JPS61200163A - Polyphenylene ether resin composition having flame retardance - Google Patents

Abstract

PURPOSE:A composition having improved flame retardance and preventing volatility of a flame-retardant, obtained by blending a composition comprising a polyphenylene ether resin or further polystyrene resin with a specific naphthyl phosphate compound. CONSTITUTION:A resin composition comprising (A) polyphenylene ether resin, preferably poly (2,6-dimethyl-1,4-phenylene) ether, etc. or (B) the component A and a polystyrene resin such as rubber modified polystyrene, etc., is blended with (C) 1-50wt.%, preferably 1-25wt.% one or more of naphthyl phosphate compounds shown by the formula (X is 0, 1, or 2; R5 is 1-8C alkyl, or phenyl, and naphthyl or phenyl may be replaced with 1-3C alkyl), to give the aimed composition.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention has excellent flame retardancy, substantially prevents the volatility of flame retardants, and furthermore maintains excellent heat resistance and mechanical strength. The present invention relates to a polyphenylene ether resin composition. More specifically, the present invention relates to a flame-retardant polyphenylene ether resin composition comprising a polyphenylene ether resin or a resin composition of a polyphenylene ether resin and a polystyrene resin mixed with at least one specific naphthyl phosphate compound.

[Conventional technology]

Polyphenylene ether is a resin with excellent properties such as heat resistance, rigidity, and electrical properties, and is used in a wide range of applications as a useful engineering plastic. However, polyphenylene ether is inferior in moldability and impact resistance, and furthermore, it is difficult to say that it has sufficient flame retardancy by itself.

U.S. Pat.
．． It is disclosed in various documents such as No. 383,455. However, it is well known that the flame retardancy of polyphenylene ether is greatly impaired by adding styrene resins and elastomers.

Therefore, in order to use polyphenylene ether or a resin composition consisting of polyphenylene ether and styrene resin and/or elastomer for applications that require flame retardancy, it is essential to include a flame retardant. well known. Flame retardants that have been conventionally recognized as effective are mainly phosphorus-containing compounds and halogen-containing compounds.

For example, JP-A-49-52947, JP-A-55-
The use of aromatic phosphoric acid esters is proposed in JP-A No. 75248, JP-A-55-16081, and JP-A-57-30737.

When phosphoric acid esters are blended into polyphenylene ether as a flame retardant, they exhibit excellent flame retardant effects and also improve molding processability due to their plasticizing effect. It is unavoidable that mechanical strength such as tensile strength will decrease significantly, and an even bigger problem is that these phosphate esters volatilize from the resin phase during molding, contaminate the mold, and even deteriorate the appearance of the molded product. It is also a loss. This is due to the fact that the molding material containing polyphenylene ether requires a relatively high temperature of 250 to 300° C., which poses a serious problem in practical terms. Taking triphenyl phosphate and tricresyl phosphate as an example,
Even after these are kneaded into the resin phase, about 2096 of them may volatilize when heated to around 600°C.

As a technique to solve the problem of volatility of phosphoric acid esters, Japanese Patent Application Laid-open No. 1189557/1983 discloses
The use of aromatic phosphate ester polymers has been proposed.

Although the use of this polymer solves the problem of volatility, on the other hand, which is thought to be due to the structure of these polymers, the blending of these polymers leads to a decrease in the melt flowability of polyphenylene ether, making it difficult to form and process. A new problem arises: the loss of sexuality.

On the other hand, there are many known techniques regarding halogen-containing compounds; for example, JP-A-48-7945 proposes a method of blending hexabromobenzene and antimony oxide; Japanese Unexamined Patent Publication No. 52-
No. 57255 also discloses a method of adding a similar aromatic halogen compound. Halogen-containing compounds have almost no plasticizing effect on polyphenylene ether, and when blended with polyphenylene ether, it hardly impairs its heat resistance, an advantage that phosphoric acid esters do not have. Pat11, ? −−j, ζ
Jishi Ihachi F; 75 The drawback is that No. C Kanbei Chocho Mackerel Tozume Tgo is not appreciated. Furthermore, when a halogen-containing compound is used as a flame retardant, plumes may be generated due to the migration of the halogen-containing compound to the surface of the molded product.
It is well known that problems such as corrosion of molding machines and molds due to thermal decomposition products of halogen-containing compounds occur.

Furthermore, Japanese Patent Publication No. 4B-58768 discloses a method of using a kx phosphate ester and an aromatic halogen compound in combination; The shortcomings have not been improved yet.

[Problem that the invention seeks to solve]

The present inventors have solved the above-mentioned drawbacks that occur when conventionally known phosphorus-containing compounds or halogen-containing compounds are blended as flame retardants into polyphenylene ether-based resins or resin compositions of polyphenylene ether-based resins and polystyrene-based resins. As a result of further investigation to solve the problem, we decided to use naphthyl phosphate as a filling agent and 1. In addition to providing excellent flame retardancy, volatilization of the flame retardant from the resin composition is substantially prevented, and it also exhibits good moldability and excellent heat resistance. It has been found that the properties and mechanical strength can be maintained.

[Means for solving problems]

That is, the present invention provides (a) a polyphenylene ether resin or V, (b) a resin composition containing (a) and a polystyrene resin, and (c) a naphthyl phosphate compound represented by the following general formula (1). At least one general formula (wherein, It may be substituted with one to three alkyl groups.)
A novel flame-retardant polyphenylene ether resin composition is produced by blending the following.

The polyphenylene ether resin used in the SL fat composition of the present invention is a monocyclic phenol represented by the general formula (fl) (wherein R1 is a lower alkyl group having 1 to 3 carbon atoms, R2 and R3 are hydrogen atoms) Polyphenylene ether obtained by oxidative polycondensation of one or more of the following: or a lower alkyl group having 1 to 6 carbon atoms. Polyphenylene ether obtained by graft polymerizing a vinyl aromatic compound to this polyphenylene ether. This includes graft copolymers with This polyphenylene ether may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by general formula (I) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-
Methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,6-dimethylphenol, 2゜6-diethylphenol, 2,5-dipropylphenol , 2-methyl-3-ethylphenol, 2-methyl-
3-propylphenol, 2-ethyl-6-methylphenol, 2-ethyl-5-7'-methylphenol, 2-
7'pyl-3-methylphenol, 2-propyl-3
-Ethylphenol, 2,3.6-1-dimethylphenol, 2,3.6-)dimethylphenol, 2゜3.6-
Examples include doliprovirphenol, 2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-6-probylphenol, and the like.

Examples of polyphenylene ether obtained by polycondensation of one or more of these monocyclic phenols include poly(2,6-dimethyl-1,4-phenylene) ether and poly(2゜6-diethyl-1,4). -phenylene) ether, BoIJ (2,6-diprobyl-1,4-phenylene) ether, poly(2-methyl-6-nityl-1,4-)unilene) ether, poly(2-methyl-6
-broby-1,4-phenylene)ether, poly(2
-ethyl-6-propyl-1,4-phenylene) ether, 2,6-dimethylphenol/2,3.6-dolimethylphenol copolymer, 2,6-dimethylphenol/2,3.6- Doryethylphenol copolymer, 2.6
-diethylphenol/2,3.6-1-limethylphenol copolymer, 2,6-diprobylphenol/2.
3.6-)limethylphenol copolymer, poly(2,6
2,6-dimethylphenol/2,3. ．． 4-) A graft copolymer obtained by graft-polymerizing styrene onto a trimethylphenol copolymer can be mentioned. In particular, poly(2,6-cymethyl-1.
The polyphenylene used in the present invention is 4-phenylene) ethyl, 2,6-dimethylphenol/2,3゜6-drimethylphenol copolymer, and a graft copolymer obtained by grafting styrene onto each of the former two. It is preferable as an ether resin.

In the resin composition of the present invention, the polystyrene resin forming the resin composition with the polyphenylene ether resin has the following general formula (III) (wherein R4 is a hydrogen atom or a lower alkyl group, and Z is a halogen atom or a lower represents an alkyl group, and p is 0 or a positive integer of 1 to 3.)
It refers to a resin containing at least 25% by weight of the structural unit represented by the following formula in its polymer. Examples of such polystyrene-based resins include polystyrene, rubber-modified polystyrene (impact-resistant polystyrene), poly-p-methylstyrene, rubber-modified poly-p-methylstyrene, and styrene-modified polystyrene.
Butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-acrylic acid rubber-acrylonitrile copolymer, styrene-α-methylstyrene copolymer, styrene-butadiene block copolymer, styrene-maleic anhydride copolymer, rubber-modified styrene-maleic anhydride copolymer etc., and two or more of these may be used in combination.

The naphthyl phosphate compound used in the resin composition of the present invention includes phosphate compounds having at least one naphthyl structure in the molecule represented by the general formula (1). In the resin composition of the present invention, the naphthyl phosphate compound represented by general formula (1) may be used alone or as a mixture of two or more.

In general formula (I), X=2, that is, examples of mononaphthyl phosphate compounds include 1-t or 2-naphthyl diphenyl phosphate, 1-t or 2-naphthyl diethyl phosphate, 1- or 2-naphthyl diethyl phosphate, Renyl phosphate, 1- or 2-naphthyl dimethyl phosphate, 1- or 2-naphthyl diethyl phosphate, 1-1 or 2-naphthyl dipropyl phosphate, 1- or 2-naphthyl dibutyl phosphate-1-1
Examples include 1--j or 2-naphthyldioctyl phosphate.

In general formula (I), X=1, that is, as an example of a bisnaphthyl phosphate compound, bis(1- or 2-
naphthyl) phenyl phosphate, bis(1- or 2-
-naphthyl)talesyl phosphate, bis(1- or 2-naphthyl)xylenyl phosphate, bis(1- or 2-naphthyl)methyl phosphate, bis(1- or 2-naphthyl)ethyl phosphate, bis(1- or 2-naphthyl)ethyl phosphate, 2-naphthyl)propyl phosphate, bis(1-
or 2-naphthyl)butyl phosphate, bis(1-
or 2-naphthyl) octyl phosphate.

Further, in general formula (I), x=0, that is, as an example of a trisnaphthyl phosphate compound, tris(1
- or 2-naphthyl) phosphate.

In these naphthyl phosphate compounds, one or both of the two rings of the naphthyl group may be substituted with an alkyl group having 1 to 3 carbon atoms.

Among the naphthyl phosphate compounds mentioned above, general formula (
Mono- or bis-naphthyl phosphate compounds in which X=1 or 2 in 1) and R5 is a phenyl group or an alkyl-substituted phenyl group and tris-naphthyl phosphate compounds in which X=O in general formula (I) are the objects of the present invention. It is more suitably used.

In the resin composition of the present invention, 21! When using a mixture of Ii or more, the combination of the mono-, bis-, and tris-naphthyl phosphate compounds can be selected as appropriate.

By the way, the naphthyl phosphate compound used in the resin composition of the present invention is usually produced by reacting a naphthol compound alone or, if desired, a mixture of a naphthol compound and a phenol compound or an aliphatic alcohol compound with phosphorus oxychloride. be done. Such manufacturing methods are described, for example, in U.S. Pat.
56,471 and West German Patent No. 567.954
It is disclosed in the specification of No. When a mixture is used as a raw material, the content of mono-, bis-, or tris-naphthyl phosphate compounds can be changed by appropriately changing the mixing ratio or the reaction order of the raw materials. When a mono-, bis-, or tris-naphthyl phosphate compound is used alone, the desired naphthyl phosphate compound may be isolated from the reaction product by a well-known separation operation such as distillation. On the other hand, as described above, in one embodiment of the resin composition of the present invention, it is possible to use two or more types of naphthyl phosphate compounds represented by the general formula (I) in combination, and specific examples of such an embodiment As an example, a product obtained from the above mixture as a raw material,
The bis and tris naphthyl phosphate compound mixture product can also be used as is. When there is no need to strictly adjust the mixing ratio of mono-, bis-, or tris-naphthyl phosphate compounds, it is practical to use the mixed product as it is.

Generally speaking, in the resin composition of the present invention, 2 of the naphthyl phosphate compound represented by the general formula (1) is
When using a mixture of two or more species, it is desirable that the content of the mononaphthyl phosphate compound is 50% by weight or more.

In the resin composition of the present invention, in addition to the naphthyl phosphate compound, a triaryl phosphate compound or a trialkyl phosphate compound represented by the general formula (1'V) 0=P+0R5)3......(tV
) [In the formula, R5 is the same as in general formula (I)] may be present together in an amount as long as the effects of the present invention are not inhibited. A triaryl phosphate compound or a trialkyl phosphate compound produced as a by-product by reacting a mixture of a naphthol compound and a phenol compound or an aliphatic alcohol compound with phosphorus oxychloride may be used as is as a mixed product with a naphthyl phosphate compound. If desired, a separately prepared triarylphosphate compound or trialkylphosphate compound may be added to the naphthylphosphate compound.

In the resin composition of the present invention, the naphthyl phosphate compound is present in an amount of 1 to 50% by weight, preferably 1 to 25% by weight.
The remainder is occupied by polyphenylene ether resin or a resin composition of this and polystyrene resin. In a resin composition of polyphenylene ether resin and polystyrene resin, the former is 1% in the resin composition.
It accounts for ~99% by weight, preferably 10-90% by weight, and more preferably 20-80% by weight.

Other components such as various additives, fillers, and elastomers may be added to the gooseberry combination of the present invention depending on the purpose. For example, sterically hindered phenols, organic phosphites, phosphonites, phosphonasic acids, cyclic phosphonites, hydrazine derivatives, amine derivatives, carbamate derivatives, thioethers, phosphoric triamides,
Stabilizers such as benzoxazole derivatives and metal sulfides;
Ultraviolet absorbers such as benzotriazole derivatives, benzophenone derivatives, salicylate derivatives, sterically hindered amines, and oxalic acid diamide derivatives; Olefin waxes as lubricants such as polyethylene wax and polypropylene wax; triphenyl phosphate, tricresyl phosphate , talesyl diphenyl phosphate,
Phosphate-based flame-retardant plasticizers typified by phosphates produced from a mixture of isopropylphenol and phenol, dimers of talesyl diphenylphosphate, etc.;
Brominated flame retardants represented by decabromo biphenyl, pentabromotoluene, decabromo biphenyl ether, brominated polystyrene, etc.; Pigments represented by titanium oxide, zinc oxide, carbon black, etc.; Glass fiber, glass peas, asbestos, etc. million last night, mica, talc,
Inorganic fillers represented by clay, calcium carbonate, silica, etc.; Metal flakes represented by copper, nickel, aluminum, zinc flakes, etc.; Metals represented by aluminum fibers, aluminum alloy fibers, brass fibers, stainless steel fibers, etc. Fiber: Examples include organic fillers such as carbon fiber and aromatic polyamide fiber.

Further, the elastomer is an elastomer in a general sense, for example, as described in "
Properties and 5structures
of Polymers” (John W.
ILEY & 5ons, Inc., 1960) 71
The definition adopted on page 78 can be cited, and an elastomer is one whose Young's modulus at room temperature is 105 to 10 dyn.
es/d (0.1 to 102 oKg/c++l). Specific examples of elastomers include:
A-B-A' shaped elastomer block copolymer, A-B-A in which the double bond of the polybutadiene portion is hydrogenated
l m Elastomeric block copolymers, polybutadiene, polyisoprene, copolymers of diene compounds and vinyl compounds, radial teleblock copolymers, nitrile rubber, ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDM), Thiokol rubber,
Polysulfide rubber, acrylic acid comb, polyurethane rubber, graft copolymer of butyl rubber and polyethylene,
polyester elastomer, polyamide elastomer,
Examples include polyurethane elastomer.

Particularly desirable is an A-B-A' shaped elastomer block copolymer. The terminal blocks A and B of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block or a conjugated diene block in which most of the double bonds are hydrogenated, It is desirable that the molecular weight of the B block is greater than the combined molecular weight of the A and A' blocks. The terminal blocks A and A1 may be the same or different and are thermoplastic homopolymers or copolymers derived from vinyl aromatic hydrocarbons in which the aromatic moieties may be monocyclic or polycyclic. Examples of such vinyl aromatic hydrocarbons include styrene, alpha-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. central block B
#i Conjugated diene hydrocarbon, such as 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3
- elastomeric polymers derived from pentagene and mixtures thereof. Each end block A and A
' preferably has a molecular weight of about 2,000 to about 1,000
,000, while the molecular weight of central block B preferably ranges from about 25°000 to about 1,000,000.
is within the range of

When preparing the polyphenylene ether resin composition of the present invention, any conventionally known method may be used. For example, after mixing each component with a same-speed mixer such as a turnpull mixer or a Henschel mixer, extrusion is performed. A method of kneading with a machine, a Banbury mixer, etc. is appropriately selected.

〔Example〕

The resin composition of the present invention will be specifically explained below using Examples and Comparative Examples.

Reference Example 1 2-naphthol 289.9 (2 moles) and phosphorus oxychloride 3079 (2 moles) were charged in a reactor, 3 g of anhydrous aluminum chloride was added thereto, and the mixture was stirred for 5 hours while passing nitrogen gas. The temperature of the contents was raised to 150°C, and then the temperature was raised to 165°C over 3 hours to carry out the reaction. After once cooling the obtained reaction product to room temperature, phenol 5769 (4 mol) was added, stirring was added while gradually raising the temperature, and the contents were raised to 190°C over 6 hours while passing nitrogen gas. Warm it up for another 6 hours.
The reaction was completed by raising the temperature to 00°C.

After cooling the obtained reaction product, it was dissolved in approximately the same volume of carbon tetrachloride, and the obtained solution was shaken three times with a 6% concentration caustic soda aqueous solution, washed, and then shaken with water. I took it and washed it.

Carbon tetrachloride is distilled off from the neutralized and purified solution by vacuum distillation, and then 3.511H,! i' About 70.9 of the fraction at 175 to 180° C. under reduced pressure was distilled off to obtain a naphthyl phosphate mixture (hereinafter referred to as “naphthyl phosphate mixture A”).

The composition of the obtained naphthyl phosphate mixture A was determined by GC-
As a result of confirmation by mass analysis, it was found to be the following mixture.

Component of X=O: 2% by weight Component of x==1: Component of 27-fold quadrature 2.6-dimethylphenol/2,3.6-dolimethylphenol copolymer (2
, 5,6-drimethylphenol accounts for 5 moles96) 50 parts by weight at 25°C using chloroform as a solvent.
46 parts by weight of rubber-modified polystyrene having a polystyrene matrix with an intrinsic viscosity of 0.89 (dll&) and a gel content of 16.5% by weight; 5 parts by weight of an ethylene-propylene copolymer (with a styrene to butadiene geometrical ratio of 50,770 and a viscosity of 1500 cps measured on a Brookfield Model RTV viscometer from a 20% toluene solution at 25°C) as 0.1 g
Reduced specific viscosity measured at 25°C at a concentration of /l 00 ml is 2) 1 part by weight of naphthyl phosphate mixture A
19 parts by weight, tetrakis(2,4-di-tert-butylphenyl)-4゜41-biphenylene diphosphonite 0.3 parts by weight, 2.21-methylene-bis(4-methyl-6-tert-butylphenol) ) 0.6 parts by weight and 5 parts of titanium oxide were thoroughly mixed in a Henschel mixer, the resulting mixture was pelletized using a twin-screw extruder, and then the resulting pellets were molded to a thickness using an injection molding machine. 1.5 birds, width 12.7 birds and length 127m
A test piece of m was molded. Using the obtained test piece, UL-
A combustion test according to the 94 standard was conducted and the average burning time was measured. Similarly, a test piece with a thickness of about 6 mm was molded to measure the heat distortion temperature, and a dumbbell piece with a thickness of about 6 mm was molded to measure the tensile strength.

The melt flow value was measured at 230℃ using a Koka type flow tester.
, 60~load, and the heating loss rate was measured as the weight loss rate at 500°C with a heating rate of 10°C per minute using a thermobalance.

The measurement results for each oak are shown in Table-1.

Reference Example 2 Production of naphthyl phosphate mixture B The operation of Reference Example 1 was repeated except that 1-naphthol was used instead of 2-naphthol in Reference Example 1, and a naphthyl phosphate mixture (hereinafter referred to as [naphthyl phosphate mixture BJ, !: ) was obtained.

The composition of the obtained naphthyl phosphate mixture B was analyzed using the same method as in Reference Example 1, and the composition was as follows.

X=O component: 1% by weight X=1 component: 28% by weight X==2 component: 65% by weight X=3 component = 6% by weight Example 2 In Example 1, the naphthyl phosphate mixture Naphthyl phosphate mixture B obtained in Reference Example 2 in place of A
Various test pieces were obtained by repeating the operation of Example 1 except for using the following.

Various performances measured in the same manner as in Example 1 are shown in Table-1.

Reference Example 3 The naphthyl phosphate mixture obtained in Reference Example 1 was subjected to vacuum distillation to obtain a
A fraction with a boiling point of 220°C was collected. This fraction was 2-naphthyldiphenyl phosphate.

Example 6 Various test pieces were obtained by repeating the procedure of Example 1 except that 2-naphthyl diphenyl phosphate obtained in Reference Example 3 was used in place of naphthyl phosphate mixture A.

Various performances measured in the same manner as in Example 1 are shown in Table-1.

Comparative Examples 1.2 and 3 In Example 1, triphenyl phosphate (Comparative Example 1), tricresyl phosphate (Comparative Example 2) and tricylenyl phosphate (Comparative Example 5) were used in place of naphthyl phosphate mixture A, respectively. The procedure of Example 1 was repeated except that:

Various performances are also listed in Table-1.

Reference Example 4 Production of naphthyl phosphate mixture C In a reactor, 376 g (4 moles) of phenol, 307!9 (2 moles) of oxychloride, and anhydrous aluminum chloride were placed in a reactor.
5I and the reaction was carried out in the same manner as in Reference Example 1. After distilling off unreacted phosphorus oxychloride from the reaction product, the reaction product was once cooled to room temperature, and then 2-naphthol 340, S? (2 mol) was added, and the reaction was completed in the same manner as in Reference Example 1.

The obtained reaction product was neutralized and purified in the same manner as in Reference Example 1, and carbon tetrachloride was further distilled off from the reaction solution under reduced pressure to obtain a naphthyl phosphate mixture (hereinafter referred to as "naphthyl phosphate mixture C"). Obtained.

The composition of the obtained naphthyl phosphate mixture C was analyzed using the same method as in Reference Example 1, and the composition was as follows.

Component of X=O: 0% by weight Component of X=1 = 21 weight%) Component of X=2 = 56% by weight Component of x=3 = 23% by weight Example 4 2,6- used in Example 1 Dimethylphenol/2,5
．． 40 parts by weight of 6-1-limethylphenol copolymer,
57 parts by weight of the rubber-modified polystyrene used in Example 1,
2 parts by weight of the elastomer block copolymer used in Example 1, 1 part by weight of the ethylene-propylene copolymer used in Example 1, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl Enylene diphosphonite 0.34 parts by weight, 2.2'-methylene-bis(4-
To 0.57 parts by weight (methyl-6-tert-butylphenol) and 7 parts by weight of titanium oxide, 09 parts by weight of the naphthyl phosphate mixture obtained in Reference Example 4 was added, and these were thoroughly mixed in a Henschel mixer. Various test pieces were molded in the same manner as in Example 1.

Various performances measured in the same manner as in Example 1 are shown in Table 1-2.

Comparative Examples 5 and 6 The procedure of Example 4 was repeated, except that triphenyl phosphate (Comparative Example 5) and tricresyl phosphate (Comparative Example 6) were used in place of naphthyl phosphate mixture C, respectively. .

Each performance is also listed in Table-2.

Comparative Example 7 The procedure of Example 4 was repeated except that naphthyl phosphate mixture C was not used in Example 4.

Each performance is also listed in Table-2.

Table 2 Reference Example 5 The procedure of Reference Example 1 was repeated except that 432.9 (4 mol) of mixed cresol was used in place of 376 g of phenol, and a naphthyl phosphate mixture (hereinafter referred to as "naphthyl phosphate mixture D") was prepared. call).

The composition of the resulting naphthyl phosphate mixture was analyzed using the same method as in Reference Example 1, and the following x = 00 components were found:
= 2% by weight x = 1 component: 25 weight jl: 96
(ru/!i+) of poly(2,6-cymethyl-1.
4-phenylene) ether 100 parts by weight, tetrakis(2,4-di-tert-butylphenyl)-4,4'
- Biphenylene diphosphonite 0.3 parts by weight, 2.
After thoroughly mixing 0.6 parts by weight of 2'-methylene-bis(4-methyl-6-tert-butylphenol) and 10 parts by weight of the naphthyl phosphate mixture obtained in Reference Example 5 with a Henschel mixer, Example 1 was prepared. Various test pieces were molded using the same procedure.

Various performances measured in the same manner as in Example 1 are shown in Table 3.

Reference Example 6 A reactor was charged with 2-naphthol 4549 (3 mol), phosphorus oxychloride 153 g (1 mol), and anhydrous aluminum chloride 1.5 g, and the contents were evaporated over 5 hours while stirring and passing nitrogen gas. Raise the temperature to 150℃, then 8
The temperature was raised to 200℃ over time, and then further heated to 240℃ for 5 minutes.
The reaction was carried out for a period of time to complete the reaction.

The obtained reaction product was dissolved in benzene, and the insoluble matter was separated by F. The P solution was thoroughly shaken and washed with a 3% by weight aqueous solution of caustic soda, and further shaken and washed with water. Benzene was distilled off under reduced pressure from the neutralized and purified solution to obtain a crystalline product.

The obtained crude product was recrystallized using a benzene-petroleum ether mixed solvent to obtain crystals of tris(2-naphthyl)phosphate having a melting point of 110 to 111°C.

Example 6 The procedure of Example 5 was repeated except that the tris(2-naphthyl) phosphate obtained in Reference Example 6 was used in place of the naphthyl phosphate mixture.

Various performances measured in the same manner as in Example 1 are shown in Table 3.

Comparative Example 8 The procedure of Example 5 was repeated except that triphenyl phosphate was used instead of the naphthyl phosphate mixture.

Each performance is also listed in Table-6.

Table 3 [Effects of the Invention] As can be seen from the results of Examples and Comparative Examples, the phosphate compound of the present invention having at least one naphthyl structure in the molecule is effective in the polyphenylene ether resin composition of the present invention. It can be seen that it imparts a flame retardant effect and does not impair heat resistance, mechanical strength and moldability.

In particular, the heating loss rate is significantly lower than that of conventionally known phosphate compounds such as triphenyl phosphate, and this is because the naphthyl phosphate compound used in the present invention does not volatilize from the polyphenylene ether resin composition even at high temperatures. Characterized by exhibiting extremely useful phenomena

Claims (1)

[Claims] (a) polyphenylene ether resin or (b) (a)
) and a polystyrene resin (c
) A polyphenylene ether resin composition having excellent flame retardancy and comprising at least one naphthyl phosphate compound represented by the following general formula (I). General formulas▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (In the formula, x represents 0 or an integer of 1 to 2, R_5 represents a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group, and the above naphthyl group and phenyl group represent 0 or an integer of 1 to 2 carbon atoms. 3 may be substituted with an alkyl group.)