obtained by decomposing the separated graft rubber phase using an osmium tetroxide-hydroperoxide system. 3 mixed solvents
The mixture was added to 25 ml, shaken and dispersed, centrifuged, separated into soluble and insoluble components, and the amount and acrylonitrile content of each was determined. The amount of acrylonitrile in the resin phase of this rubber reinforced resin and ABS resin was also determined.

[Table] Example 1 Intrinsic viscosity [η] at 30°C in chloroform is 0.62
50 parts of poly(2,6-dimethyl-1,4-phenylene) ether, 50 parts of the above rubber reinforcing resin, 0.5 part of Sumilizer BHT (hindered phenol manufactured by Sumitomo Chemical Co., Ltd.) as a stabilizer, and Mark PEP8 ( 0.5 part of distearyl pentaerythritol diphosphorite (Adeka Argus) was mixed in a blender, extruded into pellets using an extruder set at 300°C, and evaluated. As a comparison, a product with the same formulation except that the rubber reinforcing resin was replaced with the above ABS resin was also evaluated at the same time. The results are shown in Table-2. The composition of the present invention has higher impact strength,
and has excellent appearance. Furthermore, the colorability is improved and the solvent resistance is also at an excellent level. Conventionally known blends of ABS resin and polyphenylene ether are very brittle and have poor appearance and colorability.

[Table] Example 2 40 parts of the same polyphenylene ether as in Example 1, 40 parts of the above-mentioned rubber reinforcing resin of the present invention, and 20 parts of polystyrene (Asahi Kasei Styron 685) were added to Example 2.
The same stabilizer as in 1 was added and extruded into pellets using an extruder set at 300°C for evaluation. In addition, as a comparison, a product having the same composition except that the rubber reinforcing resin was replaced with the above ABS resin was evaluated in the same manner. The results are shown in Table-3.

[Table] Even products obtained by adding polystyrene to polyphenylene ether and the rubber reinforcing resin of the present invention maintain extremely excellent levels of impact strength, solvent resistance, appearance, and colorability. Example 3 40 parts of the polyphenylene ether of Examples 1 and 1, 30 parts of the above rubber reinforcing resin of the present invention, and 30 parts of a styrene-acrylonitrile copolymer with an acrylonitrile content of 4 wt% for dilution were added to the same stability as in Example 1. The mixture was extruded into pellets using an extruder set at 300°C and evaluated in the same manner as in Example 1. The results are shown below. Falling weight impact strength 800Kg-cm Solvent resistance Cyclohexane absorption crack occurrence 0.05wt% Gloss of non-dumbbell piece 90% Colorability (rank) black and white A A Styrene-acrylonitrile copolymer with acrylonitrile content of 4ωt% for dilution Even if the rubber content in the composition is reduced to 12 ωt%, a composition with very high impact strength and excellent solvent resistance, appearance, and colorability can be obtained. Comparative Example 1 Polymerization was carried out in exactly the same manner as in Example 1, except that 13 parts of acrylonitrile and 47 parts of styrene were used. Conversion rate of added monomers to polymer is 92%
It was hot. The polymer was recovered from this product through the same treatment. The analysis results of this polymer are shown below.

[Table] 30 parts of this polymer, 30 parts of polystyrene (Asahi Kasei Stylon 685), 40 parts of the same polyphenylene ether as in Example 1, and a stabilizer were added to form a pellet, and evaluated in comparison with Example 3. The results are shown below. Falling weight impact strength 250Kg-cm Solvent resistance Cyclohexane absorption crack occurrence 0.08ωt% Gloss of non-dumbbell piece 56% Colorability black and white B A Graft phase with acrylonitrile content of 10% by weight is small at 9wt% If it is, the impact strength and appearance are lower than the products of the present invention and are unsatisfactory. Solvent resistance and coloring properties are at a fair level. Comparative Example 2 A HIPS type resin containing no acrylonitrile was produced as follows. That is, 40 parts of polybutadiene latex having a weight average particle diameter of 3,500 Å in terms of solid content and 100 parts of water were charged into a reactor, and the temperature was raised to 70° C. in a nitrogen atmosphere while stirring. After reaching 70°C, the monomer phase containing 60 parts of styrene and 0.1 part of dodecyl mercaptan, and 0.3 parts of potassium persulfate were added to 50 parts of water.
Each of the aqueous solutions dissolved in 1 part was added continuously over a period of 6 hours, and after the addition was completed, the temperature was kept at 70°C for another 2 hours to complete the polymerization. The conversion rate of the added styrene monomer into polymer was 92%. The amount of grafting of this polymer was 54 wt%, and the amount of acrylonitrile in the graft phase and resin phase was 0. 30 parts of this HIPS type resin, 30 parts of polystyrene (Asahi Kasei Stylon 685), 40 parts of the same polyphenylene ether as in Example 1, and a stabilizer were added to form a pellet, and evaluated in comparison with Example 3. The results are shown below. Falling weight impact strength 600Kg-cm Solvent resistance Cyclohexane absorption crack occurrence 0.27wt% Yes Gloss of damper piece 70% Colorability (rank) black and white C C HIPS type resin that does not contain any acrylonitrile has no impact strength. Although it is fair, its solvent resistance is poor, and its appearance and coloring properties are also inferior to the products of the present invention. Example 4 4-1 to 4 were carried out under exactly the same conditions as in Example 1, except that the compositions of the first monomer phase and the second monomer phase were changed as shown in Table 4. Rubber reinforced resins up to -4 were manufactured. Table 5 shows the analysis of the graft phase and resin phase of 4-1 to 4-4 and the evaluation results using the same method as in Example 1. The compositions composed of rubber reinforced resins 4-1 and 4-2 exhibited an excellent balance in impact strength, solvent resistance, and colorability. Rubber reinforcing resin 4-3, in which the content of acrylonitrile at a high level of 27 wt% in the graft phase was 21 wt%, showed a tendency for cyclohexane absorption and colorability to decrease. In addition, a rubber reinforcing resin 4-4 containing 82 wt% of acrylonitrile with a content of 29 wt% tends to have a low falling weight impact strength.

【table】

【table】

[Table] Example 5 Rubber was produced using the same composition and conditions as in Example 1, except that the amount of dodecyl mercaptan in the first monomer phase and the second monomer phase was reduced from 0.1 to 0.05. Manufacture of reinforced resin was carried out. The conversion rate of the added monomer to polymer was 92%. The analysis results of this product are shown below. Grafting amount 98wt% Graft phase insoluble phase in acetone/methanol 7/3 Amount 43wt% Acrylonitrile amount 7wt% Graft phase soluble phase in acetone/methanol 7/3 Amount 57wt% Acrylonitrile amount 29wt% Also resin phase The amount of acrylonitrile in it was 8wt%. Example 1 except for using this rubber-reinforced resin
were evaluated in exactly the same way. The results are shown below. Falling weight impact strength 1000Kg-cm Solvent resistance Cyclohexane absorption Presence or absence of cracks 0.06wt% None Gloss of dumbbell piece 83% Colorability (rank) Black and white A A Example 6 Polyphenylene ether in the composition of Example 2 Intrinsic viscosity [η] (chloroform 30℃) is 0.65
2,6-dimethylphenol (90 mol%)
The evaluation was carried out under exactly the same composition and conditions, except that a copolymer of and 2,3,6-trimethylphenol (10 mol %) was used. The results are shown below. Falling weight impact strength 750Kg-cm Solvent resistance Cyclohexane absorption Presence or absence of cracks 0.05wt% None Gloss of dumbbell piece 83% Colorability (rank) Black and white B A Example 7 Production of rubber reinforced resin used in Example 1 In the method, the styrene in the first monomer phase and the second monomer phase is 57 wt% styrene and α-methylstyrene.
A rubber-reinforced resin was produced using exactly the same composition and conditions, except that the polymerization was performed by replacing the mixed system with 43 wt%. The conversion rate of the added monomer into the polymer was 90%. The analysis results of this product are shown below. Grafting amount 64wt% Graft phase insoluble phase in acetone/methanol 7/3 Amount 41wt% Acrylonitrile amount 7wt% Graft phase soluble phase in acetone/methanol 7/3 Amount 59wt% Acrylonitrile amount 29wt% Also resin phase The amount of acrylonitrile in it was 10wt%. Evaluation was performed in exactly the same manner as in Example 2 except for using this rubber-reinforced resin. The results are shown below. Falling weight impact strength 700Kg-cm Solvent resistance Cyclohexane absorption Presence or absence of cracks 0.05wt% None Gloss of dumbbell piece 80% Coloration (rank) Black and white B A

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are diagrams schematically showing the distribution state of the amount of vinyl cyanide compound contained in the graft phase of the rubber reinforcing resin.

Claims (1)

[Claims] 1 The following components (a) and (b): (a) General formula [Formula] [Formula] (wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are A monovalent substituent such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, hydrogen, etc., excluding the same or different tertiary butyl group, and R ₅ and R ₆ are not hydrogen at the same time) as a repeating unit 10 to 80% by weight of a polyphenylene ether resin consisting of a homopolymer or copolymer whose constituent units are [ ] or [ ] and [ ] (b) 90 to 20% by weight of a rubber reinforcing resin, and the component ( Regarding b), the elastomer rubber phase is graft copolymerized with a vinyl cyanide compound and a vinyl aromatic compound, the amount of grafting is 20% by weight or more, and the graft phase is at least the following (I). ) and (b), and (b) a copolymer of a vinyl cyanide compound and a vinyl aromatic compound containing 15 to 40% by weight of vinyl cyanide compound (90 to 10% by weight). ) A copolymer of a vinyl cyanide compound and a vinyl aromatic compound with a vinyl cyanide compound content of 1 to 15% by weight (10 to 90% by weight) The average amount of vinyl cyanide compounds in the resin phase other than this graft rubber phase is 1 to 15% by weight. A polyphenylene comprising a copolymer of a vinyl cyanide compound and a vinyl aromatic compound in the range of ~15% by weight, or a blend of this copolymer and a polymer of a vinyl aromatic compound. Ether resin composition. 2 The vinyl aromatic compound has the following formula: (In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group, and Z represents a hydrogen atom, a halogen atom,
It represents a vinyl group or an alkyl group, and p represents an integer of 1 to 5. ) Claim 1
Compositions as described in Section. 3. The composition according to claim 1, wherein the polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene) ether. 4. The composition according to claim 1, wherein the polyphenylene ether is a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. 5. The composition according to claim 1, wherein the vinyl aromatic compound is styrene. 6. The composition according to claim 1, wherein the vinyl aromatic compound consists of styrene and α-methylstyrene. 7 Vinyl cyanide compound is acrylonitrile,
The composition according to claim 1, which is methacrylonitrile or a mixture of both. 8. The composition according to claim 1, wherein the vinyl cyanide compound is acrylonitrile. 9 Elastic rubber phase is polybutadiene, styrene.
Claim 1 is one or a mixture of two or more selected from butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-nonconjugated diene terpolymer, and polyacrylic acid alkyl ester. Compositions as described in Section.