JPH0680147B2 - Impact resistant polyphenylene ether resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyphenylene ether resin, A-B-A 'type in which the molecular weight of B block is smaller than the total molecular weight of A and A'block. The present invention relates to an impact-resistant polyphenylene ether-based resin composition containing a block copolymer, a vinyl aromatic hydrocarbon resin, and an elastomer and having improved moldability.

(Prior Art) Polyphenylene ether-based resins are various U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, 3,257,358, 401,1200 and various JP-A No. 50-126800. It is a known resin disclosed in a known document.

Polyphenylene ether resin is a resin having excellent heat resistance, but it requires extrusion and molding at high temperatures. Extrusion and molding processing at high temperature cause deterioration of the polyphenylene ether resin, and as a result, the excellent performance originally possessed by the polyphenylene ether resin is impaired. Further, the impact resistance of the polyphenylene ether resin is small and it is insufficient to use it as it is. US Pat. No. 3,383,435 discloses a resin composition containing a polyphenylene ether and a vinyl aromatic resin as a method for simultaneously improving such drawbacks of the polyphenylene ether resin. By blending vinyl aromatic resin and polyphenylene ether, it is possible to lower the temperature required for extrusion and molding. Further, when a rubber-modified polystyrene resin is used as the vinyl aromatic resin, the impact resistance strength of the resin composition is also improved. Since the rubber content in the composition increases with an increase in the proportion of the rubber-modified polystyrene, the degree of improvement in impact strength also increases, but the improvement in impact strength is still insufficient. Furthermore, the heat resistance is markedly reduced as the rubber-modified polystyrene increases.

Various resin compositions have been proposed as means for improving impact strength. For example, U.S. Pat. No. 3,660,531 discloses a resin composition containing polyphenylene oxide, polystyrene and rubber, and 3994856 discloses polyphenylene oxide, high impact polystyrene and elastomeric A-B-A 'type. A resin composition containing a block copolymer, 4128602 has a polyphenylene oxide,
The maximum mean diameter of rubber particles containing polystyrene and rubber dispersed in a resin composition (maximum mean diamete
Resin composition such that r) is 2μ, 4128603 contains polyphenylene oxide and high impact polystyrene, the high impact polystyrene comprising 22-80% by weight of elastomeric gel particles. A resin composition that is like that, and Japanese Patent Publication No. 57-8139 discloses a polyphenylene ether, a resin composition containing polystyrene and an acrylic resin-modified ABS, and U.S. Pat. No. 3,835,200 describes a polyphenylene ether. , A high-impact polystyrene and a resin composition containing an A-B-A 'type block copolymer in which the molecular weight of the B block is smaller than the sum of the molecular weights of the A and A'blocks are disclosed.

By the way, the present inventors have found that a resin composition containing a polyphenylene ether resin, an A-B-A 'type block copolymer and an elastomer in which the molecular weight of B block is smaller than the total of the molecular weights of A and A'blocks. Then, it was found that not only the impact strength at room temperature but also the impact strength at low temperature (for example, −40 ° C.) is improved, and a patent application has already been filed. However, when the performance of this resin composition was examined in detail, it was found that although it was naturally superior to the polyphenylene ether resin itself, its moldability was remarkably inferior. In order to improve moldability, an ABA 'type block copolymer having improved moldability and / or an elastomer having improved moldability was used in place of the above-mentioned constituents. However, the effect was not recognized. That is, even though the moldability was improved by itself, when used as one component of the polyphenylene ether resin composition, the moldability of the entire resin composition was not affected at all.

[Object of the Invention]

In the above polyphenylene ether resin composition, it is an object of the present invention to improve moldability without impairing impact strength.

[Outline of Invention]

As a result of intensive investigations by the present inventors to achieve the above-mentioned object, a polyphenylene ether resin composition containing a limited AB-A 'type block copolymer, a vinyl aromatic hydrocarbon resin and an elastomer. It was found that the moldability of the product was improved without impairing the impact strength, and the object of the present invention was achieved.

That is, the resin composition of the present invention is (a) a polyphenylene ether resin, (b) an AB-A 'type block copolymer (A and A'are polymerized vinyl aromatic hydrocarbon blocks). , B is a polymerized conjugated diene hydrocarbon block, and the molecular weight of B block is smaller than the combined molecular weight of A and A'block.) (C) Vinyl aromatic hydrocarbon resin and (d) ) An impact-resistant polyphenylene ether resin composition containing an elastomer and having improved moldability.

The polyphenylene ether resin used as the component (a) in the resin composition of the present invention means a monocyclic phenol represented by the general formula (I). (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and
R ₃ is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) A polyphenylene ether obtained by oxidative polycondensation of one or more of the above; and a graft copolymer having a polyphenylene ether as a backbone obtained by graft-polymerizing a vinyl aromatic compound on the polyphenylene ether. To do. The polyphenylene ether may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the general formula (I) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol and 2 -Methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-
Cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol , 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6-trimethylphenol, 2,3,6-triethylphenol, 2,3, 6-tripropylphenol, 2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-3-
Examples include propylphenol and the like. And, as the polyphenylene ether obtained by polycondensation of one or more of these monocyclic phenols, for example, poly (2,6-
Dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6- Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, 2,6- Dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer Polymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, graft copolymer obtained by graft-polymerizing styrene to poly (2,6-dimethyl-1,4-phenylene) ether, 2 , 6-Dimethylphenol / 2,3,6-trimethylphenol Graft copolymers of styrene on Nord copolymer obtained by graft polymerization, and the like. Particularly, poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer are preferable as the polyphenylene ether resin used in the present invention. Is.

A- used as the component (b) in the resin composition of the present invention
B-A 'type block copolymer is edited by Kennedy et al. "Polymer Chemistry of Synthetie Elastomers" Vol23
part II pp. 533-559 1969 (Interscience Publishe
rs) shows the manufacturing method. For example, by polymerizing butadiene or another conjugated diene hydrocarbon compound, and styrene or another vinyl aromatic hydrocarbon compound in a hydrocarbon solvent using an organolithium compound as an initiator, an ABA 'type block is produced. A copolymer is produced.

The vinyl aromatic hydrocarbons forming blocks A and A'are, for example, styrene, α-methylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, or a mixture thereof.

The conjugated diene hydrocarbon that constitutes block B is, for example,
It is butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, or a mixture thereof.

The molecular weight of blocks A and A'is 25,000 to 1,000,000, and the molecular weight of block B is 2,000 to 100,000.
The sum of the molecular weights of A and A'blocks is greater than that of block B. In particular, blocks A and A'of A '
The total content in the -BA 'type block copolymer is preferably 70 to 90% by weight, and the content of block B is preferably 30 to 10% by weight.

Since the proportion of block B is small, the block copolymer has a property as a resin and has a large Young's modulus. Specifically, “Properties and Structures” by AV Tobolsky
of Polymers "(John Wiley & Sons, Inc. 1960) 71-7
Greater than the Young's modulus of 10 ⁵ to 10 ⁹ dynes / cm ² (0.1 to 1020 kg / cm ² ) used to define elastomers on page 8.

The resinous block copolymer having the above-mentioned characteristics is commercially available, and is available from Asahi Kasei Kogyo Co., Ltd. under the trade name of "Asaflex". There are two grades of "Asaflexx", "Asaflexx 810" and "Asaflexx 800". "Asaflex 810" is a polystyrene-polybutadiene-polystyrene block copolymer, and the proportions of polystyrene block and polybutadiene block are 70% by weight and 30% by weight, respectively. Further, regarding the elastic modulus, it has a bending elastic modulus of 15000 kg / cm ² . "Asaflex 800" is also a polystyrene-polybutadiene-polystyrene block copolymer, and the proportions of polystyrene block and polybutadiene block are 80% by weight and 20% by weight, respectively. The flexural modulus is 21000 kg / cm ² . The morphology of "Asaflex" is different from that of ordinary impact-resistant polystyrene, and according to the electron micrograph, the diameter of the polybutadiene block agglomerates is as small as 0.01 to 0.02 µ.

The vinyl aromatic hydrocarbon resin used as the component (c) in the resin composition of the present invention is represented by the following general formula (II) (In the formula, R ₄ is a hydrogen atom or a lower alkyl group, Z is a halogen atom or a lower alkyl group, and p is 0 or 1
Is a positive integer of ˜3. ) Is a resin containing at least 25% by weight or more of the structural unit shown in the polymer,
Examples thereof include polystyrene, poly-p-methylstyrene, polychlorostyrene, acrylonitrile-styrene copolymer, and styrene-α-methylstyrene copolymer. Of these, polystyrene is preferred.

The elastomer used as the component (d) in the resin composition of the present invention has a Young's modulus at room temperature of 10 ⁵ to 10 ⁹ dynes /
A polymer having a size of cm ² (0.1 to 1020 kg / cm ² ), which is AB
-A 'type elastomeric block copolymer, A in which the double bond of the polybutadiene portion (B block) is hydrogenated
-B-A 'type elastomeric block copolymer, vinyl aromatic hydrocarbon block, and radial tereblock copolymer consisting of conjugated diene hydrocarbon block, and the double bond in the conjugated diene hydrocarbon block is hydrogenated. It means an elastomeric material selected from the above radial tereblock copolymers.

A-B-A 'type elastomeric block copolymer, or A-B- in which the double bond of block B is hydrogenated
The A'type elastomeric block copolymer is as follows. That is, the terminal blocks A and A'are polymerized vinyl aromatic hydrocarbon blocks, B is a polymerized conjugated diene block or a conjugated diene block in which most of the double bonds are hydrogenated, and The molecular weight is greater than the combined molecular weight of the A and A'blocks. The end blocks A and A'may be the same or different, and the blocks are thermoplastic homopolymers or copolymers derived from vinyl aromatic hydrocarbons whose aromatic moieties may be monocyclic or monocyclic. . Examples of such vinyl aromatic hydrocarbons include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. Central block B is an elastomeric polymer derived from conjugated diene hydrocarbons such as 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene and mixtures thereof. The molecular weight of each end block A and A'is preferably about 2,000 to about 10
The molecular weight of the central block B is preferably in the range of about 25,000 to about 1,000,000.

Such a copolymer is "Clayton" from Ciel Chemical Company,
It is commercially available under the trade name of "Clayton G", under the trade name of "Toughprene" from Asahi Kasei Kogyo Co., Ltd., and under the trade name of "JSR TR" from Japan Synthetic Rubber Co., Ltd.

The radial tereblock copolymer or the radial tereblock copolymer in which the double bond in the conjugated diene hydrocarbon block is hydrogenated is a vinyl aromatic hydrocarbon block, a conjugated diene hydrocarbon block and a coupling agent. Or a branched polymer in which a double bond in a conjugated diene hydrocarbon block is hydrogenated. More specifically, two or more chains of conjugated diene rubber extend from the coupling agent, with the opposite end of each chain from the coupling agent being attached to the vinyl aromatic polymer chain. Radial tereblock copolymers are known in the art, for example, conjugated diene compounds and vinyl aromatic compounds are polymerized in the presence of an organometallic polymerization initiator to give lithium-like activity at one end of various polymer chains. It can be prepared by preparing a copolymer containing metal atoms and then reacting the copolymer with a coupling agent having at least two active groups capable of substituting active metal atoms. As a result, a polymer having a branch of a polymer chain extending radially around the coupling agent as a nucleus is obtained. By hydrogenating the double bond of the conjugated diene hydrocarbon block in this polymer, a branched polymer in which the double bond in the conjugated diene hydrocarbon block is hydrogenated is obtained. Radial tereblock copolymers in which the double bond in the conjugated diene hydrocarbon block is not hydrogenated are available from Asahi Kasei Co., Ltd. under the trade names of "Sorprene" and "Asaprene".

(A), (b), (c) in the resin composition of the present invention,
The proportion of the component (d) in the resin component is generally 10 to 80% by weight of (a) and 10 to 10 in the combination of (b) and (c).
88% by weight, (d) 2 to 30% by weight, preferably (a) 15 to 75% by weight, and the combination of (b) and (c) is 15 to
75% by weight, (d) 5 to 25% by weight. (B) and (c)
The ratio of (b) in the combination with is 10 to 90% by weight.

In addition to the above resin components, other resins can be blended as long as the performance of the resin composition of the present invention is not impaired. Furthermore, it is possible to mix various additives, fillers and other components depending on the purpose. Examples of various additives and fillers include sterically hindered phenols, organic phosphites, phosphonites, phosphonasic acids, cyclic phosphonites, hydrazine derivatives, amine derivatives, carbamate derivatives, thioethers, phospholitutriamides, benzoxazole derivatives, and sulfurization of metals. Stabilizers such as benzotriazole derivatives, benzophenone derivatives, salicylate derivatives,
UV absorbers such as sterically hindered amines and oxalic acid diamide derivatives; lubricants such as olefin wax, metal salts of fatty acids, fatty acid amides; decabromobiphenyl, pentabromotoluene, decabromobiphenyl ether, brominated polystyrene, etc. Representative brominated flame retardants; pigments representative of titanium oxide, zinc oxide, carbon black, etc .; glass beads, asbestos, glass fibers, wollastonite,
Inorganic fillers represented by mica, talc, clay, calcium carbonate, silica, etc .; copper, nickel, aluminum,
Metal flakes typified by flakes such as zinc; metal fibers typified by aluminum fibers, aluminum alloy fibers, brass fibers, stainless fibers, etc .; organic fillers typified by carbon fibers and aromatic polyamide fibers; .
The addition amount of these varies depending on the type of compound used or the purpose of addition.

In producing the polyphenylene ether-based resin composition of the present invention, a conventionally known method may be adopted, for example, after mixing the components with a high-speed mixer represented by a turnbull mixer or a Hensiel mixer. A method of kneading with an extruder, a Banbury mixer, a roll or the like is appropriately selected.

Hereinafter, the resin composition of the present invention will be described in detail with reference to Examples. The amounts and percentages of the respective components used in the resin composition are expressed on a weight basis unless otherwise specified.

〔Example〕

Example 1 Intrinsic viscosity, 0.52 dl / g (25 ° C., in chloroform) 2,6-
42 parts by weight of dimethylphenol / 2,3,6-trimethylphenol copolymer (the latter ratio is 5 mol%), polystyrene-polybutadiene-polystyrene block copolymer (weight ratio of polystyrene part to polybutadiene part is 80/2
0, Product name "Asaflex 800", Asahi Kasei Corporation
Manufactured by Mitsubishi Monsanto Kasei Co., Ltd.
15 parts by weight of a radial tereblock copolymer of polystyrene and polybutadiene (weight ratio of styrene component and butadiene component is 30/70, trade name "Sorprene T-411", manufactured by Asahi Kasei Kogyo Co., Ltd.), Tetrakis (2,4-di-ter
t-butylphenyl) -4,4'-biphenylenediphosfonite (trade name "Sandstarve P-EPQ", manufactured by Sand Co.) 0.4 part by weight, and 2,6-di-tert-butyl-P-cresol ( 0.6 part by weight of the product name "Santage BHT" manufactured by Kawaguchi Chemical Industry Co., Ltd. was thoroughly mixed using a Hensiel mixer. The resulting mixture has a maximum cylinder temperature
An AS-30 twin screw extruder (Nakaya Kikai Seisakusho) set at 290 ° C was used to extrude into pellets, and then the maximum cylinder temperature was set at 280 ° C. Was used to mold a test piece for measuring Izod impact strength (thickness 1/8 ¹¹ ) under the condition that the injection pressure was 1050 kg / cm ² .

Using a pellet, a melt flow value (Q value), which is a measure of moldability, was measured under the conditions of 230 ° C. and 60 kg / cm ^{2 with a} Koka type flow tester (manufactured by Shimadzu Corporation). Moreover, the notched Izod impact strength was measured at 23 ° C. and −40 ° C. using the above test piece. The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that polystyrene was not used but 43 parts by weight of polystyrene-polybutadiene-polystyrene block copolymer (Asaflex 800) was used. The results are shown in Table 1.

Comparative Example 2 Example 1 was repeated except that the polystyrene-polybutadiene-polystyrene block copolymer was not used but 43 parts by weight of polystyrene (Dialex HH-102) was used. The results are shown in Table 1.

As is clear from the results in Table 1, the combined use of polystyrene improves the Q value and also improves the impact strength of the Izod, the latter against the change in the ratio of the ABA block copolymer and polystyrene. Shows the maximum value.

Example 2 In the composition of (c) of Example 1, polystyrene-polybutadiene- was used instead of the radial tereblock copolymer.
Polystyrene elastomer block copolymer (weight ratio of polystyrene part and polybutadiene part is 30/70,
Example 1 was repeated except that the product name "Clayton TR1101", manufactured by Ciel Chemical Co., Ltd.) was used. The results are shown below.

Q value 1.21 × 10 ⁻³ cc / sec Izod impact strength 23 ° C. 36.7 kg.cm/cm −40 ° C. 24.3 Example 3 In the composition of (c) of Example 1, titanium oxide (trade name “Kronos KR-380”) was added. Example 1 was repeated with the addition of 7 parts by weight of Titanium Industry Co., Ltd.). The results are shown below.

Q value 1.92 × 10 ⁻³ cc / sec Izod impact strength 23 ° C. 33.3 kg.cm/cm −40 ° C. 22.7 Example 4 In the composition of (d) of Example 1, a partially oxidized polyethylene wax (trade name " Example 1 was repeated with the addition of 1 part by weight of Sanwax E-250p ", manufactured by Sanyo Kasei Co., Ltd. The results are shown below.

Q value 5.2 × 10 ⁻³ cc / sec Izod impact strength 23 ° C. 35.4 kg.cm/cm −40 ° C. 21.8 Example 5 2,6-Dimethylphenol / 2,3,6-used in Example 1
65 parts by weight of trimethylphenol copolymer, 10 parts by weight of polystyrene-polybutadiene-polystyrene block copolymer (Asaflex 800) used in Example 1, polystyrene (trade name "Dialex HF-77", manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) ) 15 parts by weight, 10 parts by weight of polystyrene-polybutadiene-polystyrene elastomeric block copolymer (Clayton TR-1101) used in Example 2, tris (nonylphenyl) phosphite (trade name "ANTAGE TNP", Kawaguchi Chemical Industry Co., Ltd. )) And 0.6 parts by weight of 2,6-di-tert-butyl-p-cresol used in Example 1 were thoroughly mixed using a Henschel mixer. The resulting mixture is extruded into pellets with an AS-30 twin-screw extruder with the maximum cylinder temperature set at 310 ° C, then the maximum cylinder temperature is 300 ° C.
Injection pressure 1310kg using SJ-35B injection molding machine set to
A test piece for measuring Izod impact strength (thickness 1/8 ¹¹ ) was molded under the condition of / cm ² .

290 ℃, 60k with Koka type flow tester using pellet
The Q value was measured under the condition of g / cm ² . Moreover, the notched Izod impact strength was measured at 23 ° C. and −40 ° C. using the above test piece. The results are shown in Table 2.

Comparative Example 3 In Example 5, without using polystyrene,
Further, the operation of Example 5 was repeated except that the amount of the polystyrene-polybutadiene-polystyrene block copolymer (Asaflex 800) was 25 parts by weight. The results are shown in Table 2.

Comparative Example 4 The polystyrene-polybutadiene-polystyrene elastomeric block copolymer in which the ABA 'block copolymer (Asaflex 800) in C of Example 1 was used in Example 2 (the weight ratio of polystyrene part to polybutadiene part was 30 / Clayton TR1101), which is 70, was repeated. The Q value was 3.6 × 10 ^-4 cc / sec.

Comparative Example 5 The result of repeating C of Example 1 was as follows, except that the radial teleblock copolymer of polystyrene and polybutadiene was changed to polybutadiene (BR01, manufactured by Nippon Synthetic Rubber). .

23 ° C.-40 ° C. Izod impact strength 17.4 11.5 (kg · cm / cm) Comparative Example 6 In C of Example 1, a radial teleblock copolymer of polystyrene and polybutadiene was replaced with an ethylene-propylene copolymer (Mitsui Petrochemical Co., Ltd., The result of repeating C of Example 1 was as follows, except that Toughmer P-1081) was replaced.

23 ° C.-40 ° C. Izod impact strength 21.8 10.3 (kg · cm / cm) Comparative Examples 7 and 8 In Example 1, the composition ratio of polystyrene-polybutadiene-polystyrene block copolymer (Asaflex 800) and polystyrene is shown in Table 3. Example 1 was repeated, substituting the values shown. The results are shown in Table 3.

Comparative Example 9 In Example 1, the polystyrene-polybutadiene-polystyrene block copolymer (Asaflex 800) was used as a polystyrene-polybutadiene-polystyrene elastomer block copolymer (the weight ratio of polystyrene part to polybutadiene part was 40/60 A, manufactured by Asahi Kasei Kogyo Co., Ltd.) and Example 1 was repeated. The results were as follows.

23 ℃ -40 ℃ Izod impact strength 39.4 24.6 (kg ・ cm / cm) Q value 5.7 × 10 ^-4 cc / sec [Effect] Polyphenylene ether resin with improved moldability without impairing impact strength. A composition can be obtained.

Claims (1)

[Claims] 1. A polyphenylene ether-based resin (a),
(B) A-B-A 'type block copolymer (A and A'
Is a polymerized vinyl aromatic hydrocarbon block, B
Is a polymerized conjugated diene hydrocarbon block, and the B block has a molecular weight smaller than the combined molecular weight of the A and A'blocks), (c) a vinyl aromatic hydrocarbon resin, and (d) A- B-A 'type elastomeric block copolymer, A-B-A' type elastomeric block copolymer in which double bond of polybutadiene moiety (B block) is hydrogenated, vinyl aromatic hydrocarbon block and conjugated diene Elastomer selected from radial teleblock copolymers consisting of hydrocarbon block and hydrogenated double bonds in conjugated diene hydrocarbon block (Young's modulus at room temperature is 10 ⁵ ~ 10 ⁹ dyne / cm ² refers to certain such polymers with) a, and the content is 15 to 75% by weight of (a),
The content of the combination of (b) and (c) is 15 to 75% by weight,
Impact-resistant polyphenylene ether-based resin composition characterized in that the content of (d) is 5 to 25% by weight, and the proportion of (b) in the combination of (b) and (c) is 10 to 90% by weight.