JPS58129049A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:A composition, prepared by inorporating a specific copolymer of acrylonitrile with a vinyl aromatic compound in a polyphenylene ether (PPE) resin, and having improved mixing characteristics of the PEE resin with the copolymer of the acrylonitrile with the vinyl aromatic compound, solvent resistance and high practicality. CONSTITUTION:A polyphenylene ether resin composition prepared by incorporating (A) polyphenylene ether resin with (B) a copolymer of acrylonitrile with a vinyl aromatic compound containing 0-8wt% acrylonitrile, (C) a copolymer of acrylonitrile with a vinyl aromatic compound containing 10-35wt% acrylonitrile and (D) a rubbery elastomer to give 10-80wt% component (A), and 90-20wt% total of the components (B) and (C) and 0-25wt% component (D) at >=0.2 weight ratio of the component (B) to components (B) and (C). Styrene, alpha-methylstyrene, etc. may be used as the vinyl aromatic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition that is highly practical and has excellent solvent resistance.

Polyphenylene ether resin has excellent mechanical properties, electrical properties, and heat resistance, as well as low wood growth and good dimensional stability. This resin has been improved by blending it with high-impact polystyrene and has become widely used in recent years. However, polyphenylene ether resin and polyphenylene ether and impact-resistant polystyrene have the disadvantage that they easily crack (stress cracks), especially when they come into contact under stress.

For this reason, their applications are severely limited, and improvements are in great demand.

Proposals have been made to improve the stress crack resistance of such polyphenylene ether resin compositions. For example, JP-A No. 48-42047 discloses that high molecular weight polystyrene is used.
HA-B-A' in Publication No. 2851! 'The elastomer block can be made of one alloy and one alloy, as disclosed in JP-A-F$50-717.
No. 42 proposes adding a hydrogenated block copolymer. 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. In addition, US Pat. No. 3,383,435 describes acrylonitrile-butadiene-styrene copolymer (ABS resin) and poly(2,
6-dimethyl-1°4-phenylene) ether is described. However, the US patent contains 16 acrylonitrile units, 41% styrene units,
Although a blending example of ABS resin with butadiene unit 431i and polyphenylene ether is shown, as shown in the physical property comparison with polystyrene or high-impact polystyrene in the US patent, ABS resin and polyphenylene ether The compatibility with ether is extremely rapid, and the resulting composition is extremely brittle and cannot be put to practical use.

In order to obtain a resin composition that has excellent solvent resistance and is truly usable for practical use, the inventors of the present invention have conducted extensive research and mold testing, and have found that a vinyl aromatic compound containing acrylonitrile in an amount of 8% or less by weight, and acrylonitrile It has been found that a copolymer containing acrylonitrile of 10 to 35% by weight can improve the mixing characteristics of a copolymer of rylonitrile and a vinyl aromatic compound with a phenylene ether resin, and the composition of the present invention This is what I came to obtain.

That is, the present invention provides the following components (&1 to (d): (at
#IJ phenylene ether resin, (bl A copolymer of acrylonitrile and a vinyl aromatic compound containing acrylonitrile Io to 8 weight range, (al A copolymer of acrylonitrile and a vinyl aromatic compound containing 10 to 35 weights of acrylonitrile! copolymer, and (dl) consisting of a rubber-like elastic body, (&) component being 10 to SOX*, (total of bl component and (cl component being 90 to 20% by weight, (dl component being 0 to 25% by weight) in the overlapping part, and (bl component and fa
The weight ratio of the bl component to the total weight with the t component Gbl
/ (bl + (cl)) is related to a thermoplastic resin composition of 0.2 or more.

In the present invention, polyphenylene ether resin (PPE
), a homopolymer or a copolymer having the general formula; as a repeating unit and consisting of [■] or [■] and [Ten] as constituent units can be used.

A typical example of a PPE homopolymer is poly(2,6-
dimethyl-1,4-phenylene)ether, poly(2-
methyl-6-ethyl-1,4-phenylene) ether,
Poly(2,6-ethyl-1,4-)unilene) ether, poly(2-ethyl-6-nf propyl-1,4-)unilene) 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-imbrobyl-1,4-phenylene) ether, /IJ(2-methyl-6-10-1,4-)unilene) ether, Fo1J(2-methyl-6-hydroxyethyl-1,4-phenylene) ) ether, poly(2-
Examples include homopolymers such as methyl-6-chloroethyl-1,4-phenylene) ether.

The polyphenylene ether copolymer has the general formula (R
M s Ra S Director@ has the same meaning as above. )
It includes a polyphenylene ether copolymer mainly having an IJ methyllene ether structure represented by 2, 3, 6-).

These polymers can also contain various common auxiliary materials such as stabilizers, plasticizers, and the like. Furthermore, these polymers may be entirely grafted with monomers having styrene as the king moiety.

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 and it will have no practical value, and if it exceeds 80% by weight. In this case, the deterioration of workability becomes significant, so a weight range of 10 to 80% is desirable.

The copolymers of acrylonitrile and a vinyl aromatic compound used in the present invention are those containing 0 to 8 times acrylonitrile (component (b)) and those containing 10 to 35 times acrylonitrile ((C). ) component).

The vinyl aromatic compound used in the (bl component and (cl component) of the present invention has the following general formula: or an alkyl group, and p is an integer of 1 to 5. , α-methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, t@
Examples include rt-butylstyrene and chlorstyrene.

(If the acrylonitrile content in the bl component exceeds 8 weight range, the mixing properties will deteriorate and the resulting composition will become very brittle, so the acrylonitrile content in component (b) should be within the range of 0 to 8 weight range. There needs to be.

In addition, (the acrylonitrile content in the Cl component is 101jL)
If it is less than I#, the effect of improving the stress cracking resistance of the resulting composition will not be sufficient, and if it exceeds 35, only a brittle composition will be obtained. (The acrylonitrile content of the Cl component is preferably in the range of 10 to 35%.

(b1 and (cl) components can be produced by any of the methods well known to those skilled in the art, such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

(The BL component and/or the CL component are polymerized in the presence of the rubber-like elastic material shown below, and if the amount is less than 90%, the scrapability and chemical resistance will be insufficient.
If the amount exceeds 1 part by weight, the heat resistance will decrease and the practical value of the resin composition will decrease.

Of the total addition amount of (bl component and (cl component), (bl
If the proportion of the components is less than 200 parts by weight, only a very brittle resin composition can be obtained. Therefore, the weight ratio ((bl
/ (bl + lel) is preferably 0.2 or more.

Incidentally, the fractionation of copolymers with different ratios of (BL component and IEL component, that is, composition ratio) in a resin composition can generally be determined by analysis by fractionation by phase separation, fractionation by adsorption, etc. For example, J. Polym.

Sci Polym, Phys, Edition,
In 1981, it was reported that acrylonitrile-styrene copolymers having different composition ratios could be separated by column fractionation. Furthermore, according to the present inventors, MEK is used as a good solvent.
Not only can this polystyrene and acrylonitrile-styrene copolymer be separated by a precipitation fractionation method using n-hebutane as a poor solvent, but also acrylonitrile-styrene copolymers with different composition ratios can be separated.
Styrene copolymer f: was able to be separated by component a.

The rubber-like elastic body used in the present invention is / lj butadiene,
Styrene-butadiene copolymer, butadiene/I
Jronitrile copolymer, styrene-butadiene block copolymer or its hydrogenated product, ethylene-propylene copolymer, ethylene-zolopylene-ethylidenenor lunenter polymer, ethylene-zolopylene-dicyclopentadiene terpolymer, 181 or more can be selected from polyacrylic acid alkyl ester, polyisogrene, natural rubber, etc., and the addition # may be used in the range of 0 to 25 fii depending on the target strength level of the final composition.

The composition of the present invention may contain other additives, such as plasticizers, stabilizers, ultraviolet absorbers, flame retardants, colorants, mold release agents, and fibrous materials such as glass fibers and carbon fibers. Fillers such as raspise, calcium carbonate, talc, etc. may be added.

Plasticizers include polybutene, low molecular weight polyethylene,
Effective for 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. Particularly effective flame retardants that can be used 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.

Toughness is 150 x 150 x 2 injection molded at 290℃
A hemispherical missile with a radius of 1/2 inch with a load of (+w+) attached to the center of a flat plate of ! Judgment was made based on 11g1.

Stress crack resistance was measured by compression molding at 250°C.
A test piece of 00 x 12.7 x 3 (-) was attached to a linear bending mold and subjected to uniform and continuous strain, and then heated at 23℃K for 11m. All cracks that had occurred in the test piece after being immersed for 10 minutes in the test piece were observed, the curvature of the point where the crack started was determined, and the strain of the test piece at this point was calculated and evaluated as the critical strain.

Parts in Comparative Examples and Examples are parts by weight.

(Aggregation of acrylonitrile-styrene copolymer) Water 12
0 parts by weight and 1.0 parts by weight of disproportionated potassium rosin acid were charged into a reactor, and the temperature was raised to 70°C.

After that, a total of 100% of acrylonitrile and styrene
Parts by weight and 02 parts by weight of dodecyl mercaptan and an aqueous solution of potassium persulfate in which 0.5 parts by weight of potassium persulfate is dissolved in 30 parts by weight of water are added separately and continuously over 7 hours. After the addition was completed, the temperature was kept at 70°C for an additional 2 hours to complete the polymerization.

The resulting polymer latex was salted out by adding aluminum sulfate, filtered, washed with water, and dried, and used in a blending experiment.

Acrylonitrile-styrene copolymers having various acrylonitrile contents were obtained by appropriately changing the addition ratio of acrylonitrile and styrene.

The polymerization rate was 95 or higher in all cases.

(Polymerization of acrylonitrile-butadiene-styrene copolymer) 40 parts by weight of polybutadiene latex with a weight average particle size of 5000A and 100 parts by weight of water were charged into a reactor and the temperature was 70°C.
The temperature rose to .

Thereafter, an aqueous solution of potassium persulfate in which a total of 60 parts by weight of acrylonitrile and styrene, 0.1 parts by weight of dodecyl mercaptan, and 0.3 parts by weight of potassium persulfate were dissolved in 50 parts by weight of water was separately heated for 5 hours. Add continuously. After the addition was completed, the temperature was kept at 70°C for an additional 2 hours to complete the polymerization.

The resulting polymer latex was salted out by adding aluminum sulfate, filtered, washed with water, and dried, and used in a blending experiment.

By appropriately changing the addition ratio of acrylonitrile and styrene, acrylonitrile-butadiene-2-styrene copolymers having various acrylonitrile contents were obtained. The polymerization rate was 934 or higher in all cases.

Comparative Example 1 Intrinsic viscosity [η] (chloroform 30°C)
ATON-G1650 (5 parts of Hydrogen Kita styrene-butadiene block copolymer from Shell Chemical Company and 0.5 part of Sumilizer BHT (hindered phenol from Sumitomo Chemical Co., Ltd.) as a stabilizer and Mark PEP8
(Disguaryl intererythritol diphosphite manufactured by Adeka Argus)) were mixed in a Dojim blender and extruded into pellets using an extruder set at 300°C.

The drop strength and solvent resistance were as shown below.

Strength 600 kg - The composition contained no acrylonitrile and had extremely low critical strains for gasoline and cyclohexane.

Comparative Example 2 Poly(2,6-dimef) having an intrinsic viscosity [η] of 0.62
A composition consisting of 50 parts of (1.4-phenylene) ether and 0.5 parts of AN ratio (acrylonitrile weight/(acrylonitrile + nutylene compound) weight, same hereinafter) was evaluated in the same manner as Comparative Example 1 and had the following physical properties. Got the value.

Drop impact strength 10kl? -1 The composition is very similar to Sample U of Example 11 of U.S. Pat. No. 3,383,435 and is 1. The acrylonitrile-styrene copolymer component had an AN ratio of 0.28 and contained only 1ai, but its impact strength against impact was extremely low and it was brittle.

Comparative Example 3 Poly(2,6-dimef) having an intrinsic viscosity [η] of 0.62
(1,4-phenylene)ether 40m, AN ratio 0.
40 parts of acrylonitrile-butadiene-styrene copolymer (611 AN units, 54 styrene units, 40 butadiene units), 20 g of an acrylonitrile-styrene copolymer with an AN ratio of 0.10, and Sumilizer BIT0 .5 parts and 0.5s of mark PEP8
A composition consisting of was evaluated in the same manner as in Comparative Example 1, and the following physical property values were obtained.

Drop impact strength: 10 kg-(7) or less This composition also has an AN ratio of 0.0 as an acrylonitrile-styrene copolymer component. It was very brittle and did not contain anything similar to lO.

Comparative Example 4 The AN ratio of acrylonitrile-butadiene-styrene copolymer and acrylonitrile-styrene copolymer was 09
The evaluation was carried out in exactly the same manner as in Comparative Example 3 except that 05 was used, and the following physical properties were obtained.

Drop impact strength i 600 to 9-cIn The acrylonitrile-styrene copolymer component in this composition is A
It contained only those with a low N content and an AN ratio of 0.05, and the critical strain for gasoline and cyclohexane was extremely low.

Comparative Example 5 Acrylonitrile-butadiene with AN ratio of 0.40
The physical properties of a composition obtained in the same manner as in Comparative Example 3 except that 40 parts of a styrene copolymer and 20 parts of an acrylonitrile-styrene copolymer having an AN ratio of 0.05 were used were as follows.

Drop impact strength 80 kg-cm Example 1 Evaluation was completely the same as in Comparative Example 3 except that the AN ratio of the acrylonitrile-butadiene-styrene oligopolymer and the acrylonitrile-styrene copolymer was set to 0.20 and 0.05, respectively. The following physical property values were obtained.

Drop impact strength: 250 Y-σ As described above, it can be seen that the composition of the present invention has an excellent balance between impact resistance and stress crack resistance.

Example 2 The following physical property values were obtained by conducting the same evaluation as in Comparative Example 3, except that the AN ratios of the acrylonitrile-butadiene-styrene copolymer and the acrylonitrile-styrene copolymer were set to 0.15 and 0.05, respectively. .

Falling S break strength 300k17 - Confucian Example 3 The evaluation was carried out in exactly the same manner as in Example 2 except that the acrylonitrile-styrene copolymer was changed to polystyrene-Styron 685 (GP polystyrene manufactured by Asahi Dow Co., Ltd.) with an AN ratio of 0. The following physical property values were obtained.

Chicken Example 4 40 parts of the acrylonitrile-butadiene-styrene copolymer of Comparative Example 3 with an AN ratio of 0.10 and 20 parts of the acrylonitrile-styrene copolymer with an AN ratio of 0 and 1O were mixed with AN ratios of 0.30 and 0. Comparative Example 3 except that the acrylonitrile-butadiene-styrene co-3 with 05 was substituted at 3
A composition was obtained in the same manner as above. The physical properties of this composition were as follows.

Drop impact strength: 400 kg~Example 5 Completely the same evaluation as Comparative Example 3 except that the AN ratios of the acrylonitrile-butadiene-styrene copolymer and the acrylonitrile-styrene copolymer were set to 0.05 and 0.20, respectively. The following physical properties were obtained.

Drop impact strength 200kl? - Bullet Example 6 40 parts of poly(2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity [η] of 0.66, ANNO3
A composition consisting of 30 parts of 15 and 0.05 acrylonitrile-styrene copolymers, 15 parts of KRATON-G1650't as a 15-gum rubbery elastic body, and 1.0 part of Sumilizer B HT was prepared in the same manner as in Comparative Example 1. The following physical property values were obtained.

Drop impact strength 250 to 9-F (polymerization of acrylonitrile-styrene-α-methylstyrene copolymer) 120 parts by weight of water and 1.0 parts by weight of disproportionated potassium rosin acid were placed in a reactor and heated to 70°C. It was warm. After that, add 51 parts of acrylonitrile and 550.5 parts of styrene to 3 parts of water.
An aqueous solution of potassium persulfate dissolved in 1° part of the solution was added separately and continuously over a period of 10 hours. After the addition was completed, the temperature was kept at 70°C for an additional 3 hours to complete the polymerization. The polymerization rate is 9
3, the acrylonitrile content in the polymer was low.

The obtained monomer latex was salted out by adding aluminum sulfate, filtered, washed with water, dried, and used in a blending experiment.

(Polymerization of acrylonitrile-butadiene-styrene-α-methylstyrene copolymer) 40 parts by weight of polybutadiene latex with a weight average particle size of 5000 A and 100 parts by weight of water were charged into a reactor and the mixture was heated at 70°C.
The temperature rose to .

After that, 12 parts by weight of acrylonitrile, 20 parts by weight of styrene
parts by weight, 1 part by weight of α-methylstyrene, 0.1311 t part of dodecyl fish captan, and 0 parts of potassium persulfate.
．． An aqueous solution of potassium persulfate, 3 parts by weight dissolved in 50 parts by weight of water, is added separately and continuously over a period of 7 hours.

After the addition was completed, the mixture was further kept at 70° C. for 2 hours to complete the polymerization. The polymerization rate of the obtained polymer was 95, and the amount of acrylonitrile was 122 parts by weight. The obtained polymer latex was salted out by adding aluminum sulfate, filtered, washed with water, dried, and used in a blending experiment.

Example 7 ANN as a substitute for acrylonitrile-styrene copolymer
Evaluations were carried out in exactly the same manner as in Example 1, except that O305 acrylonitrile-styrene-α-methylstyrene copolymer was used, and the following physical property values were obtained.

Drop impact strength 220k17-tM (
Cyclohexane 0.42 Example 8 40 parts of acrylonitrile-butadiene-styrene copolymer of Comparative Example 3 and acrylonitrile-styrene copolymer 2
0 part and 40 parts of acrylonitrile-butadiene-styrene-α-methylstyrene copolymer of ANNO320 and A
A composition was obtained in the same manner as in Comparative Example 3, except that NNO305 was replaced with 20 parts of acrylonitrile-styrene-α-methylstyrene copolymer. The physical properties of this composition were as follows.

Drop impact strength 180kl? - Confucian Example 9 2,6-dimethylphenol (90 molar width) whose intrinsic viscosity [η] (chloroform at 30°C) is 0.65 and 2.3
．． 40 parts of a copolymer with 6-1 trimethylphenol (10 molar width), 40 parts of an acrylonitrile-butadiene-styrene copolymer of ANNO320, 20 parts of an acrylonitrile-styrene copolymer of ANNO305, and 0.5 part of Sumilide BHT. A composition comprising 0.5 part of Mark PEP8 was evaluated in the same manner as in Comparative Example 1, and the following physical property values were obtained.

Drop impact strength: 290 Yen As described above, it can be seen that the composition obtained in this example has an excellent balance between toughness and oil resistance.

Comparative Example 6 Intrinsic viscosity [η10.64 PoIJ (2,6-dimethyl-1,4-phenylene)ether 40111, real 11n
A composition was prepared by the method of Comparative Example 1 using 60 parts of the polystyrene used in Example 3, and the physical properties were measured as follows.

Heat distortion temperature 121°C (ASTM0648) Comparative Example 7 60 parts of acrylonitrile-styrene copolymer which is ANNO315, poly(
2,6-dimethyl-1,4-)unilene)ether 40
A composition was obtained using the same method as in Comparative Example 1. The physical properties of the obtained composition were as follows.

Heat distortion temperature 103℃ (A8TMD648) Poly(2,6-cymethyl-1゜4-) with intrinsic viscosity 0.64
phenylene) ether, 30 parts of ANNO315 acrylonitrile-styrene copolymer, ANNO305
A composition was obtained in the same manner as in Comparative Example 1 using 30 parts of acrylonitrile-styrene copolymer. The physical properties of the obtained composition were as follows.

Heat deformation temperature: 125°C As described above, it can be seen that even when the rubber-like elastic body is not contained at all, the composition of the present invention is a composition with an excellent balance between heat resistance and oil resistance, especially heat resistance. .

Agent Masaru San's husband 1 other person

Claims (1)

[Scope of Claims] (1) The following components (at to (d): fat polyphenylene ether resin, (bl copolymer of acrylonitrile and vinyl aromatic compound containing 0 to 8 weight of acrylonitrile, (cl acrylonitrile 110) A copolymer consisting of acrylonitrile and a vinyl aromatic compound containing ~35% by weight, and (di) consisting of a rubber-like elastic body, with an ial component ranging from 10 to 80% by weight, and a total of (bl component and (cl component) ranging from 90% to 90% by weight). 20 weight range, (di acid component is in the range of 0 to 25 weight ill, and Tbl component and I
Heavy electric ratio polyphenylene ether resin composition of Tbl component for a total type lid with clfi component. (2) The vinyl aromatic compound has the following formula: (wherein, R represents a hydrogen atom, a halogen atom, or an alkyl group, 2 represents a hydrogen atom, a halogen atom, a vinyl group, or an alkyl group, and p#'11 to 5 The composition according to claim 1, which is an integer of . (3) The composition according to claim 1, wherein the rubber-like elastic body is grafted with a part of component (b) and/or component (cl). 2,6-dimethyl-1,4-)unilene) ether, l? A composition according to claim 1. 2. The composition of claim 1, wherein the (5-polyphenylene ether) is a copolymer of 2,6-dimethylphenol and 2,3,6-)limethylphenol. (6) The composition according to claim 1, wherein the vinyl aromatic compound is styrene. (7) Claim 1, wherein the vinyl aromatic compound is composed of styrene and α-methylstyrene. (81=7') The composition according to claim 1, wherein the mucous elastomer is polybutadiene, styrene-butadiene copolymer, or ethylene-f-robylene copolymer.