JP2000256551A - Flame-retardant polyphenylene ether-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which excels in flame-retardancy, contains no halogen, has high melting point and low volatility, and does not lower its mechanical properties, molding processability, etc., by including a specific resin and a crosslinked phosphazene-based flame retardant. SOLUTION: This composition is obtained by including (A)100 pts.wt. of a resin comprising (i)1-99 pts.wt. of a polyphenylene ether resin and (ii) 99-1 pts.wt. of a polystyrene-based resin and (B) 1-30 pts.wt. of crosslinked phosphazene-based flame retardant. The component B is preferably such a compound that a compound of formula I (m is 3-25; Ph is phenyl) and/or formula II [X1 is N=P(O)OPh or the like; Y1 is P(OPh)4 or the like; n is 3-10,000] is crosslinked with a crosslinking group such as o-phenylene, the crosslinking group interposes between two Os as a result of eliminating the phenyl group of the phosphazene compound, the content of the phenyl groups is 50-99.9% based on the total phenyl groups of the compound(s) of formula I and/or formula II, and there is no free hydroxyl group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polyphenylene ether-based resin composition and a flame-retardant polyphenylene ether-based resin molded product.

[0002]

2. Description of the Related Art Polyphenylene ether resins are used for automotive parts, electric and electronic products, OA equipment, office equipment, communication equipment and the like because of their excellent mechanical properties, electrical properties, heat resistance and the like. . In these applications, it is necessary to make the resin flame-retardant due to problems such as heat generation and ignition of internal components.

In order to impart flame retardancy to a polyphenylene ether-based resin, it is common to add a flame retardant before molding the resin. As the flame retardant, inorganic hydroxides, organic halogen compounds, halogen-containing organic phosphorus compounds, red phosphorus, organic phosphoric esters, phosphazene compounds and the like are known.

However, halogen-containing compounds such as organic halogen compounds and halogen-containing organic phosphorus compounds have excellent flame-retardant effects. However, they thermally decompose during molding of a resin to generate hydrogen halide, thereby causing corrosion of a mold and resin. Causes deterioration and coloring of the toner. In addition, when the resin is burned due to incineration, fire, or the like, there is a problem in that harmful gases such as hydrogen halide, smoke and dioxin are generated, and environmental pollution is caused. The use of antimony trioxide together with the halogen-containing compound significantly improves the flame retardancy, so that antimony trioxide is generally used as a flame retardant aid. However, since antimony trioxide is suspected of being a carcinogenic compound, there is a problem when used in combination with a halogen-containing compound.

On the other hand, halogen-free flame retardants include inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide, red phosphorus, organic phosphoric esters, phosphazene compounds and the like. However, inorganic hydroxides exhibit flame retardancy due to water generated by thermal decomposition, and thus have a low flame retardant effect.
Therefore, it must be added in a large amount, but there is a disadvantage in that the addition of a large amount impairs the inherent properties of the resin. Although red phosphorus has a high flame retardant effect, it has a disadvantage that the resin composition is colored red. Organophosphates are widely used because of their relatively good flame-retardant effects. Representative examples include triphenyl phosphate (TPP) and resorcinol bis (diphenyl phosphate) (RDPP). Yes (Special Publication 53-4
No. 18, JP-A-53-73248). However, since these organic phosphates are liquids or low-melting-point solids, they have high volatility, greatly reduce the heat resistance of the resin, and have problems such as blocking and bleeding (juicing) during kneading. .

[0006]

[Problems to be Solved by the Invention]
Japanese Patent Application Publication No. JP-A-2002-157, describes a polyphenylene ether-based resin composition in which a phosphazene-based compound is blended with a polyphenylene ether-based resin. In this publication, the blending of a phosphazene-based compound effectively suppresses a decrease in the heat resistance of a composition containing polyphenylene ether or a polystyrene-based resin as a resin component, and is more difficult than phosphate esters. It is disclosed that flammability is achieved. However, according to the technology described in the publication, in a composition containing polyphenylene ether and a polystyrene resin as a resin component, a resin composition having a high polystyrene resin content (for example, a polystyrene resin content of 30 to 90% by weight) is used. % Of the resin composition).
Flame retardancy evaluation V-0 in the flame retardancy test specified in 94
Achieving high flame retardancy cannot achieve flame retardancy.

Japanese Patent Application Laid-Open No. Hei 7-216235 discloses that thermoplastic resins (1) phosphazene compounds and (2)
A flame-retardant resin composition containing a salt of cyanuric acid or isocyanuric acid and a melamine compound as a flame retardant is described. The publication describes that the resin composition does not generate volatile components such as hydrogen halide and has high flame retardancy, mechanical properties, and hydrolysis resistance. However, in this publication, although polyphenylene oxide resin (PPO, that is, polyphenylene ether (PPE) resin), which is relatively easily flame-retarded, is specifically described as flame-retardant, polystyrene which is extremely difficult to be flame-retarded is described. There is no specific description that the modified PPE resin containing the base resin is made flame-retardant. The present inventor has proposed a modified PPE resin having a high polystyrene resin content (polystyrene resin content: 3).
When the flame retardant is added to the modified PPE resin (0 to 90% by weight), the modified PPE resin has sufficient flame retardancy (flame retardancy test in a flame retardancy test specified in UL-94). It was impossible to impart high flame retardancy to achieve V-0).

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that a resin comprising polyphenylene ether resin and polystyrene resin is blended with a crosslinked phosphazene-based flame retardant. It has been found that sufficient flame retardancy can be imparted to the resin. In addition, the present inventor has found that by blending a crosslinked phosphazene-based flame retardant and a triazine skeleton-containing compound with a resin composed of a polyphenylene ether resin and a polystyrene-based resin, a higher degree of flame retardancy can be imparted to the resin.

According to the present invention, (A) 1 to 99 parts by weight of polyphenylene ether resin and polystyrene resin 99
(B) with respect to 100 parts by weight of the resin consisting of
There is provided a flame-retardant polyphenylene ether-based resin composition comprising 1 to 30 parts by weight of a crosslinked phosphazene-based flame retardant.

Further, according to the present invention, (A) 100 parts by weight of a resin composed of 1 to 99 parts by weight of a polyphenylene ether resin and 99 to 1 part by weight of a polystyrene resin,
Flame retardant in which (B) a composition containing 1 to 30 parts by weight of a crosslinked phosphazene-based flame retardant, and (C) a triazine skeleton-containing compound in an amount of 30 parts by weight or less based on 100 parts by weight of the resin as the component (A) A polyphenylene ether-based resin composition is provided.

According to the present invention, the flame-retardant polyphenylene ether-based resin composition may further contain (D) 50 parts by weight or less of an inorganic filler and / or (E) 30 parts of an organic phosphorus compound containing no halogen. A flame-retardant resin composition blended in an amount of not more than part by weight is provided.

Further, according to the present invention, there is provided a flame-retardant polyphenylene ether-based resin molded article obtainable by molding the above-mentioned various flame-retardant polyphenylene ether-based resin compositions.

According to the present invention, even a polyphenylene ether-based resin having a high content of a highly flammable polystyrene-based resin does not contain halogen, has a high melting point, low volatility, mechanical properties, and moldability. And the like, do not lower the inherent properties of the resin, have no problems such as blocking or bleeding during kneading, do not cause dripping during combustion, and have a flame retardancy rating V in the flame retardancy test specified in UL-94. It is possible to obtain a resin composition having a high flame retardancy to achieve −0.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION [Resin Component] The polyphenylene ether resin which is the component (A) of the present invention has, for example, the following general formula:

[0015]

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Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ] It is a polymer which consists of a structural unit represented by these. In the polyphenylene ether resin of the present invention, the structural unit is 1
It may be a homopolymer composed of a kind or a copolymer composed of two or more kinds of the above structural units.

As a specific example of such a polyphenylene ether resin, 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, copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol,
Copolymer of 2,6-dimethylphenol and 2,3,6-triethylphenol, copolymer of 2,6-diethylphenol and 2,3,6-trimethylphenol, 2,6
-Dipropylphenol and 2,3,6-trimethylphenol, among which poly (2,6
-Dimethyl-1,4-phenylene ether) is particularly preferred.

These polyphenylene ether resins can be easily synthesized, for example, according to the experimental method described in “Experimental Chemistry Lecture”, Vol. 28, Vol. 28, Polymer Synthesis, page 182, 4th edition.

The polystyrene resin, which is another component (A) of the present invention, has, for example, the following general formula:

[0020]

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Wherein R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁶ is a halogen atom or carbon number 1 to
3 represents an alkyl group. 1 shows 0 or the integer of 1-3. Is a resin containing at least 25% by weight or more of the structural unit represented by the formula (1) in the polymer.

Specific examples of such a polystyrene resin include polystyrene, rubber-modified polystyrene (high impact polystyrene), styrene-butadiene copolymer, and styrene-butadiene-acrylonitrile copolymer. Among them, impact-resistant polystyrene is preferably used. The polystyrene resin of the present invention includes polybutadiene-styrene copolymer rubber, EPD
Rubber-modified polystyrene modified with a rubber component such as M is included.

The mixing ratio of polyphenylene ether to polystyrene resin is usually 1 to 99 parts by weight of polyphenylene ether resin and 99 to 100 parts by weight of polystyrene resin.
１1 part by weight.

[Crosslinked phosphazene-based flame retardant] The crosslinked phosphazene-based flame retardant as the component (B) of the present invention includes:
For example, general formula (1)

[0025]

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[Wherein m represents an integer of 3 to 25]. Ph represents a phenyl group. A phenoxyphosphazene represented by the general formula (2):

[0027]

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Wherein X ¹ represents a group —N 基 P (OPh) ₃ or a group —N ＝ P (O) OPh, and Y ¹ represents a group —P (OPh) ₄
Or a group -P (O) (OPh) ₂ . n is 3 to 100
Indicates an integer of 00. Ph is the same as above. At least one phosphazene compound selected from the group consisting of linear phenoxyphosphazenes represented by the following formulas: o-phenylene group, m-phenylene group, p-phenylene group and general formula (3)

[0029]

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Wherein A is —C (CH ₃ ) ₂ —, —SO
_{It represents 2-} , -S- or -O-. a represents 0 or 1. A compound cross-linked by at least one type of cross-linking group selected from the group consisting of bisphenylene groups represented by the formula (a): Interposed between atoms, (b)
The phosphazene compound (1) having a phenyl group content of
And / or 50 based on the total number of all phenyl groups in (2).
To 99.9%, and (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule. In the above general formula (2),
n is preferably an integer of 3 to 1000.

According to the present invention, the general formula (4)

[0032]

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Wherein m is the same as above. And the general formula (5)

[0034]

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[Wherein X ² is a group -N = PCl ₃ or a group -N =
Represents P (O) Cl, and Y ² represents a group —PCl ₄ or a group —P
(O) Cl ₂ is shown. n is the same as above. At least one dichlorophosphazene compound selected from the group consisting of linear dichlorophosphazenes represented by the general formula (6):

[0036]

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[Wherein M represents an alkali metal. An alkali metal phenolate represented by the general formula (7):

[0038]

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Wherein M is the same as above. An alkali metal diphenolate represented by the general formula (8):

[0040]

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Wherein A, a and M are as defined above. And a mixture with at least one diphenolate selected from the group consisting of alkali metal diphenolates, and then further reacting the resulting compound with the alkali metal phenolate.

That is, the crosslinked phenoxyphosphazene compound of the present invention is selected from the group consisting of the cyclic dichlorophosphazene represented by the general formula (4) and the linear dichlorophosphazene represented by the general formula (5). At least one dichlorophosphazene compound is prepared from an alkali metal phenolate represented by the general formula (6), an alkali metal diphenolate represented by the general formula (7), and an alkali metal diphenolate represented by the general formula (8). It is produced by reacting a mixture with at least one diphenolate selected from the group (first step), and further reacting the obtained compound with the above alkali metal phenolate (second step).

According to the study of the present inventor, the reactivity of the alkali metal diphenolate represented by the general formulas (7) and (8) with the dichlorophosphazene compound is determined by the alkali represented by the general formula (6). It was found to be extremely lower than that of the metal phenolate. More specifically, when a dichlorophosphazene compound and an alkali metal phenolate represented by the general formula (6) are mixed and heated, phenoxyphosphazene in which a chlorine atom is substituted by a phenoxy group is formed. Substitution reaction hardly occurs even when mixed and heated with the alkali metal diphenolate represented by the formula (7) and / or the general formula (8). This is considered to be due in part to the extremely low solubility of the alkali metal diphenolate in the solvent and the complete separation in the reaction system.

Therefore, for example, in the method described in JP-A-51-47042, that is, a method in which a dichlorophosphazene compound is reacted with an alkali metal phenolate and then an alkali metal diphenolate, the reaction with an alkali metal phenolate is carried out. It is very difficult to completely replace the remaining chlorine atom with the alkali metal diphenolate. Even if one OM group of the alkali metal diphenolate reacts with the chlorine atom in the dichlorophosphazene compound, the remaining one end is The OM group hardly reacts with another chlorine atom, and this OM group is converted into an OH group, and as a result, a phosphazene compound in which a hydroxyl group remains is generated.

On the other hand, according to the present invention, a specific structure is employed in which a mixture of an alkali metal phenolate and an alkali metal diphenolate is reacted with a dichlorophosphazene compound, and then the obtained compound is further reacted with an alkali metal phenolate. Thereby, M of both OM groups of the alkali metal diphenolate is eliminated without leaving a free hydroxyl group in the molecule, and two oxygen atoms are bonded to a phosphorus atom in the dichlorophosphazene compound,
Crosslinked (ie, increased molecular weight) phenoxyphosphazene compounds are produced.

The dichlorophosphazene compounds represented by the general formulas (4) and (5) used as one of the raw materials in the production method of the present invention are described in, for example,
-87427, JP-B-58-19604,
JP-B-61-1363, JP-B-62-20124
It can be manufactured according to a known method described in Japanese Patent Application Laid-Open Publication No. H10-15095. As an example, it can be produced by reacting ammonium chloride and phosphorus pentachloride (or ammonium chloride, phosphorus trichloride and chlorine) in chlorobenzene at about 120 to 130 ° C. and dehydrochlorinating. .

As the alkali metal phenolate represented by the general formula (6), conventionally known alkali metal phenolates can be widely used, for example, sodium phenolate, potassium phenolate,
Lithium phenolate and the like can be mentioned. These alkali metal phenolates can be used alone or in combination of two or more.

In the alkali metal diphenolate represented by the general formula (7), the two groups —OM (M is the same as above) may be in any of ortho, meta or para positional relationship. Specific examples of the alkali metal diphenolate include, for example, alkali metal salts such as resorcinol, hydroquinone, and catechol. Among these, sodium salts and lithium salts are preferred. As the alkali metal diphenolate, one type can be used alone, or two or more types can be used in combination.

Examples of the alkali metal diphenolate represented by the general formula (8) include 4,4′-isopropylidene diphenol (bisphenol-A) and 4,4′-
Sulfonyl diphenol (bisphenol-S), 4,
Examples thereof include alkali metal salts such as 4'-thiodiphenol, 4,4'-oxydiphenol, and 4,4'-diphenol. Among these, sodium salts and lithium salts are preferred. As the alkali metal diphenolate, one type can be used alone, or two or more types can be used in combination.

In the present invention, the alkali metal diphenolate represented by the general formula (7) and the alkali metal diphenolate represented by the general formula (8) may be used alone or in combination. You may.

In the first step of the production process of the present invention, the chlorine atoms in the dichlorophosphazene compound are not completely consumed by the reaction with the alkali metal phenolate and the alkali metal diphenolate, that is, the chlorine atoms in the dichlorophosphazene compound are not consumed. It is desirable to control the amount of the alkali metal phenolate and the alkali metal diphenolate so that is still remained by the reaction with the alkali metal phenolate and the alkali metal diphenolate. Thereby, both of the alkali metal diphenolate-
An OM group (M is as defined above) is attached to the phosphorus atom of the dichlorophosphazene compound. In the first step, the amount of the alkali metal phenolate and the alkali metal diphenolate to be used is usually about 0.05 to 0.9 equivalent, preferably 0.1 to 0.9, in terms of the total amount of both phenolates based on the chlorine amount of the dichlorophosphazene compound. It may be about 1 to 0.8 equivalent.

In the second step of the production method of the present invention, the alkali metal phenolate is used so that all the chlorine atoms and free hydroxyl groups in the compound produced in the first step are completely consumed by the reaction with the alkali metal phenolate. It is desirable to adjust the amount of used. In the present invention, the amount of the alkali metal phenolate used is usually about 1 to 1.5 equivalents, preferably about 1 to 1.2 equivalents, based on the chlorine amount of the dichlorophosphazene compound.

In the present invention, the ratio of the alkali metal phenolate (total amount used in the first step and the second step) to the alkali metal diphenolate (alkali metal diphenolate / alkali metal phenolate, molar ratio) is usually from 1/2000 to 1/2000. About 1/4, preferably 1/20 to 1 /
6 may be used.

The reactions of the first step and the second step are each usually carried out at a temperature of about room temperature to about 150 ° C., preferably about 80 to 140 ° C., and usually for about 1 to 12 hours, preferably about 3 to 12 hours.
It ends in about 7 hours. The reaction in the first step and the reaction in the second step are usually performed in an organic solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene. Will be

The crosslinked phenoxyphosphazene compound of the present invention produced by the above reaction is, for example, washed, filtered,
It can be easily isolated and purified from the reaction mixture according to a usual isolation method such as drying.

The decomposition temperature of the crosslinked phenoxyphosphazene compound of the present invention is in the range of 250 to 350 ° C.

The content ratio of the phenyl group in the crosslinked phenoxyphosphazene compound of the present invention is determined by the ratio of the total phenyl group in the cyclic phenoxyphosphazene of the general formula (1) and / or the linear phenoxyphosphazene of the general formula (2). 50 to 99.9% based on the total number, preferably 70 to 9
0%.

[0058] In general formula (2) terminal groups X ¹ and Y ¹ in varies depending on the reaction conditions, etc., under normal reaction conditions, when performing mild reaction, for example, non-aqueous systems is, X ¹ But-
N = P (OPh) ₃ , Y ¹ has a structure of —P (OPh) ₄ , and under severe reaction conditions such that moisture or an alkali metal hydroxide is present in the reaction system, or a severe reaction in which a transfer reaction occurs. When the reaction was carried out under the conditions, X ¹ was -N = P
(OPh) ₃ , Y ¹ is —P (OPh) ₄ , and X ¹
There -N = P (O) OPh, Y 1 is -P (O) (OPh) ₂
It is in a state where those having the structure of are mixed.

The crosslinked phenoxyphosphazene compound of the present invention is useful as a flame retardant.

The flame retardant comprising the crosslinked phenoxyphosphazene compound of the present invention does not contain a halogen. Therefore, it does not decompose during the molding of the resin to generate hydrogen halide, thereby causing corrosion of the mold, deterioration and coloring of the resin. When the resin burns due to a fire or the like, no harmful gas such as hydrogen halide or smoke is generated. Further, the crosslinked phenoxyphosphazene compound of the present invention has low volatility, does not lower the molding temperature of the resin, and causes problems such as blocking and bleeding (juicing) during kneading and dripping during burning. There is no.

Further, the flame retardant comprising the crosslinked phenoxyphosphazene compound of the present invention does not reduce the molecular weight of the resin, and the blending of the flame retardant can improve the mechanical properties such as impact resistance, heat resistance, moldability and the like. It hardly lowers the inherent properties of the resin.

[Triazine Skeleton-Containing Compound] The triazine skeleton-containing compound as the component (C) of the present invention is used together with a phosphazene-based flame retardant and is a component (flame retardant aid) for further improving the flame retardancy. is there.

In the present invention, conventionally known triazine skeleton-containing compounds can be widely used as long as they have a triazine skeleton in the molecule. Specific examples of the triazine skeleton-containing compound include, for example, melamine (formula (9)), melam (formula (10)), melem (formula (11)), and melon (deammonification of three to three molecules of melem). Product), melamine cyanurate (following formula (12)), melamine phosphate (following formula (13)), succinoguanamine (following formula (14)), melamine resin (following formula)
(15)) and the like, and melamine cyanurate is particularly preferable from the viewpoints of volatility resistance and dispersibility.

[0064]

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[Flame-retardant polyphenylene ether-based resin composition] The compounded amount of the crosslinked phosphazene-based flame retardant (B) to be blended in the flame-retardant polyphenylene ether-based resin composition of the present invention is as follows: 1 to 99 parts by weight of polyphenylene ether resin and polystyrene resin 99 to
The amount is 1 to 30 parts by weight based on 100 parts by weight of the resin composed of 1 part by weight.

The compounding amount of the triazine skeleton-containing compound (C) in the flame-retardant polyphenylene ether-based resin composition of the present invention is 1 to 99 parts by weight of the polyphenylene ether resin (A). And 30 parts by weight or less based on 100 parts by weight of a resin composed of 99 to 1 part by weight of a polystyrene resin. That is, the flame-retardant polyphenylene ether-based resin composition of the present invention further containing the triazine skeleton-containing compound of the component (C) is 1 to 99 parts by weight of the polyphenylene ether resin as the component (A) and 99 to 100 parts by weight of the polystyrene resin. 100 parts by weight of a resin consisting of 1 part by weight, 1 to 30 parts by weight of a crosslinked phosphazene-based flame retardant as the component (B), and a triazine skeleton-containing compound 30 as the component (C)
It is not more than 0.1 parts by weight, preferably 0.1 to 30 parts by weight.

A particularly preferred composition of the flame-retardant polyphenylene ether-based resin composition of the present invention is 100 parts by weight of a resin comprising 1 to 70 parts by weight of a polyphenylene ether resin (A) and 99 to 30 parts by weight of a polystyrene resin. 1 to 30 parts by weight of the crosslinked phosphazene-based flame retardant of the component (B) and the triazine skeleton-containing compound 30 of the component (C)
It is not more than 0.1 parts by weight, preferably 0.1 to 30 parts by weight.

[Inorganic Filler] The flame-retardant polyphenylene ether-based resin composition of the present invention contains an inorganic filler in order to improve the mechanical properties of the resin and / or to further improve the anti-dripping property. Can be blended.

As the inorganic filler, conventionally known resin fillers can be widely used, for example, mica, kaolin, talc, silica, clay, barium sulfate, barium carbonate, calcium carbonate, calcium sulfate, calcium silicate, titanium oxide, glass Beads, glass balloons, glass flakes, glass fiber, fibrous alkali metal titanate (potassium titanate fiber, etc.), fibrous transition metal borate (aluminum borate fiber, etc.), fibrous alkaline earth metal borate ( Magnesium borate fiber, etc.), zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, gypsum whisker, aluminum silicate (mineral name mullite) whisker, calcium silicate (mineral name wollastonite) whisker, silicon carbide whisker, titanium carbide whisker,
Examples thereof include silicon nitride whiskers, titanium nitride whiskers, carbon fibers, alumina fibers, alumina-silica fibers, zirconia fibers, and quartz fibers.

Among these inorganic fillers, fibrous alkali metal titanate, fibrous transition metal borate, fibrous alkaline earth metal borate, zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, aluminum silicate whisker Calcium silicate whiskers, silicon carbide whiskers, titanium carbide whiskers, silicon nitride whiskers, titanium nitride whiskers, and the like, and those having shape anisotropy such as mica are preferable, and fibrous alkali metal titanate, fibrous boric acid Transition metal salts, fibrous alkaline earth metal borates, titanium oxide whiskers, calcium silicate whiskers and the like are particularly preferred.

One of these inorganic fillers can be used alone, or two or more can be used in combination.

Among these inorganic fillers, those having shape anisotropy such as whiskers and mica can be preferably used.

The mixing ratio of the inorganic filler to the polyphenylene ether-based resin is not particularly limited. However, considering the balance between the improvement in mechanical properties and the improvement in flame-retardant performance, the polyphenylene ether-based resin 1
50 parts by weight or less, preferably 1 to 50 parts by weight, per 100 parts by weight
It is good to use parts by weight.

[Organic phosphorus compound containing no halogen]
The flame-retardant polyphenylene ether-based resin composition of the present invention may further contain a halogen-free organic phosphorus compound (hereinafter referred to as “halogen-free organic phosphorus compound”) in order to further improve the flame retardancy. it can.

Conventionally, it is known that halogen-free organic phosphorus compounds improve the flame retardancy of a matrix such as a resin. However, when the present inventor uses the crosslinked phosphazene-based flame retardant and the halogen-free organic phosphorus compound used in the present invention in combination, a synergistic effect is exhibited,
It has been found that the flame retardant effect is significantly enhanced.

The halogen-free organic phosphorus compounds include
Conventionally known ones can be widely used. For example, Tokiko 6-1
No. 9003, JP-A-2-115262, JP-A-5-1079, JP-A-6-322277, U.S. Pat. No. 5,122,556, and the like.

More specifically, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate, tolyl dixylyl phosphate , Tris (norylphenyl) phosphate, phosphate esters such as (2-ethylhexyl) diphenyl phosphate, hydroxyl group-containing phosphate esters such as resorcinol diphenyl phosphate and hydroquinone diphenyl phosphate, 1,3-phenylenebis (2,6-dixylenyl) Phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), bis Enol-A bis (diphenyl phosphate), bisphenol-S bis (diphenyl phosphate), resorcinol bis (dixylyl phosphate), hydroquinone bis (dixylyl phosphate), bisphenol-A bis (ditolyl phosphate), biphenol-A bis (diki Condensed phosphoric acid ester compounds such as silyl phosphate) and bisphenol-S bis (dixylyl phosphate); phosphine or phosphine oxide compounds such as trilauryl phosphine, triphenyl phosphine, tolyl phosphine, triphenyl phosphine oxide, and tolyl phosphine oxide; Can be mentioned.

Among these halogen-free organic phosphorus compounds, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, 1,3-phenylenebis (2,6-dixylenylphosphate), resorcinol bis (diphenylphosphate), hydroquinone Condensed phosphoric acid ester compounds such as bis (diphenyl phosphate), bisphenol-A bis (diphenyl phosphate), resorcinol bis (dicylyl phosphate), hydroquinone bis (dicylyl phosphate), bisphenol-A bis (ditolyl phosphate), triphenyl Phosphine oxide compounds such as phosphine oxide and tolyl phosphine oxide are preferred, and in particular, triphenyl phosphate, 1,3-phenylenebis (2,6- Dixylenyl phosphate), resorcinol bis (diphenyl phosphate), resorcinol bis (dixylyl phosphate), triphenyl phosphine oxide and the like are preferable.

As the halogen-free organic phosphorus compound, one type can be used alone, or two or more types can be used in combination.

The mixing ratio of the halogen-free organic phosphorus compound to the polyphenylene ether resin is not particularly limited. However, in consideration of the balance between the improvement of mechanical properties and the improvement of flame retardancy, the polyphenylene ether resin is usually used. The amount is preferably 50 parts by weight or less, preferably 30 parts by weight or less, more preferably 1 to 30 parts by weight per 100 parts by weight.

[Various Additives] The flame-retardant polyphenylene ether-based resin composition of the present invention exhibits an excellent flame-retardant effect without using a compound containing halogen such as chlorine or bromine as a flame-retardant component. It is also possible to add a commonly used known flame retardant additive in an appropriate combination within a range that does not impair its excellent effect.

The additive for flame retarding is not particularly limited as long as it exhibits a flame retarding effect.
Metal oxides such as tin oxide, iron oxide, molybdenum oxide, copper oxide and manganese dioxide; aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum hydroxide treated with oxalic acid, magnesium hydroxide treated with nickel compounds, etc. Alkali metal salts or alkaline earth metal salts such as metal hydroxide, sodium carbonate, calcium carbonate, barium carbonate and sodium alkyl sulfonate, chlorinated paraffin, perchlorocyclopentadecane, tetrabromobisphenol-A, epoxy resin, bis ( Organic chlorine compounds or organic bromine compounds such as tribromophenoxy) ethane and bis (tetrabromophthalimino) ethane;
Antimony trioxide, antimony tetroxide, antimony pentoxide, antimony compounds such as sodium antimonate, red phosphorus, halogen-containing phosphate compound, halogen-containing condensed phosphate compound or phosphonate compound, guanidine sulfamate, ammonium sulfate,
Nitrogen-containing compounds such as ammonium phosphate, ammonium polyphosphate, and alkylamine phosphate; boron compounds such as zinc borate, barium metaborate and ammonium borate; silicone compounds; silicon compounds such as silica; and heat-expandable graphite. Can be.

One of these additives for flame retardancy can be used alone, or two or more can be used in combination.

Further, the flame-retardant polyphenylene ether-based resin composition of the present invention may be blended with various conventionally known resin additives as long as the excellent properties are not impaired. As the resin additive, for example, a flame retardant other than the above, polytetrafluoroethylene resin (PTFE)
Anti-drip agents (anti-drip agents), ultraviolet absorbers, light stabilizers, antioxidants, light-blocking agents, metal deactivators, quenchers, etc.
Examples thereof include heat stabilizers, lubricants, release agents, colorants, antistatic agents, antioxidants, plasticizers, impact strength improvers, and compatibilizers. For the purpose of imparting anti-fogging property, anti-mold property, anti-bacterial property, or other functions, various conventionally known additives may be further added.

[Production of Flame-Retardant Resin Composition of the Present Invention] The flame-retardant polyphenylene ether-based resin composition of the present invention is obtained by adding the crosslinked phosphazene-based flame retardant and, if necessary, a triazine skeleton-containing compound to a polyphenylene ether-based resin. It can be obtained by weighing and adding a predetermined amount or an appropriate amount of an inorganic filler, a halogen-free organic phosphorus compound, various additives for flame retardation, and other additives, and mixing and kneading by a known method. . For example, an extruder such as a single-screw extruder or a twin-screw extruder, a Banbury mixer, a pressure kneader,
The resin composition of the present invention can be obtained by kneading using a kneader such as a two-roll mill. When it is necessary to mix a liquid, the mixture can be kneaded with the above-described extruder or kneader using a known liquid injection device.

[Flame-retardant resin molded article of the present invention] A flame-retardant polyphenylene ether-based resin molded article can be obtained by molding the flame-retardant polyphenylene ether-based resin composition of the present invention. For example, from a conventionally known molding means such as press molding, injection molding, and extrusion molding, a resin plate, a sheet,
Of course, it is possible to produce extruded products of various shapes such as films and odd-shaped products, and also using a co-extrusion kneader and the like,
It is also possible to manufacture a resin plate having a two-layer or three-layer structure.

The flame-retardant polyphenylene ether-based resin composition and the flame-retardant polyphenylene ether-based resin molded product of the present invention thus obtained can be used for electric / electronic / communication, agricultural / forestry / fishery, mining, construction, food, textile, Clothing, medical, coal,
It can be used in a wide range of industrial fields such as oil, rubber, leather, automobiles, precision equipment, wood, furniture, printing, musical instruments, etc.

More specifically, the flame-retardant polyphenylene ether-based resin composition and the flame-retardant polyphenylene ether-based resin molded article of the present invention can be used for a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone , Facsimile, copier, ECR (electronic cash register), calculator, electronic organizer, electronic dictionary, card, holder,
Office and OA equipment such as stationery, washing machine, refrigerator, vacuum cleaner,
Home appliances such as microwave ovens, lighting equipment, game consoles, irons, kotatsu, etc., AV equipment such as TVs, VTRs, video cameras, radio cassettes, tape recorders, minidiscs, CD players, speakers, liquid crystal displays, connectors, etc.
Relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, and other electrical and electronic components and communication devices, automobiles, vehicles, ships, aircraft, etc. And used for applications such as building materials.

[0089]

The present invention will be described in more detail with reference to Synthesis Examples, Examples, Comparative Examples and Reference Examples. In the following,
“Parts” and “%” mean “parts by weight” and “% by weight”, respectively. Also, "-Ph" and "-Ph
“−” Means “phenyl group” and “phenylene group”, respectively. Furthermore, various evaluations in the Examples and the like
It is a value measured as follows.

1. Thermal deformation temperature: Measured under a load of 18.6 kgf / cm ² according to ASTM D-648 and used as an index of heat resistance.

2. Flame retardancy: UL-94 test method (Test f
or Flammability of Plastic Materials for Parts in
An evaluation test was performed using a test piece having a thickness of 1/16 inch, a length of 5 inches and a width of 0.5 inch based on Devices and Appliances UL94, Fourth Edition). The evaluation criteria are shown below. V-0: All of the following conditions (A) to (E) are satisfied. (A) Flaming (continue burning with flame) after contact with any of the five test pieces in one set is 10 seconds or less. (B) A total of framing after 10 times of flame contact, twice for each set of 5 test pieces, is within 50 seconds. (C) Do not frame any of the five test pieces per set up to the clamp. (D) None of the five test pieces in a set drip flaming particles that ignite cotton 305 mm below. (E) Glowing (not burning with a flame, but remaining as a red-hot glow) within 30 seconds after the second flame contact for all five test pieces in one set. V-1: All of the following conditions (A) to (E) are satisfied. (A) The framing after contact with any of the five test pieces in one set is within 30 seconds. (B) A total of framing after flame contact of 10 times, twice for each set of 5 test pieces, is within 250 seconds. (C) and (D) are the same as V-0. (E) Glowing within 60 seconds after the second flame contact for all five test pieces in one set. V-2: All of the following conditions (A) to (E) are satisfied. (A), (B), (C) and (E) are the same as V-1. (D) At least one of the five test pieces in one set is 305 m
Drop flaming grains that ignite the cotton under m. NG: One of the conditions of V-2 is not reached.

3. Volatile gas and discoloration during molding: visually confirmed.

The following polyphenylene ether, polystyrene resin, halogen-free organic phosphorus compound and inorganic filler were used. Polyphenylene ether (PPE): poly (2,6-dimethyl-1,4-phenylene ether), intrinsic viscosity [η] 0.56 dl / g. High impact polystyrene (HIPS): (Product name: HIP
SH550, manufactured by Nippon Polystyrene Co., Ltd.) Polystyrene (GPPS): (trade name: GPPS G6)
90N, manufactured by Nippon Polystyrene Co., Ltd.) Aromatic phosphate: (triphenyl phosphate (TPP), manufactured by Wako Pure Chemical Industries, Ltd.) Aromatic condensed phosphate: 1,3-phenylenebis (2,6-diki Silenyl phosphate) (trade name PX-
200, manufactured by Daihachi Chemical Industry Co., Ltd.) Inorganic filler: potassium titanate fiber (trade name: Tismo N, manufactured by Otsuka Chemical Co., Ltd.) wollastonite (trade name: Vistal W, manufactured by Otsuka Chemical Co., Ltd.) .

Synthesis Example 1 (Synthesis of phenoxyphosphazene compound having a crosslinked structure by p-phenylene group) 103.5 g (1.1 mol) of phenol, 44.0 g (1.1 mol) of sodium hydroxide, 50 g of water and toluene The toluene solution of sodium phenolate was prepared by heating and refluxing 500 ml of the mixture and removing only water out of the system.

In parallel with the above reaction, 16.5 g (0.15 mol) of hydroquinone, 94.1 g (1.0 mol) of phenol, lithium hydroxide 3
1.1 g (1.3 mol), water 52 g and toluene 600
Then, the mixture was heated and refluxed, and only water was removed from the system to prepare a toluene solution of a lithium salt of hydroquinone and phenol. To this toluene solution was added dichlorophosphazene oligomer (trimer 62%, tetramer 12
%, Pentamer and hexamer 11%, heptamer 3%, octamer to 12%) 1.0 unit mol (115.9 g)
580 g of a 20% chlorobenzene solution containing
After the dropwise addition at 0 ° C. or lower, the reaction was stirred at 110 ° C. for 3 hours. Next, the toluene solution of sodium phenolate prepared above was added under stirring, and the reaction was continued at 110 ° C. for 4 hours.

After the completion of the reaction, the reaction mixture was washed three times with 1.0 liter of a 3% aqueous sodium hydroxide solution and then three times with 1.0 liter of water, and the organic layer was concentrated under reduced pressure. The obtained product is heated at 80 ° C. and 3 mmHg or less at 1
Heating and vacuum drying for 1 hour gave 211 g of a slightly yellow crosslinked phenoxyphosphazene powder.

The crosslinked phenoxyphosphazene obtained above had a hydrolyzed chlorine content of 0.04% and a weight average molecular weight (M
w) The composition by 1100 (polystyrene conversion, GPC analysis), phosphorus content and CHN elemental analysis value is almost [N =
P (-O-p-Ph- O-) 0. 15 (-O-Ph) 1.7]
Turned out to be.

TG / DTA analysis (thermogravimetric analysis) did not show a clear melting point, the decomposition onset temperature was 306 ° C., and the 5% weight loss temperature was 311 ° C.

The residual hydroxyl groups were quantified by the acetylation method. As a result, the residual hydroxyl groups were below the detection limit (1 × 10 ⁻⁶ equivalent / g of hydroxyl equivalent per 1 g of sample).
The detection limit is the same in the following synthesis examples.

Synthesis Example 2 (Synthesis of Phenoxyphosphazene Compound Having Cross-Linked Structure by 2,2-Bis (p-oxyphenyl) isopropylidene Group) 65.9 g (0.7 mol) of phenol and 50 of toluene
0 ml was placed in a 1-liter four-necked flask, and while stirring, while maintaining the internal liquid temperature at 25 ° C., 0.65 ml of sodium metal was added.
14.9 g of gram atoms were finely cut and charged. After completion of the charging, stirring was continued at 77 to 113 ° C. for 8 hours until the sodium metal completely disappeared to prepare a sodium phenolate solution.

In parallel with the above reaction, bisphenol-A
57.1 g (0.25 mol), 103.5 g of phenol
(1.1 mol) and tetrahydrofuran (THF) 80
0 ml was placed in a 3 liter four-necked flask, and while stirring, the internal liquid temperature was kept at 25 ° C. or lower, and the lithium metal 1.6 was added.
11.1 g of gram atoms were finely cut and charged. After the completion of the charging, stirring was continued for 8 hours at 61 to 68 ° C. until the lithium metal completely disappeared. To this slurry solution, dichlorophosphazene oligomer (concentration: 37%, 313 g of chlorobenzene solution, composition: 75% trimer, 17% tetramer)
%, 5 and hexamer 6%, heptamer 1%, octamer or more 1%) 1.0 unit mol (115.9 g) while stirring, keeping the internal liquid temperature at 20 ° C. or less. After dropping over 1 hour, the mixture was reacted at 80 ° C. for 2 hours. Then, under stirring,
While maintaining the internal liquid temperature at 20 ° C., a sodium phenolate solution prepared separately was added over 1 hour, and then added at 80 ° C.
For 5 hours.

After completion of the reaction, the reaction mixture was concentrated to remove THF, and 1 liter of toluene was newly added. After washing this toluene solution three times with 1 liter of 2% NaOH and then three times with 1.0 liter of water, the organic layer was concentrated under reduced pressure. The resulting product was heated and vacuum dried at 80 ° C. and 3 mmHg or less for 11 hours to obtain 229 g of a white powder of crosslinked phenoxyphosphazene.

The crosslinked phenoxyphosphazene obtained above had a hydrolyzed chlorine content of 0.07% and a weight average molecular weight (M
w) 1130 (polystyrene conversion, GPC analysis), phosphorus content and composition based on CHN elemental analysis value are [N = P (-O
-Ph-C (CH ₃ ) ₂ -Ph-O-) _0.25 (-OP
h) _1.50 ].

The TG / DTA analysis did not show a clear melting point, the decomposition onset temperature was 308 ° C., and the 5% weight loss temperature was 31.
3 ° C. The amount of residual hydroxyl groups was below the detection limit (acetylation method).

Synthesis Example 3 (Synthesis of phenoxyphosphazene compound having a crosslinked structure by metaphenylene group) Using resorcinol instead of hydroquinone, the reaction and treatment were carried out in the same manner as in Synthesis Example 1 to obtain 209 g of a white powder of crosslinked phenoxyphosphazene. Was.

The crosslinked phenoxyphosphazene obtained above had a hydrolyzed chlorine content of 0.08% and a weight average molecular weight (M
w) The composition based on 1080 (polystyrene conversion, GPC analysis), phosphorus content and CHN elemental analysis value is [N = P (−
Om-Ph-O-) _0.15 (-O-Ph) _1.7 ].

The TG / DTA analysis did not show a clear melting point, the decomposition onset temperature was 304 ° C., and the 5% weight loss temperature was 31.
1 ° C. The amount of residual hydroxyl groups was below the detection limit (acetylation method).

Synthesis Example 4 (Synthesis of Phenoxyphosphazene Having Cross-Linked Structure by 4,4′-Sulfonyldiphenylene Group (Bisphenol-S Residue)) 103.5 g (1.1 mol) of phenol and THF 5
00 ml into a 1 liter four-necked flask,
While maintaining the internal liquid temperature at 25 ° C.,
25.3 g of gram atoms were cut into small pieces and charged. After completion of the charging, stirring was continued at 65 to 72 ° C for 5 hours until the metallic sodium completely disappeared.

In parallel with the above reaction, 94.1 g (1.0 mol) of phenol and 6.26 g (0.025 mol) of bisphenol-S were added to THF in a 1-liter four-necked flask in THF.
Dissolved in 500 ml, charged 24.1 g of 1.05 g atom of sodium metal at 25 ° C. or less, heated to 61 ° C. over 1 hour after completion of charging, continued stirring at 61 to 68 ° C. for 6 hours, A phenolate mixed solution was prepared. This solution was treated with dichlorophosphazene oligomer (3
62% of mer, 12% of tetramer, 11% of pentamer and hexamer,
To a 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) of 3% of heptamer and 12% of octamer and 12% was added dropwise under cooling and stirring at 25 ° C. or lower.
The mixture was stirred and reacted at 1 to 73 ° C for 5 hours. Next, after dripping the sodium phenolate solution prepared previously, 71-73.
The reaction was continued at 3 ° C. for 3 hours to prepare sodium phenolate.

After completion of the reaction, the reaction mixture was concentrated, redissolved in 500 ml of chlorobenzene, washed 3 times with 5% aqueous NaOH, washed with 5% sulfuric acid, washed with 5% aqueous sodium bicarbonate, and washed 3 times with water. This solidified to give 216 g of a pale yellow wax-like crosslinked phenoxyphosphazene.

The crosslinked phenoxyphosphazene obtained above had a hydrolyzed chlorine content of 0.05% and a weight average molecular weight (M
w) 1030 (in terms of polystyrene), and the composition is almost [N = P (-O-
_{Ph-SO 2 -Ph-O-)} 0.0 25 (-O-Ph) 1.95]
It was decided. TG / DTA analysis; melting temperature Tm: 103 ° C, decomposition onset temperature: 321 ° C, 5% weight loss temperature: 332 ° C Remaining hydroxyl group amount: below detection limit (acetylation method).

Synthesis Example 5 (Synthesis of phenoxyphosphazene having a crosslinked structure by 4,4′-sulfonyldiphenylene group (bisphenol-S residue)) 37.6 g (0.4 mol) of phenol and 0.4 g of sodium metal Using 9.2 g of an atom, a sodium phenolate was prepared in the same manner as in Synthesis Example 4.

Also, 160.0 g of phenol (1.70 g)
Mol), 12.5 g (0.05 mol) of bisphenol-S and 1.8 g atom of sodium metal (41.4 g).
Using g), a mixture of sodium phenolate and sodium diphenolate was prepared in the same manner as in Synthesis Example 4. The mixture is treated with dichlorophosphazene oligomers (62% trimer, 12% tetramer, pentamer and hexamer 11).
%, Tert-mer 3%, octamer or more 12%) to 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) under cooling and stirring at 25 ° C. or lower, Thereafter, the same operation as in Synthesis Example 4 was carried out to obtain 218 g of a pale yellow wax-like crosslinked phenoxyphosphazene, and the analysis confirmed that the compound was the following. [N = P (-O-Ph -SO 2 -Ph-O-) 0.05 (-
O-Ph) _1.90 ] Residual chlorine: 0.01% or less Weight average molecular weight Mw: 1080 (in terms of polystyrene) TG / DTA analysis; melting temperature Tm: 103 ° C, decomposition start temperature: 320 ° C, 5% weight loss temperature: 334 ℃ Residual hydroxyl group: below the detection limit.

Synthesis Example 6 (Synthesis of phenoxyphosphazene having a crosslinked structure by 4,4'-sulfonyldiphenylene group (bisphenol-S residue)) 37.6 g (0.4 mol) of phenol and 0.4 g of sodium metal Using 9.2 g of an atom, a sodium phenolate was prepared in the same manner as in Synthesis Example 4.

Further, 141.2 g (1.50 g of phenol)
Mol), 37.5 g (0.15 mol) of bisphenol-S and 1.8 g of sodium metal and 41.4 g of an atom were prepared in the same manner as in Synthesis Example 4 to prepare a mixture of sodium phenolate and sodium diphenolate. . This mixture is treated with a dichlorophosphazene oligomer (trimer 6
20% chloro containing 1.0 unit mol (115.9 g) of 2%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12% mixture. Benzene solution 58
To 0 g, the mixture was added dropwise under cooling and stirring at 25 ° C. or lower, and the same operation as in Synthesis Example 4 was performed to obtain 217 g of a pale yellow wax-like crosslinked phenoxyphosphazene, and the analysis confirmed that the compound was the following. . [N = P (-O-Ph -SO 2 -Ph-O-) 0.15 (-
O-Ph) _1.70 ] Residual chlorine: 0.03% Weight average molecular weight Mw: 1150 (in terms of polystyrene) TG / DTA analysis; Melting temperature Tm: Undetectable; decomposition onset temperature: 318 ° C; 5% weight loss temperature: 335 ° C Residual hydroxyl group amount (acetylation method): below the detection limit.

Synthesis Example 7 (Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-Oxydiphenylene Group) 94.1 g (1.0 mol) of phenol and 1.0 g of sodium metal and 23.0 g of atom were used. In the same manner as in Synthesis Example 4, sodium phenolate was prepared.

Further, 94.1 g (1.0 mol) of phenol, bis (4-hydroxyphenyl) ether 20.g.
A mixture of sodium phenolate and sodium diphenolate was prepared in the same manner as in Synthesis Example 4 using 2 g (0.10 mol) and 27.6 g of a 1.2 g atom of sodium metal. This mixture is mixed with dichlorophosphazene oligomer (trimer 62%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12%).
Drops were added dropwise to 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) under cooling and stirring at 25 ° C. or lower, and the same operation as in Synthesis Example 4 was carried out to obtain a pale yellow wax of crosslinked phenoxyphosphazene. As a result of analysis, it was confirmed that the following compound was obtained.

[N = P (-O-Ph-O-Ph-O-)
_0.1 (-O-Ph) _1.8 ] Residual chlorine: 0.01% or less Weight average molecular weight Mw: 1100 (in terms of polystyrene) TG / DTA analysis; Melting temperature Tm: Undetectable; decomposition onset temperature: 321 ° C, 5% weight loss Temperature: 328 ° C. Residual hydroxyl group amount (acetylation method): below the detection limit.

Synthesis Example 8 (Synthesis of phenoxyphosphazene having a crosslinked structure by 4,4′-oxydiphenylene group) Using 94.1 g (1.0 mol) of phenol and 1.2 g atom of metal sodium, 27.6 g, was used. In the same manner as in Synthesis Example 4, sodium phenolate was prepared.

Further, 94.1 g (1.0 mol) of phenol, bis (4-hydroxyphenyl) ether 40.g.
A mixture of sodium phenolate and sodium diphenolate was prepared in the same manner as in Synthesis Example 4 using 4 g (0.20 mol) and 1.2 g atom of metal sodium (27.6 g). This mixture is mixed with dichlorophosphazene oligomer (trimer 62%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12%).
Drops were added dropwise to 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) under cooling and stirring at 25 ° C. or lower, and the same operation as in Synthesis Example 4 was carried out to obtain a pale yellow wax of crosslinked phenoxyphosphazene. 212 g of a product was obtained, and it was confirmed by analysis that the following compound was obtained.

[N = P (-O-Ph-O-Ph-O-)
_0.2 (-O-Ph) _1.6 ] Residual chlorine: 0.02% Weight average molecular weight Mw: 1220 (in terms of polystyrene) TG / DTA analysis; Melting temperature Tm: Not detectable; decomposition onset temperature: 306 ° C, 5% weight loss Temperature: 321 ° C. Residual hydroxyl group amount (acetylation method): below the detection limit.

Synthesis Example 9 (Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-thiodiphenylene Group) Using 94.1 g (1.0 mol) of phenol and 1.0 g of metal sodium, 23.0 g of atoms, In the same manner as in Synthesis Example 4, sodium phenolate was prepared.

Further, 94.1 g (1.0 mol) of phenol and 21.8 g (0.1 mol) of 4,4′-thiodiphenol were used.
0 mole) and 1.2 grams of metallic sodium atom 27.6
Using g, a mixture of sodium phenolate and sodium diphenolate was prepared in the same manner as in Synthesis Example 4.
The mixture is treated with dichlorophosphazene oligomers (62% trimer, 12% tetramer, 11% pentamer and 11% hexamer, 7%
The mixture was added dropwise to 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) under cooling and stirring at 25 ° C. or lower. The same operation as in Example 4 was performed to obtain 215 g of a pale yellow highly viscous crosslinked phenoxyphosphazene, and the analysis confirmed that it was the following compound.

[N = P (-O-Ph-S-Ph-O-)
_0.1 (-O-Ph) _1.8 ] Residual chlorine: 0.07% Weight average molecular weight Mw: 1210 (in terms of polystyrene) TG / DTA analysis; Melting temperature Tm: Not detectable; decomposition onset temperature: 337 ° C, 5% weight loss Temperature: 342 ° C. Residual hydroxyl group amount (acetylation method): below the detection limit.

Synthesis Example 10 (Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-thiodiphenylene Group) Using 94.1 g (1.0 mol) of phenol and 1.0 g atom of metal sodium, 23.0 g of 23.0 g, In the same manner as in Synthesis Example 4, sodium phenolate was prepared.

Further, 94.1 g (1.0 mol) of phenol and 43.7 g (0.2 mol) of 4,4'-thiodiphenol were used.
0 mole) and 1.2 grams of metallic sodium atom 27.6
Using g, a mixture of sodium phenolate and sodium diphenolate was prepared in the same manner as in Synthesis Example 4.
The mixture is treated with dichlorophosphazene oligomers (62% trimer, 12% tetramer, 11% pentamer and 11% hexamer, 7%
The mixture was added dropwise to 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) under cooling and stirring at 25 ° C. or lower. The same operation as in Example 4 was performed to obtain 217 g of a pale yellow highly viscous crosslinked phenoxyphosphazene, and the analysis confirmed that the compound was the following.

[N = P (-O-Ph-S-Ph-O-)
_0.2 (-O-Ph) _1.6 ] Residual chlorine: 0.01% Weight average molecular weight Mw: 1320 (in terms of polystyrene) TG / DTA analysis; Melting temperature Tm: Not detectable; decomposition onset temperature: 341 ° C, 5% weight loss Temperature: 347 ° C. Residual hydroxyl group amount (acetylation method): below the detection limit.

Synthesis Example 11 (Synthesis of Phenoxyphosphazene Having Cross-Linked Structure by 4,4′-Diphenylene Group) Synthesis Example using 94.1 g (1.0 mol) of phenol and 1.0 g atom of metal sodium and 23.0 g of atom. In the same manner as in 4, a sodium phenolate was prepared.

Further, Synthesis Example 4 was used by using 94.1 g (1.0 mol) of phenol, 18.6 g (0.10 mol) of 4,4′-diphenol and 1.2 g atom of sodium metal and 27.6 g. Similarly, a mixture of sodium phenolate and sodium diphenolate was prepared. This mixture is treated with a dichlorophosphazene oligomer (trimer 6
20% chloro containing 1.0 unit mol (115.9 g) of 2%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12% mixture. Benzene solution 58
0 g was added dropwise under cooling and stirring at 25 ° C. or lower, and the same operation as in Synthesis Example 4 was performed to obtain 208 g of a pale yellow highly viscous crosslinked phenoxyphosphazene, and the analysis confirmed that the compound was the following compound. .

[N = P (-O-Ph-Ph-O-) _0.1
(-O-Ph) _1.8 ] Residual chlorine: 0.01% Weight average molecular weight Mw: 1210 (in terms of polystyrene) TG / DTA analysis; melting temperature Tm: not detectable; decomposition onset temperature: 338 ° C., 5% weight loss temperature : 349 ° C Amount of residual hydroxyl groups (acetylation method): below the detection limit.

Synthesis Example 12 (Synthesis of Phenoxyphosphazene Having Cross-Linked Structure by 4,4′-Diphenylene Group) Synthesis Example using 94.1 g (1.0 mol) of phenol and 1.0 g atom of metal sodium and 23.0 g of atom. In the same manner as in 4, a sodium phenolate was prepared.

Using 94.1 g (1.0 mol) of phenol, 37.2 g (0.20 mol) of 4,4'-diphenol and 1.2 g atom of metal sodium, 27.6 g of the compound of Synthesis Example 4, Similarly, a mixture of sodium phenolate and sodium diphenolate was prepared. This mixture is treated with a dichlorophosphazene oligomer (trimer 6
20% chloro containing 1.0 unit mol (115.9 g) of 2%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12% mixture. Benzene solution 58
To 0 g, the mixture was added dropwise under cooling and stirring at 25 ° C. or lower, and the same operation as in Synthesis Example 4 was performed to obtain 211 g of a pale yellow highly viscous crosslinked phenoxyphosphazene, and the analysis confirmed that it was the following compound. .

[N = P (-O-Ph-Ph-O-) _0.2
(-O-Ph) _1.6 ] Residual chlorine: 0.01% Weight average molecular weight Mw: 1350 (in terms of polystyrene) TG / DTA analysis; melting temperature Tm: not detectable; decomposition start temperature: 336 ° C., 5% weight loss temperature : 347 ° C Residual hydroxyl group amount (acetylation method): below the detection limit.

Example 1 A resin component consisting of 80 parts of poly (2,6-dimethyl-1,4-phenylene ether), 10 parts of impact-resistant polystyrene (HIPS) and 10 parts of polystyrene (GPPS) was mixed with 100 parts by weight. 5 parts of the crosslinked phenoxyphosphazene compound produced in Synthesis Example 1 was added as a flame retardant, mixed with a mixer, and then melt-kneaded using a 25 mm biaxial kneader to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/16 inch was prepared from this composition by injection molding, evaluated for flame retardancy based on the UL-94 test method, and evaluated for heat distortion temperature according to ASTM D-648. A measurement was made. As a result, the flame retardancy was V-0 and the heat distortion temperature was 150 ° C., and no juicing was observed during molding.

Examples 2 to 12 A flame-retardant resin composition was obtained in the same manner as in Example 1 except that the crosslinked phenoxyphosphazene compound produced in Synthesis Examples 2 to 12 was used.

Example 13 Example 1 was repeated except that 15 parts of wollastonite was further added.
In the same manner as in the above, a flame-retardant resin composition was obtained.

Example 14 In place of the bridged phenoxyphosphazene compound prepared in Synthesis Example 1, 3 parts of the bridged phenoxyphosphazene compound prepared in Synthesis Example 2 and 1,3-phenylenebis (2,6-
A flame-retardant resin composition was obtained in the same manner as in Example 1 except that 1 part of (dixylenyl phosphate) (PX-200) was used.

Comparative Examples 1-3 Instead of the crosslinked phenoxyphosphazene compound produced in Synthesis Example 1, 5 parts of TPP (Comparative Example 1) or PX-200
A flame-retardant resin composition was obtained in the same manner as in Example 1 except that 5 parts (Comparative Example 2) was added or no flame retardant was added (Comparative Example 3).

Using the flame-retardant resin compositions obtained in Examples 2 to 14 and the flame-retardant resin compositions obtained in Comparative Examples 1 to 3, production and evaluation of test pieces were performed in the same manner as in Example 1. Was done. Table 1 shows the results.

The resin composition of Comparative Example 1 exhibited juicing during molding. Further, the resin composition of Comparative Example 3 did not show any flame retardancy.

[0142]

[Table 1]

In Table 1, the resin component was PPE / PS resin = 8
It is a mixture of 0/20. Wollastonite is an inorganic filler, and PX-200 and TPP are halogen-free organic phosphorus compounds.

Example 15 A resin component 10 comprising 50 parts of poly (2,6-dimethyl-1,4-phenylene ether), 25 parts of high impact polystyrene (HIPS) and 25 parts of polystyrene (GPPS)
To 0 parts by weight, 15 parts of the crosslinked phenoxyphosphazene compound produced in Synthesis Example 1 and 10 parts of melamine cyanurate as a flame retardant aid were added and mixed with a mixer.
The mixture was melt-kneaded using a twin-screw kneader to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/16 inch was prepared from this composition by injection molding. The flame retardancy was evaluated based on the UL-94 test method, and the heat distortion temperature was measured according to ASTM D-648. A measurement was made. As a result, the flame retardancy was V-0 and the heat distortion temperature was 101 ° C., and no juicing was observed during molding.

Examples 16 to 26 The procedure of Example 15 was repeated, except that the crosslinked phenoxyphosphazene compound prepared in Synthesis Examples 2 to 12 was used instead of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 1. A resin composition was obtained.

Example 27 In place of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 1, the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 3 was used, and 15 parts of potassium titanate fiber (Tismo N) was further added. In the same manner as in Example 15, a flame-retardant resin composition was obtained.

Example 28 In place of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 1, 10 parts of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 4 and 1,3-phenylenebis (2,6
-Dixylenyl phosphate) (PX-200) except that 2 parts were used, to obtain a flame-retardant resin composition in the same manner as in Example 15.

Comparative Examples 4 to 15 Instead of the crosslinked phenoxyphosphazene compound produced in Synthesis Example 1, 15 parts of TPP (Comparative Example 4) or PX-20
0 15 parts (Comparative Example 5), only the flame retardant is not blended and the blending amount of the flame retardant auxiliary is 20 parts (Comparative Example 6), or both the flame retardant and the flame retardant auxiliary Was prepared in the same manner as in Example 15 except that the compound was not blended (Comparative Example 7) to obtain a flame-retardant resin composition.

Using the flame-retardant resin compositions obtained in Examples 16 to 28 and the flame-retardant resin compositions obtained in Comparative Examples 4 to 7, preparation and evaluation of test pieces in the same manner as in Example 15 Was done. Table 2 shows the results.

In the resin composition of Comparative Example 4, juicing was observed at the time of molding. Further, the resin composition of Comparative Example 7 did not show any flame retardancy.

[0152]

[Table 2]

In Table 2, the resin component was PPE / PS resin = 5
It is a 0/50 mixture.

Example 29 A resin component 10 comprising 20 parts of poly (2,6-dimethyl-1,4-phenylene ether), 40 parts of impact-resistant polystyrene (HIPS) and 40 parts of polystyrene (GPPS)
To 0 parts by weight, 20 parts of the crosslinked phenoxyphosphazene compound produced in Synthesis Example 1 as a flame retardant and 20 parts of melamine cyanurate as a flame retardant aid are mixed by a mixer, and then melt-kneaded using a 25 mm biaxial kneader. Thus, a flame-retardant resin composition was obtained.

A test piece having a thickness of 1/16 inch was prepared from this composition by injection molding, evaluated for flame retardancy based on the UL-94 test method, and evaluated for heat distortion temperature according to ASTM D-648. A measurement was made. As a result, the flame retardancy was V-0 and the heat distortion temperature was 82 ° C., and no juicing was observed during molding.

Examples 30 to 40 The procedure of Example 29 was repeated, except that the crosslinked phenoxyphosphazene compound prepared in Synthesis Examples 2 to 12 was used instead of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 1. A resin composition was obtained.

Example 41 20 parts of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 5 was used in place of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 1, and 15 parts of potassium titanate fiber (Tismo N) was further added. Except for Example 29
In the same manner as in the above, a flame-retardant resin composition was obtained.

Example 42 In place of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 1, 12 parts of the crosslinked phenoxyphosphazene compound prepared in Synthesis Example 6 and triphenyl phosphate (TP
P) A flame-retardant resin composition was obtained in the same manner as in Example 29 except for using 4 parts.

Comparative Examples 8 to 11 Instead of the crosslinked phenoxyphosphazene compound produced in Synthesis Example 1, 20 parts of TPP (Comparative Example 8) or PX-20
0 20 parts (Comparative Example 9) or only the flame retardant was not blended and the blending amount of the flame retardant auxiliary was 30 parts (Comparative Example 1)
0) or a flame-retardant resin composition was obtained in the same manner as in Example 29 except that both the flame retardant and the flame retardant auxiliary were not used (Comparative Example 11).

Using the flame-retardant resin compositions obtained in Examples 29 to 42 and the flame-retardant resin compositions obtained in Comparative Examples 8 to 11, preparation and evaluation of test pieces in the same manner as in Example 29 Was done. Table 3 shows the results.

In the resin composition of Comparative Example 8, severe juicing was observed at the time of molding. Further, the resin composition of Comparative Example 11 did not show any flame retardancy.

[0162]

[Table 3]

In Table 3, the resin component was PPE / PS resin = 2
It is a mixture of 0/80.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/5399 C08K 5/5399 C08L 25/04 C08L 25/04 85/02 85/02 85/02 (72) Inventor Tadao Yabuhara Tokushima 463 Kagasuno, Kawauchi-cho, Tokushima-shi, Japan Otsuka Chemical Co., Ltd.Tokushima Research Laboratories (72) Inventor Takashi Kameshima 463, Kasuno-cho, Kawauchi-machi, Tokushima-City, Tokushima Pref. 463 Kagasuno, Ichikawauchi-cho Otsuka Chemical Co., Ltd. Tokushima Research Laboratory (72) Inventor Hiroyuki Takase 463 Kagasuno, Kawauchi-machi, Tokushima-shi, Tokushima Pref. Otsuka Chemical Co., Ltd. Tokushima Research Laboratories F term (reference) 4F071 AA22 AA51 AB01 AB26 AC12 AC15 AE07 AE17 AF47 AH07 AH12 BA01 BB05 BB06 BC07 4J002 BC03X CH07W CQ013 DE188 DG048 DJ018 DJ038 DJ048 DJ058 EU187 EW049 EW139 EW156 FD018 FD133 FD136 FD139 GN00 GQ00

Claims (6)

[Claims] 1. A polyphenylene ether resin (A)
(B) 1 to 30 parts by weight of a crosslinked phosphazene-based flame retardant is blended with 100 parts by weight of a resin composed of 9 parts by weight and 99 to 1 part by weight of a polystyrene resin. Composition. (2) 100 parts by weight of the resin (A),
The flame-retardant polyphenylene ether-based resin composition according to claim 1, wherein the compound (C) contains a triazine skeleton-containing compound in an amount of 30 parts by weight or less. (3) 100 parts by weight of the resin (A),
(D) The inorganic filler is compounded in an amount of 50 parts by weight or less.
Or the flame-retardant polyphenylene ether-based resin composition according to claim 2. 4. The resin (A), based on 100 parts by weight of the resin,
4. The flame-retardant polyphenylene ether-based resin composition according to claim 1, wherein (E) a halogen-free organic phosphorus compound is blended in an amount of 30 parts by weight or less. 5. The crosslinked phosphazene flame retardant of the component (B) is represented by the general formula (1): ## STR1 ## [In the formula, m represents an integer of 3 to 25. Ph represents a phenyl group. A phenoxyphosphazene represented by the general formula (2): [Wherein X ¹ is a group -N = P (OPh) ₃ or a group -N = P
(O) OPh, wherein Y ¹ is a group -P (OPh) ₄ or a group-
P (O) (OPh) ₂ is shown. n shows the integer of 3-10,000. Ph is the same as above. At least one phosphazene compound selected from the group consisting of linear phenoxyphosphazenes represented by the formula:
Phenylene group, p-phenylene group and general formula (3) [-C is A in the formula _{(CH 3) 2 -, -} SO 2 -, - shows S- or -O-. a represents 0 or 1. A compound crosslinked by at least one type of crosslinking group selected from the group consisting of bisphenylene groups represented by the formula (a):
And (b) the phenyl group content is 50 to 99.9% based on the total number of all phenyl groups in the phosphazene compound (1) and / or (2).
5. The flame-retardant polyphenylene ether-based resin composition according to claim 1, which is (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule. 6. A flame-retardant polyphenylene ether-based resin composition obtained by molding the flame-retardant polyphenylene ether-based resin composition according to claim 1, claim 2, claim 3, claim 4, or claim 5. Resin molding.