JPS6412303B2 - - Google Patents

Description

[Detailed description of the invention]

[] BACKGROUND OF THE INVENTION Technical Field The present invention relates to a flame-retardant resin composition, and more specifically, a polyphenylene ether resin comprising a polyphenylene ether resin and another polymeric substance that is compatible with the polyphenylene ether resin. This invention relates to flame retardant compositions. Polyphenylene ether resin has excellent electrical and mechanical properties, high heat distortion temperature, and self-extinguishing properties, and is attracting attention as an extremely useful engineering plastic material. However, since this resin has a high melting temperature and high melt viscosity, high molding temperature and pressure are required during molding, making molding by melting difficult. Therefore, in practical use, polyphenylene ether resins are used by blending styrene resins and other polymeric substances that are compatible with polyphenylene ether resins to improve moldability. However, since the polymer material blended with the polyphenylene ether resin in this way is a relatively easily flammable resin such as polystyrene, the self-extinguishing property of the polyphenylene ether resin itself is lost, and it becomes extremely flammable. This causes the problem that it becomes easily flammable. Prior Art To solve this problem, aromatic phosphate compounds, such as triphenyl phosphate, have been used as flame retardants, but these compounds also act as plasticizers and their addition improves flame retardancy. At the same time, a problem arises in that the heat distortion temperature of the polyphenylene ether resin composition is significantly lowered. Therefore, the reality is that no satisfactory flame retardant composition has been obtained for polyphenylene ether resin compositions. [] Summary of the Invention The present invention is based on the discovery of a new high molecular weight flame retardant that can be added to a polyphenylene ether resin composition without deteriorating its physical properties. Polyphenylene ether made flame retardant by adding phosphoric acid ester oligomer to the blended polymer material in any proportion to the composition to improve moldability, which is a disadvantage of polyphenylene ether resin. A resin composition is provided. That is, in the present invention, the basic structure is

[Formula] (Here, R represents an aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue having 2 to 10 carbon atoms.) Phosphoric acid with a number average molecular weight of 500 to 5000 This is a flame-retardant resin composition characterized in that 0.1 to 20 parts by weight of an ester oligomer compound is added. The polyphenylene ether resin composition of the present invention is endowed with excellent flame retardancy and exhibits little deterioration in thermal properties caused by the addition of conventionally known flame retardants. [] Specific description of the invention (1) Polyphenylene ether resin The polyphenylene ether resin used in the present invention has the general formula It has a cyclic structural unit represented by, in which the ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is a positive integer of at least 50, and Q is an independent Hydrocarbon groups that do not contain hydrogen, halogen, or tertiary α-carbon atoms, halohydrocarbon groups that have at least two carbon atoms between the hagen atom and the phenyl nucleus, hydrocarbon oxy groups, and halogen atoms and phenyl Represents a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having at least two carbon atoms between them and the nucleus. Typical examples of polyphenylene ether include poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, and poly(2,6-dilauryl-1,4-phenylene) ether.
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 equivalents. Methods for producing polyphenylene ethers corresponding to these general formulas are known and are described, for example, in US Pat. No. 3,306,874, US Pat. No. 3,306,875, US Pat. For the purposes of the present invention, a particularly preferred group of polyphenylene ethers are those having alkyl substituents in the two ortho positions to the ether oxygen atom, i.e. each Q in the ortho position is an alkyl group, most preferably a number of carbon atoms. is a polyphenylene ether of the above general formula having 1 to 4 alkyl groups. Typical examples 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, among which the most preferable is poly(2,6
-dimethyl-1,4-phenylene) ether. (2) Polymeric Substance In the present invention, a polyphenylene ether resin composition in which a polymeric substance having compatibility with the polyphenylene ether resin is mixed with the polyphenylene ether resin can be used. Examples of polymeric substances that are compatible with polyphenylene ether resin include polystyrene, impact-resistant polystyrene, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, etc. , these polymeric substances are used in an amount of 1 to 1 part by weight per 99 to 1 part by weight of polyphenylene ether resin.
99 parts by weight, preferably polyphenylene ether
It is mixed at a ratio of 20 to 80 parts by weight to 80 to 20 parts by weight. (3) Phosphate ester oligomer compound The phosphate ester oligomer compound used as a flame retardant in the present invention has a basic structure of

It has a drying unit of the formula: where R represents an aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue having 2 to 10 carbon atoms. In the case of alicyclic hydrocarbon residues, those having 5 to 10 carbon atoms are usually used. The phosphate ester oligomer compound having the above structure preferably has a number average molecular weight of 500 to 5,000, particularly preferably 800 to 3,000. Number average molecular weight is 500
The smaller the size, the greater the degree to which the heat distortion temperature is lowered when used as the composition of the present invention;
On the other hand, when the number average molecular weight is greater than 5000, the flame retardant effect decreases. The phosphate ester oligomer compound used in the present invention can be synthesized as follows. That is, it is obtained by reacting phenylphosphonic acid dichloride and a _C2 - _C10 aliphatic diol or alicyclic diol at a temperature of 20-100° C. for 1-10 hours in a nitrogen atmosphere.
At this time, amines such as pyridine and triethylamine can be used as a catalyst if necessary. The degree of polymerization, i.e., the molecular weight, of the resulting oligomer can be determined by adding an appropriate amount of diphenylphosphonic acid monochloride as a molecular weight regulator, or by adjusting the charging ratio of phenylphosphonic acid dichloride and a C ₂ to _{C 10} aliphatic diol or alicyclic diol. It can be controlled by adjusting. In addition, the number average molecular weight was measured using gel permeation chromatography, and from the obtained chromatogram, using the relationship between the molecular weight and runoff time of monodisperse polystyrene with a known molecular weight, using a known calculation method (Tsugio Takeuchi, Obtained by Sadao Mori: Chromatography, published by Kodansha). Note that other polymeric substances may be added to the composition of the present invention as necessary. These polymeric substances include polyethylene, polypropylene, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, nylon, styrene-grafted polyethylene, styrene-grafted polypropylene, styrene-grafted acrylonitrile-styrene copolymer, styrene-grafted acrylonitrile-butadiene, Examples include styrene copolymers, styrene graft polyisobutene, and the like. (4) Blending method The blending method for obtaining the flame-retardant polyphenylene ether resin composition of the present invention is as follows:
Various methods generally used for blending plasticizers, stabilizers, colorants, etc. can be applied, and for example, a mixer such as an extruder or a plastomill can be used. Specifically, each of the above components is mixed and charged into an extruder with a screw diameter of 25 mm, and the cylinder temperature is
The desired flame-retardant polyphenylene ether resin composition can be obtained by extruding at 240-330°C and a screw rotation speed of 20-40 rpm. In addition, using a plastomill that maintains the temperature of the melting part cell at 240 to 330℃, the screw rotation speed is
The desired product can also be obtained by melt-mixing at 20-40 rpm for 5-15 minutes. In the following examples, the flame retardancy of the obtained resin compositions was determined by the following combustion test in accordance with the US UL standard, Subject 94. Combustion Test A test piece 6 inches long, 1/2 inch wide, and 1/16 inch thick was tested in a room with no moving air.
Fix the top end and hang vertically. Apply the flame of a Bunsen burner adjusted to produce a 3/4 inch blue flame for 10 seconds from the bottom of the specimen. Ten
After a few seconds, the burner is removed, and the burning time of the test piece after removal is recorded, and this is taken as the first ignition burning time. Immediately after the flame of the test piece is extinguished, apply the burner flame to the lower end of the test piece for 10 seconds in the same manner, and record the time until the flame extinguishes again, and use this as the second ignition combustion time. Also, place a piece of cotton one foot below the specimen and record whether the cotton ignites during the test with a drop of flaming resin. The above test is performed on five test pieces, and flame retardancy is determined as follows based on the test results. 94VE-O: The maximum burning time is within 10 seconds, the average burning time of the 5 test pieces is within 5 seconds, and none of the 5 test pieces ignites the cotton. 94VE: Maximum burning time within 30 seconds, average burning time within 25 seconds, no cotton ignition. 94VE-: Burning time is the same as 94VE-, however,
At least one of the specimens causes cotton to ignite. 94HB: Average burning time is 25 seconds or more or maximum burning time is 30 seconds or more. Further, the heat distortion temperature was measured in accordance with ASTM-D-648 as follows. Heat distortion temperature: A test piece with a length of 126 mm, a width of 12.6 mm, and a thickness of 6.3 mm.
With a bending stress of 18.6Kg/ ^cm2 applied, the test piece was heated at a heating rate of 2℃ per minute, and the amount of deflection was 0.254.
Find the temperature when it reaches mm and use it as the heat distortion temperature. Number average molecular weight Measured using high speed gel permeation chromatography (ALC/GPC244 manufactured by Nippon Waters) under the following conditions. (a) Column: Shodex A802 + A803 manufactured by Showa Denko (b) Solvent: tetrahydrofuran (c) Sample concentration: 1% by weight (d) Flow rate: 1 ml/min In addition, in the following examples, the part showing the amount used All parts are by weight. Example 1 Production of phosphate ester oligomer Ethylene glycol 62 in a 300ml four-necked flask
I prepared a section. phenylphosphonic acid dichloride while blowing nitrogen gas into the liquid and making it bubble.
156 parts were dropped into the flask at room temperature, and the reaction was allowed to occur while hydrogen chloride produced as a by-product was released from the system by bubbling nitrogen gas. After completing the dropwise addition, heat the reaction solution to 80℃.
The reaction was continued for 4 hours. The resulting reaction product is washed with water and dried to reveal the basic structure. Compound (A) was obtained. The number average molecular weight of this substance is
It was 950. Production of the composition: 40 parts of poly(2,6-dimethyl-1,4-phenylene) ether with an intrinsic viscosity of 0.50 dl/g (measured in chloroform at 25°C), 60 parts of high-impact polystyrene (475D manufactured by Asahi Dow), and 7 parts of the above compound (A),
Melt mixing was performed for 10 minutes at a screw rotation speed of 40 rpm in a plastomill maintained at 70°C to obtain the desired polyphenylene ether resin composition. The results of the combustion test and heat distortion temperature of the obtained resin composition are shown in Table 1. Example 2 The same procedure as Example 1 was carried out except that the weight ratio of polyphenylene ether resin and high impact polystyrene was 50:50. The results for the compositions obtained are shown in Table 1. Example 3 In the production of phosphate ester oligomer in Example 1, the basic structure was changed in exactly the same manner except that 76 parts of prolene glycol was used instead of ethylene glycol. Compound (B) was obtained. The number average molecular weight of this substance is
It was 1350. Table 1 shows the results for a resin composition obtained using this compound (B) in the same manner as in Example 1. Example 4 In the production of the phosphate ester oligomer of Example 1, 90 parts of 1,4-butanediol was used instead of ethylene glycol, and the basic structure was changed. Compound (C) was obtained. The number average molecular weight of this product was 800. Table 1 shows the results for a resin composition obtained using this compound (C) in the same manner as in Example 1. Example 5 In the production of the phosphate ester oligomer of Example 1, 222 parts of 1,6-hexanediol was used instead of ethylene glycol, and the basic structure was changed. Compound (D) was obtained. The number average molecular weight of this product was 1100. Table 1 shows the results for a resin composition obtained using this compound (D) according to the formulation of Example 1. Example 6 In the production of the phosphate ester oligomer of Example 1, 144 parts of cyclohexanedimethanol was used instead of ethylene glycol, and the basic structure was changed. Compound (E) was obtained. The number average molecular weight of this substance is
It was 3000. Table 1 shows the results for a resin composition obtained using this compound (D) in the same formulation as in Example 1. Example 7 A resin composition was prepared in the same manner as in Example 1, except that an acrylonitrile-butadiene-styrene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd., JSR-15) was used instead of the high-impact polystyrene used in Example 1. I got it. The combustion test results and heat distortion temperatures are shown in Table 1. Comparative Example 1 A composition containing the polyphenylene ether resin of Example 1 and high-impact polystyrene and containing no flame retardant was measured. As shown in Table 1,
No flame resistance was observed. Comparative Example 2 Similar measurements were carried out using triphenyl phosphate as a flame retardant instead of compound (A) in Example 1. As shown in Table 1, although flame retardancy was imparted, the heat distortion temperature was significantly lowered. Comparative Example 3 The same polyphenylene ether resin composition as in Example 2 but not containing compound (B) was measured. As shown in Table 1, no flame resistance was observed. Comparative Example 4 In Example 2, the same amount of triphenyl phosphate was used as a flame retardant instead of compound (A),
The obtained resin composition was measured. Although a flame retardant effect was obtained, the heat distortion temperature was significantly lower than in Comparative Example 3. Comparative Examples 5 and 6 Comparative Examples 5 and 6 were carried out in the same manner as in Example 1, but the amounts of compound (A) were changed to 0.05 parts and 25 parts, respectively. As shown in Table 1, no flame retardant effect was obtained when blending 0.05 parts, and a large decrease in heat distortion temperature occurred when blending 25 parts. Comparative Example 7 The reaction was carried out in the same manner as in Example 1, except that the amount of phenylphosphonic acid dichloride used was reduced to 15.6 parts. The number average molecular weight of the obtained compound (A-2) was 330. As shown in Table 1, the composition obtained using this low molecular weight compound (A-2) in the same manner as in Example 1 had the same flame retardant effect as in Example 1. , the heat distortion temperature had decreased. Comparative Example 8 A reaction was carried out in the same manner as in Example 1 except that the amount of phenylphosphonic acid dichloride used was increased to 195 parts, and a high molecular weight compound (A -3) was obtained. As shown in Table 1, the composition obtained using this high molecular weight compound (A-3) in the same manner as in Example 1 did not have a flame retardant effect.

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Claims (1)

[Claims] 1. A polyphenylene ether resin composition comprising a polyphenylene ether resin and another polymeric substance that is compatible with the polyphenylene ether resin.
Per 100 parts by weight, a number of dried units having the basic structure [Formula] (where R represents an aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue having 2 to 10 carbon atoms) A flame-retardant resin composition characterized in that 0.1-20 parts by weight of a phosphate ester oligomer compound having an average molecular weight of 500-5000 is added.