JPH0524940B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION The present invention relates to polyphenylene ether compositions, particularly polyphenylene ether compositions with improved moldability. Polyphenylene ether has excellent electrical and mechanical properties, a high heat distortion temperature, and self-extinguishing properties, and is attracting attention as an extremely useful engineering plastic material. However, it has low impact strength and is somewhat brittle. Furthermore, since this resin has a high melting temperature and high melt viscosity, high molding temperatures and pressures are required during molding, making molding by melting difficult. As one method for improving the moldability of polyphenylene ether, attempts have been made to blend it with other resins. For example, Tokuko Sho 43-17812
The publication describes blending a high impact polystyrene resin with polyphenylene ether. Although this composition has improved moldability and impact resistance, it is said that the moldability is still insufficient. Another method to improve the moldability of polyphenylene ether is to add a plasticizer to polyphenylene ether.
For example, Publication No. 49-5220 discloses an aromatic organic acid ester having good compatibility with polyphenylene ether resin, a polyester having an aromatic group, an organic phosphate ester having an aromatic group, and It has been shown that moldability can be improved by blending a compound selected from chlorinated aromatic hydrocarbons into polyphenylene ether or a composition of polyphenylene ether and styrenic resin. However, when a plasticizer (for example, an organic phosphate ester having an aromatic group) is blended with polyphenylene ether or a composition of polyphenylene ether and styrene resin, moldability is improved, but performance will be significantly reduced. this is,
Because the blended plasticizer is extremely uniformly dispersed (molecularly dispersed) in a matrix made of polyphenylene ether or a composition of polyphenylene ether and styrene resin, the glass transition temperature (Tg) of the matrix is ) is considered to decrease, resulting in a decrease in heat resistance. The present inventors considered that it is desirable for the additive to have the following properties in order to suppress this decrease in thermal performance (heat resistance) and improve moldability (fluidity). (1) During molding, that is, under the fluid state of the system, it must have good compatibility with matrix components and exhibit the same fluidity-improving effect as a plasticizer. (2) During use, i.e. under flow stopped conditions (matrix
(temperature range below Tg), it should phase separate from the matrix components and do not lower the Tg of the matrix. However, in order to prevent a decrease in mechanical strength, the interfacial adhesive force with the matrix must be strong to a certain extent even when phase separation occurs, and the material must have affinity with the matrix. The present inventors have arrived at the present invention as a result of intensive studies from this viewpoint. [] Summary of the invention The present invention provides polyphenylene ether, or
The object of the present invention is to provide a means for improving the moldability of a composition of polyphenylene ether and styrene resin. That is, the present invention is a mixture of a polyphenylene ether or a composition of polyphenylene ether and a styrene resin, and a carboxy compound having the structure of the following formula. This is a polyphenylene ether composition with improved moldability, characterized in that the compound is contained in an amount of 0.5 to 20 parts by weight. Ar: aromatic hydrocarbon residue having 6 to 20 carbon atoms. n: An integer selected from 0 to 6. m: 1 or 2 -R ¹ (R ¹ : -H, methyl group or phenyl group) -R ² (R ² : -H or -OH) [] Specific description of the invention (1) Polyphenylene ether Book The polyphenylene ether used in the invention has the general formula The ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is at least 50, and Q is each independently hydrogen, halogen, Hydrocarbon groups containing no tertiary α-carbon atoms, halohydrocarbon groups having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy groups and between the halogen atom and the phenyl nucleus Indicates a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having at least 2 carbon atoms. Typical examples of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-
1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,
4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-dibutyl-
1,4-phenylene)ether, poly(2,6
-dibropenyl-1,4-phenylene) ether, poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,
6-dimethoxy-1,4-phenylene) ether, poly(2,6-diethoxy-1,4-phenylene) ether, poly(2-methoxy-6-
Ethoxy-1,4-phenylene)ether, poly(2-ethyl-6-stearyloxy-1,
4-phenylene) ether, poly(2,6-dichloro-1,4-phenylene) ether, poly(2-methyl-6-phenyl-1,4-phenylene) ether, poly(2,6-dibenzyl-
1,4-phenylene) ether, poly(2-ethoxy-1,4-phenylene) ether, poly(2-chloro-1,4-phenylene) ether,
Poly(2,5-dibromo-1,4-phenylene) ether and the like. Also, 2,6-dimethylphenol and 2,3,
Copolymer of 6-trimethylphenol, 2,6
-Copolymers such as a copolymer of dimethylphenol and 2,3,5,6-tetramethylphenol and a copolymer of 2,6-diethylphenol and 2,3,6-trimethylphenol can also be mentioned. . Furthermore, the polyphenylene ether used in the present invention is a polyphenylene ether defined by the above general formula and a styrene monomer (for example,
It also includes modified polyphenylene ethers such as those grafted with styrene, p-methylstyrene, α-methylstyrene, etc.). Methods for producing polyphenylene ethers corresponding to the above are known, for example, in US Pat.
Specifications of No. 3306874, No. 3306875, No. 3257357, and No. 3257358 and Japanese Patent Publication No. 1973-
No. 17880 and JP-A-50-51197. A group of polyphenylene ethers preferred for the purposes of the present invention are those with alkyl substituents in the two positions ortho to the ether oxygen atom and those with 2,6-dialkylphenols and 2,6-dialkylphenols.
Copolymers of 3,6-trialkylphenol and also graft polymers obtained by grafting styrene monomers onto these polyphenylene ether skeletons. (2) Styrenic resin The styrene resin used in the present invention includes homopolymers such as polystyrene, poly-α-methylstyrene, and poly-p-methylstyrene, butadiene rubber, styrene-butadiene copolymer, and ethylene-propylene. copolymers, high-impact polystyrene modified with various rubbers such as ethylene-propylene-diene terpolymers, styrene-butadiene copolymers, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-
Examples include acrylonitrile-butadiene copolymer, styrene-methylmethane acrylate copolymer, etc., and these styrene resins are mixed in a proportion of 0 to 2000 parts by weight per 100 parts by weight of polyphenylene ether resin. (3) Addition of other polymers Other polymers can be added to polyphenylene ether or a composition of polyphenylene ether and styrene resin for the purpose of improving impact resistance. Polymers to be added include natural or synthetic rubber-like elastomeric polymers, such as natural rubber, polyisoprene, polybutadiene, copolymers of styrene and conjugated dienes such as butadiene (including block copolymers), Ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene terpolymers, etc. can be used. In addition, a polymer that has been given sensitivity by introducing a polar group can also be used. In addition to using a polymer that has been given sensitivity to a rubber-like elastic polymer, polyethylene, ethylene-vinyl acetate copolymer,
It is also possible to use a polymer obtained by imparting sensitivity to a polyolefin polymer such as polypropylene. As a means of imparting sensitivity, it is possible to graft an unsaturated organic acid or its anhydride (for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, or anhydride thereof) or an unsaturated silane compound to the above polymer. This can be done by Furthermore, a polymer imparted with sensitivity can also be obtained by block or random polymerization of ethylene with a vinyl monomer or vinyl silane having a polar group such as an unsaturated organic acid such as acrylic acid or an ester thereof. . When using rubber-modified polystyrene, the amount of the rubber-like elastic polymer or the polymer imparted with sensitivity is such that the total amount including the rubber content derived from it is 0.5 to 50% by weight based on the total amount of all polymer components. %, preferably about 2 to 40% by weight. Further, when using a polymer imparted with sensitivity, it is preferable to add an inorganic chamber filler. When a sensitized polymer and an inorganic filler are used together, the sensitized polymer is dispersed in the matrix of polyphenylene ether or a composition of polyphenylene ether and styrene resin, imparting sensitivity. By forming a special structure in which an inorganic filler is selectively filled in the polymer, it is possible to obtain excellent physical properties such as mechanical strength. As the inorganic filler, inorganic powders known as fillers for synthetic resins, such as titanium oxide, zinc oxide, talc, clay, calcium carbonate, and silica, can be used. The average particle size of the inorganic filler is preferably about 0.05 to 1.0μ, and is 0.5 to 0.6% by weight, preferably 1 to 1% by weight, based on the entire composition obtained by mixing.
45% by weight is used. Furthermore, as other polymers, polyphenylene ether or polyolefin graft-polymerized with a styrene resin can also be used. Polyphenylene ether graft polyolefin is a glycidylated polyphenylene ether obtained by reacting with epichlorohydrin.
Polyolefins having a carboxyl group or an acid anhydride group in the main chain or side chain, such as ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified It can be obtained by grafting onto ethylene/vinyl acetate copolymer or the like. In addition, polyphenylene ether graft polyolefins are polyolefins having glycidyl groups in their side chains, such as ethylene/glycidyl methacrylate copolymers, ethylene/vinyl acetate,
It can also be obtained by grafting polyphenylene ether onto a glycidyl methacrylate copolymer or the like. Polystyrene-grafted polyolefins include styrene-based copolymers having a carboxylic acid group or cyclic acid anhydride group in the main chain or side chain of polystyrene, such as styrene/maleic anhydride copolymer, styrene/citraconic anhydride copolymer, etc. Coalescence, styrene/itaconic anhydride copolymer, styrene/asconitic anhydride copolymer,
Styrene/acrylic acid copolymer, styrene/methacrylic acid copolymer, etc. are combined with polyolefins having a glycidyl group in the side chain, such as ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, etc. It can be obtained by grafting. The amount added is based on the total amount of polyphenylene ether, or the composition of polyphenylene ether and styrene resin, and the polyphenylene ether grafted polyolefin and/or polystyrene grafted polyolefin.
0.1 to 50% by weight, preferably 1 to 30% by weight of polyphenylene ether grafted polyolefin;
Polystyrene graft polyolefin 1-80
% by weight, preferably in the range from 1 to 30% by weight. Grafted polyolefin can be added after graft polymerization in advance, but when using polyolefin having glycidyl groups,
Polyphenylene ether or styrenic resin having carboxylic acid or its anhydride group
The graft reaction can be carried out by kneading at a high temperature of 150°C or higher. Therefore, by kneading a composition of glycidyl group-containing polyolefin and polyphenylene ether or polyphenylene ether and styrene resin at high temperature, each component is mixed uniformly and at the same time the graft reaction progresses. A composition containing the polyphenylene ether-grafted polyolefin and/or polystyrene-grafted polyolefin produced by the method can be obtained all at once, and is the most preferred method from an economical point of view. (4) Carboxy compound The carboxy compound used in the present invention has a structure represented by the following formula. Ar: aromatic hydrocarbon residue having 6 to 20 carbon atoms. n: An integer selected from 0 to 6. m: 1 or 2 -R ¹ (R ¹ : -H, methyl group or phenyl group) -R ² (R ² : -H or -OH) Examples of Ar include phenyl group, phenylene group, naphthyl group, etc. It will be done. The carboxy compound of the present invention is intended to be compatible with the matrix component under the fluid state during molding, and to crystallize and phase separate from the matrix component when used. Therefore, it is desirable that the melting point of the carboxy compound of the present invention is slightly lower than the molding temperature. Generally, the molding temperature of the polyphenylene ether composition is 105-350°C, preferably 200-300°C. Therefore, the carboxy compound used in the present invention has a melting point of 105 to 350°C, preferably
It is desirable that the temperature be within the range of 150°C to 300°C. However, if the molding temperature is outside the above range due to the addition of a stabilizer or plasticizer, a carboxy compound with a different melting point can be used accordingly. The amount added is 0.5 to 20 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of all polymers.
10 parts by weight is preferred. (5) Additives In the present invention, other additives may be used depending on the purpose. Examples of additives include stabilizers, plasticizers, flame retardants,
There are various inorganic fillers, mold release agents, colorants, etc. The polyphenylene ether composition of the present invention has the advantage of improved fluidity, and has the advantage of being easy to mold even if other additives are added. [] Examples The present invention will be specifically described below with reference to Examples. Example 1 50 parts by weight of poly-2,6-dimethyl-1,4-phenylene ether (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity 0.50 in chloroform at 25°C) and high impact polystyrene (manufactured by Mitsubishi Yuka Co., Ltd., several parts by weight) Average molecular weight 55000,
Weight average molecular weight 200000, microgel content 14.5% by weight) 50 parts by weight and the following structural formula: 3-Hydroxy-2-naphthoic acid (manufactured by Yamato Kagaku Co., Ltd., melting point measured with melting point meter MP-1 type:
218℃) and 5 parts by weight at 260℃ using a Brabender.
The mixture was melt-kneaded for 7.5 minutes. After kneading, the melt index (250°C, 10 kg load) representing molding processability (fluidity) was measured, and a specified test piece was prepared using a press, and the heat distortion temperature was measured (18.6 kg/cm ² loads).
The results are shown in Table-1. Comparative Example 1 Table 1 shows the results obtained in the same manner as in Example 1 except that 3-hydroxy-2-naphthoic acid was not used.
Shown in 1. Comparative Example 2 Instead of 3-hydroxy-2-naphthoic acid, triphenyl phosphate (melting point: 50
Table 1 shows the results obtained in the same manner as in Example 1, except that 5 parts by weight (°C) was used. As is clear from Table 1, 3-hydroxy-
By using 2-naphthoic acid, fluidity (moldability) is significantly improved and a decrease in heat resistance is suppressed. Although the plasticizer improves the fluidity, the heat resistance is greatly reduced, and the effect of the present invention can be understood.

[Table] Example 2 Instead of 3-hydroxy-2-naphthoic acid,
4,4-bis(p-hydroxyphenyl)-n-
Except for using 5 parts by weight of valeric acid (melting point: 177°C),
Table 2 shows the results obtained in the same manner as in Example 1.

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Claims (1)

[Scope of Claims] 1. Polyphenylene ether or a composition of polyphenylene ether and styrene resin;
A polyphenylene ether composition having improved moldability, characterized in that the carboxy compound is mixed with a carboxy compound having the structure of the following formula, and the carboxy compound is present in an amount of 0.5 to 20 parts by weight per 100 parts by weight of the polymer. Ar: aromatic hydrocarbon residue having 6 to 20 carbon atoms. n: An integer selected from 0 to 6. m: 1 or 2 -R ¹ (R ¹ : -H, methyl group or phenyl group) -R ² (R ² : -H or -OH)