JPH03185058A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of a specific resin component, a random copolymer of a vinyl aromatic compound and a conjugated diene compound, etc., having improved compatibility and excellent rigidity, heat-resistance, chemical resistance, etc., and useful as automobile parts, etc. CONSTITUTION:The objective composition can be produced by compounding 97-65wt.% of a resin component composed of (A) 5-95wt.% of a polyphenylene ether and (B) 95-5wt.% of a polyolefin with (C) 3-35wt.% of a random copolymer composed of a vinyl aromatic compound (preferably styrene) and a conjugated diene compound, having a number-average molecular weight of 5,000-1,000,000 and a molecular weight distribution of <=10 and containing 30-75wt.% of the vinyl aromatic compound or the hydrogenation product of the copolymer and, as necessary, adding various plasticizers, heat-stabilizers, etc. Preferably, the composition is further compounded with 0.2-5 pts.wt. (based on 100 pts.wt. of A+B+C) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene which is a phosphorus compound to improve the color tone of the composition.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is applicable to the electrical/electronic field, the automobile field, etc., which has excellent heat resistance, impact resistance, chemical resistance, and moldability, and has improved color tone. The present invention relates to a thermoplastic resin composition that can be used as a raw material for various molding materials.

[Conventional technology]

Although polyphenylene ether has excellent transparency, mechanical properties, electrical properties, and heat resistance, low water absorption, and excellent dimensional stability, the melt-molded product shows a reddish-brown color and has poor color tone, and has poor moldability and impact resistance. However, by blending it with polystyrene and non-impact polystyrene, the problems of moldability and impact resistance are improved.
For example, it is widely used in industrial parts, electrical/electronic parts, office equipment, automobile parts, precision parts, etc.

However, although the classical polyphenylene ether resin composition (disclosed in U.S. Pat. No. 3,383,435) consisting of polyphenylene ether and impact polystyrene has improved impact resistance, it has poor chemical resistance. It has disadvantages that are inferior to.

For this reason, for example, U.S. Pat.
No. 994,856 describes improvement in impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and styrene resin with a hydrogenated block copolymer, and U.S. Pat.
No. 45377 describes polyphenylene ether or polyphenylene ether and styrenic resin blended with a premix consisting of polyolefin/hydrogenated block copolymer=20 to 80 parts by weight/80 to 20 parts by weight and hydrogenated block copolymer. There is a description of improvement of impact resistance and solvent resistance by
No. 66,055 and US Pat. No. 4,239,673 describe improved impact resistance by blending polyphenylene ethers with hydrogenated block copolymers and polyolefins. and U.S. Patent No. 4
383082 and European Published Patent No. 11
No. 5712 describes blending polyphenylene ether with a polyolefin and a hydrogenated block copolymer to improve impact resistance.

Also, JP-A-63-113058, JP-A-63-
Publication No. 225642, JP-A-1. -98647 publication,
JP-A-1-204939 and JP-A-Hei! -2214
Publication No. 44 proposes a resin composition with excellent chemical resistance and processability by blending a specific hydrogenated block copolymer to modify a resin composition consisting of a polyolefin resin and a polyphenylene ether resin. .

On the other hand, the present applicant has published Japanese Patent Application Laid-Open No. 63-218748,
JP-A-63-245453 and JP-A-64-4
No. 0556 proposed a resin composition with excellent chemical resistance and processability, consisting of polyphenylene ether and polyolefin, using a specific block copolymer as a compatibilizer.

Furthermore, the present applicant has disclosed JP-A-59-98160, JP-A-59-98161, and JP-A-60-99161 in order to improve the color tone of the polyphenylene ether resin composition described above during melt molding. In the publication, we proposed a polyphenylene ether resin composition with excellent color tone using various phosphorus compounds.

Furthermore, in Japanese Patent Publication No. 59-27775, the present applicant has disclosed a flame-retardant material comprising a graft copolymer obtained by grafting a styrene compound to polyphenylene ether and 9°10-dihydro-9-oxa-10 phosphor phenanthrene. proposed a synthetic graft copolymer composition.

[Problem to be solved by the invention]

However, the prior art regarding resin compositions blended with these polyphenylene ethers and polyolefins has poor solvent resistance, impact resistance, and Although the effect of improving properties is recognized, the performance is insufficient, and in particular, these resin compositions are substantially composed of 50% by weight or more of phenylene ether and 20% by weight or less of polyolefin. When produced using the prior art, the layer peeling phenomenon occurs significantly, and the color tone of the resulting composition is also insufficient with the prior art, which does not meet the performance requirements of plastics, which are becoming more sophisticated year by year as various industrial materials. leaving a mark.

The object of the present invention is to improve the compatibility between polyphenylene ether and polyolefin, which was not possible in the prior art described above.
The purpose of the present invention is to provide a polyphenylene ether alloy that has improved properties such as delamination (layer peeling phenomenon) and a high level of chemical resistance, and furthermore, to provide a polyphenylene ether alloy that has improved color tone in addition to these performances.

[Means to solve the problem]

In view of the current situation, the present invention aims to improve polyphenylene ether without impairing its basic properties as much as possible.
In order to improve chemical resistance, which is a drawback, the present applicant has already proposed Japanese Patent Publication No. 59-27775 and Japanese Patent Application Laid-open No. 59-981.
60, JP-A-59-98161, JP-A-6
Publication No. 0-99161.63-218748, 63-2
As a result of further intensive studies based on JP-A No. 45453 and JP-A-64-40556, we have found that a specific random copolymer and its hydrogenated product can be used to modify a resin composition consisting of polyphenylene ether and polyolefin. By using it as a riser, we have found that a thermoplastic resin composition with excellent compatibility (layer peeling phenomenon), impact resistance, and chemical resistance under stress can be obtained. The present inventors have discovered that by providing a phosphorus compound having the above properties, a thermoplastic resin composition can be obtained which has further improved color tone in addition to these properties, and has arrived at the present invention.

That is, the present invention provides: 1. (a) Polyphenylene ether 5 to 95 ff
i% (b) Resin component consisting of 95 to 5% by weight of polyolefin 97 to 65% by weight (c) Vinyl aromatic compound-conjugated diene compound random copolymer containing 30 to 75% by weight of vinyl aromatic compound or its hydrogen 2. (a) Polyphenylene ether 5-951
Amount % (b) Resin component consisting of 95-5% by weight of polyolefin 97-65% by weight
(c) Vinyl aromatic compound-conjugated diene compound random copolymer containing 30 to 75% by weight of vinyl aromatic compound or hydrogenated product thereof 3 to 35% by weight (d)9.
A thermoplastic resin composition comprising 0.2 to 5 parts by weight of 10-dihydro-9-oxa-10-phosphaphenanthrene based on a total of 100 parts by weight of the above components (a) to (C). It provides:

The present invention will be described in detail below.

The polyphenylene ether (hereinafter simply abbreviated as PPE) used as component (a) of the present invention has a bonding unit: (Here, R1, R2, R3, and R4 are each
selected from the group consisting of hydrogen, halogen, hydrocarbon, or substituted hydrocarbon groups, which may be the same or different, and have a reduced viscosity (0.5 g/d
i, chloroform dissolution, 30"C measurement) is 0, 15~
0.7(1) range, more preferably 0.20-0.60
homopolymers and/or copolymers within the range of Specific examples of this PPE include poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like. Among these, poly(2°6-dimethyl-1,4-phenylene ether) is preferred.

The method for producing such PPE is not particularly limited as long as it can be obtained by a known method. For example, using a complex of a cuprous salt and an amine by Hay described in U.S. Pat. No. 3,306,874 as a catalyst, For example 2
．． It can be easily produced by oxidative polymerization of 6-xylenol, and is also available in US Pat. No. 3,306,875, US Pat. No. 3,257,357, and US Pat.
Specification No. 257358, and Japanese Patent Publication No. 17880/1983
No. 50-51197, JP-A No. 63-
It can be easily produced by the method described in Japanese Patent No. 152628 and the like.

In addition to the above-mentioned PPE, the PPE used as component (a) of the present invention can also be prepared by combining the PPE with a vinyl aromatic compound or an α,β-unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator. It may be a known modified (0.01 to 10% by weight grafted or added) PPE obtained by reacting in the presence of a molten state, a solution state, a slurry state at a temperature of 80 to 350 °C, and It may be a mixture of the above-mentioned PPE and the modified PPE in any proportion. Among them, JP-A-63-15
PPE in which a styrene monomer is added to the PPE terminal with a chroman structure by the method described in Japanese Patent No. 2628 is preferably used.

In addition, as the PPE of this (a) component, an additional 9°10
-dihydro-9-oxa-10-phosphaphenanthrene P P E 1001! It is also possible to provide PPE treated with a phosphorus compound, which is obtained by adding 0.2 to 5 parts by weight of the phosphorus compound and melt-kneading the phosphorus compound.

Next, (b) li32. of the present invention. Examples of the polyolefin used as a component include high-density polyethylene, ultra-high molecular weight high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene with a density of less than 0.90, isotactic polypropylene, ethylene, and propylene. , other α-olefins, copolymers of two or more compounds returned from unsaturated carboxylic acids or derivatives thereof, such as ethylene/butene-1 cofI polymer elastomers, ethylene (meth)acrylic acid copolymers, ethylene - (meth)acrylic acid ester copolymer, propylene/ethylene (random, block) copolymer resin, propylene/1-hexene copolymer, propylene/4-methyl-1-pentene copolymer, and poly(4 -Methyl-
1-pentene), polybutene-1, etc., and these can be used not only alone but in combination of two or more.

Next, the random copolymer used as component (C) a in the present invention is a copolymer obtained by random copolymerization of a vinyl aromatic compound and a conjugated diene compound.

The random copolymer of component (e) contains 30 to 15111% of a vinyl aromatic compound, preferably 35 to 7% by weight, and more preferably 40 to 65% by weight of a vinyl aromatic compound. Ratio of the amount of polymer blocks of vinyl aromatic compounds in the total amount of copolymerized vinyl aromatic compounds (hereinafter abbreviated as block ratio, block ratio - ■ polymer blocks of vinyl aromatic compounds contained in the copolymer) Amount ÷
■Total amount of vinyl aromatic compounds contained in the copolymer x 10
0%) is substantially 30% or less, more preferably 15% or less.

In addition, as a method of knowing the polymer block amount of the vinyl aromatic compound contained in the copolymer (2), for example, L,
M, KOLTHOFF, at al, , J, P
olym, Set, 1.429 (1946), or by the method described in Japan Rubber Association Line 54, 9, 564 (1984). It can be obtained by ozonolysis of the amalgam.

In addition, methods for determining the total amount of vinyl aromatic compounds contained in the copolymer (①) include determining the refractive index of the random copolymer, or setting it to the absorption wavelength derived from the vinyl aromatic compound (for example, styrene). It can be easily measured by using an ultraviolet absorption photometer (254 nm).

As the vinyl aromatic compound constituting this random copolymer, for example, one or more than 2i can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, etc. Styrene is preferred. Further, as the conjugated diene compound, for example, one or more types are selected from butadiene, isoprene, 1,3-pentadiene, 2゜3-dimethyl-1,3-butadiene, etc. Among them, butadiene, isoprene, and Combinations of these are preferred.

In this random copolymer, the microstructure of the bonding form of the conjugated diene compound, which is the copolymerization component, can be arbitrarily selected. For example, in the case of butadiene,
1,2-vinyl bond is 5-60%, preferably 8-45%
%.

The number average molecular weight of the random copolymer of component (c) used in the present invention having the above structure is s, ooo to 1.000.
,000, preferably 10. Goo~aoo', oo
o, more preferably 30,000~soo, ooo
The molecular weight distribution [ratio of weight average molecular weight (My) to number average molecular weight (Mn) (Mv/Mn)) is 1O or less. Furthermore, the molecular structure of the random copolymer (c) with Iff of 1 may be linear, branched, radial, or any combination thereof.

The method for producing these random copolymers is not particularly limited, and any known production method such as radical polymerization method, ionic polymerization method, etc. may be used as long as it has the above-mentioned structure. It doesn't matter.

As an example of such a random copolymer, there are those commercially available from Asahi Kasei Kogyo ■ under the trade names ``Tufden'' and ``Asaburen.''

Furthermore, the component (c) provided in the present invention is obtained by further hydrogenating the random copolymer described above to obtain at least 50% or more, preferably 80% or more of the olefinic double bonds contained in the random copolymer, and aromatic A hydrogenated product in which 25% or less of group unsaturated bonds are hydrogenated (hereinafter abbreviated as hydrogenated random copolymer) can be used.

As a method for hydrogenating such a random copolymer, for example,
Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 6636-1973, Japanese Patent Publication No. 20814-1977, Journal
of Poly+eer 5science, Part
B Letters, Volume 11,427
'434, (1973), and Special Publication No. 63-540
The hydrogenated random copolymer of the present invention can be obtained by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst etc. by the method described in Publication No. 1 etc. The method is not limited to the methods listed above.

Next, 9°10 used as component (d) in the present invention
-Dihydro-9-oxa-10-phosphaphenanthrene is a phosphorus compound having the following structure, and is an essential component for improving the color tone of the obtained thermoplastic resin composition of the present invention.

The present invention is a thermoplastic resin composition consisting of the above-mentioned components (a) to (d), and the blending amount of each resin component is 5 to 95% by weight of component (a) and component (b).
95-5% by weight (a) + (b) components
Component (e) for 97-65% by weight
3~35f! You can choose from the quantity percentages.

If the content of component (a) exceeds 95% by weight, the improvement in chemical resistance and processability will be insufficient, and the resulting resin composition will suffer from unfavorable delamination.

In addition, if the content of component (b) exceeds 95% by weight,
Although it certainly satisfies the chemical resistance performance, it reflects the performance of the polyolefin itself, and the heat resistance (deflection temperature under load: A
STM D648. (Based on the load of 18.6 kg) cannot be expected to be improved, which is not preferable.

If the amount of component (e) exceeds 35% by weight, the delamination phenomenon disappears, but the balance between rigidity and heat resistance deteriorates significantly, which is not preferable. In addition, if it is less than 5% by weight,
The resulting resin composition exhibits a layer peeling phenomenon, which is undesirable.

In addition to the above components (a) to (c), the present invention further provides (
As component d), 0.2 to 5 parts by weight of 9.10-dihydro-9-oxa-10-phosphaphenanthrene, which is a phosphorus compound, is blended with respect to the total ioo parts by weight of components (a) to (e). be able to. Such phosphorus compounds are 0,
If it is less than 2 parts by weight, the color tone of the resulting resin composition will not be significantly improved, and if it exceeds 5 parts by weight, no further improvement in color tone can be expected.

The thermoplastic resin composition of the present invention has the above-mentioned (a) to (c)
and (a) to (d) are compositions containing component a, but various Plasticizers, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, colorants, antistatic agents, mold release agents, and flame retardants such as aromatic halogen compounds, aromatic phosphate esters, red phosphorus, antimony dioxide, etc. Flame retardant additives, inorganic and/or organic fibrous reinforcing materials such as glass fiber and carbon fiber, and fillers such as glass peas, calcium carbonate and talc are added to impart various desired functions to the material. be able to.

The thermoplastic resin composition of the present invention can be produced by various methods. Examples include a heating melt kneading method using a single screw extruder, a twin screw extruder, a roll, a kneader Brabender plastograph, a Banbury mixer, etc. Among them, a melt kneading method using a twin screw extruder is most preferred.

The melt-kneading temperature at this time is not particularly limited, but can be normally selected arbitrarily from 150 to 350°C.

The thermoplastic resin composition of the present invention thus obtained can be molded into various parts by various conventionally known methods, such as injection molding, extrusion molding (sheets, films), and blow molding. It can be shaped. These various parts include, for example, automobile parts, and specifically include exterior parts such as bumpers, door panels, various moldings, emblems, engine hoods, hubcaps, roofs, spoilers, and various aero parts, instrument panels, Suitable for interior parts such as console boxes and trims. Furthermore, it can be suitably used as interior and exterior parts for electrical and electronic equipment, specifically as parts for various computers and their peripherals, other office automation equipment, cabinets for televisions, videos, various disc players, refrigerators, etc. ing.

〔Effect of the invention〕

Since the thermoplastic resin composition of the present invention uses a specific random copolymer as a compatibility between polyphenylene ether and polyolefin, it has good compatibility (layer peeling).
The present invention provides a resin composition with improved properties, excellent balance between rigidity (flexural modulus) and heat resistance, and excellent chemical resistance.

Furthermore, in addition to the above-mentioned effects, the resin composition of the present invention provides a resin composition with excellent color tone because it uses a specific phosphorus compound.

〔Example〕

The present invention will be explained in more detail with reference to examples, but the present invention is not particularly limited by these examples.

(1: PPE) It has an oxygen inlet at the bottom of the reactor, and a cooling coil inside.
After sufficiently purging the inside of a stainless steel reactor with stirring blades with nitrogen, 53.6 g of cupric bromide, 1110 g of di-n-butylamine, and a mixed solvent of 207 x of toluene, 16 l of n-butanol, and 47 g of methanol were added. 8.751 g of 2,6-xylenol was dissolved and charged into the reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was carried out for 180 minutes. In addition, the internal temperature is 30
Water was circulated through the cooling coil during the polymerization to maintain the temperature. After the polymerization is completed, the precipitated polymer is separated by filtration, a methanol/hydrochloric acid mixture is added to decompose the remaining catalyst in the polymer, and the polymer is sufficiently washed with methanol and then dried to obtain pale yellowish white powder PPE ( A reduced viscosity of 0.59) was obtained. This polymer is referred to as PPE■. Furthermore, PPE■ having a reduced viscosity of 0°33 was obtained using the same method as for obtaining PPE■, except that the amount of catalyst used was changed.

The PPE■ and PPE■ obtained here were each
Based on the method described in Publication No. 3-152628, P
PE 1001! After blending the fi part with the styrene 8-layer plate part, the mixture was melt-kneaded in a twin-screw extruder with a vent set at 290°C to obtain PPE (1) and PPE (2) in which styrene had a chroman structure added to the PPE terminal.

<2: Polyolefin>PO-■; Isotactic polypropylene (E-1
PO-■; Low density polyethylene (M1804; manufactured by Asahi Kasei Corporation) R2H-■; Styrene and butadiene are polymerized in cyclohexane using a -butyllithium catalyst to form bonded styrene m, 23 %, and a random copolymer with a block rate of 6% was obtained.

Using tetrahydrofuran as a randomizing agent, styrene and butadiene were polymerized in cyclohexane using See, -butyllithium catalyst, bound styrene ff 147%, block rate l.

Commercially available random styrene-butadiene copolymer bonded styrene f1165%) (Asaprene 6500, manufactured by Nippon Elastomer #) to obtain 2% random copolymer R2H-■; Commercially available random styrene-butadiene copolymer bonded styrene fi85%) (Hiker 2007;
(manufactured by Nippon Zeon ■); The above R2H-■ ~ ■ were hydrogenated according to the method described in Japanese Patent Publication No. 63-5401 to obtain hydrogenated random copolymers R3B-■ ~. R3B-■; R2H-■; R3B (4:910-dihydro-9-oxa-HCA: (manufactured by Sanko Kagaku ■) t-12 ratio l~12 Polyphenylene ether, polyolefin, random copolymer obtained in reference example Coalescence, hydrogenated random copolymer and 9.
lO-dihydro-9-oxa-10-phosphaphenanthrene (HCA) was blended with the composition shown in Tables 1 and 2, and a 58-diameter co-rotating twin-screw extruder set at 230°C to 300°C ( ZSK-58 (manufactured by W&P ■) was melt-kneaded, rapidly cooled, and then cut to obtain a pellet-shaped resin composition. Using this pellet, we used a screw in-line injection bottom machine (FAS-50) set at 260°C to 295°C.
B, manufactured by 7γtt9■), and a test piece was molded at a mold temperature of 100°C. Using this test piece, Izot impact strength (ASTM D-256; 23℃
-30℃), deflection under load of 4 degrees (ASTM D64
8) and flexural modulus (ASTM D790) were measured using each measurement method.

In addition, using a 178-inch-thick Izotz impact test test piece, a measurement method based on Bengel's quarter ellipse method (SPE Journal, 667, 1962) was used, and tempura oil was applied to the test piece at 80°C. The critical strain rate (%) for crack generation was measured.

These results are also listed in Tables 1 and 2.

From these results, the resin composition within the scope of the present invention has no delamination phenomenon, has an excellent balance of heat resistance and rigidity,
Furthermore, it has been revealed that it has excellent chemical resistance.

(Downwind margin) In addition to 100 parts by weight of the compounding composition of Example 8, 9°1
0-dihydro-9-oxa-10-phosphaphenanthrene (HCA) 0.5 parts by weight (Example 13), 1 part by weight (Example 14), 2 parts by weight (Example 15), 3.5 parts by weight
Parts by weight (Example 16) and 5 parts by weight (Example 17) were blended and subjected to melt mixing and injection molding under the same conditions as in Example 8 to obtain a test piece. When the color tone change of the test piece of Example 8 and the test piece obtained here was measured as a yellow index (Yl) value using a colorimeter for measuring object color, the yellow index (Yl) value was 39 (Example 8) and 24 (Example 8), respectively. Example 13)
, 16 (Example 14), 15 (Example 15), 13 (Example 16), and 14 (Example 17).

These results revealed that the color tone can be significantly improved by using HCA in combination.

Claims (1)

[Claims] 1. (a) 5 to 95% by weight of polyphenylene ether (b
) 97-65% by weight of a resin component consisting of 95-5% by weight of polyolefin (c) A vinyl aromatic compound-conjugated diene compound random copolymer containing 30-75% by weight of a vinyl aromatic compound or a hydrogenated product thereof 3- A thermoplastic resin composition comprising 35% by weight. 2, (a) polyphenylene ether 5-95% by weight (b
) 97-65% by weight of a resin component consisting of 95-5% by weight of polyolefin (c) A vinyl aromatic compound-conjugated diene compound random copolymer containing 30-75% by weight of a vinyl aromatic compound or a hydrogenated product thereof 3- 35% by weight (d)9,10
- A thermoplastic resin composition comprising 0.2 to 5 parts by weight of dihydro-9-oxa-10-phosphaphenanthrene based on a total of 100 parts by weight of components (a) to (c).