WO2004024844A1

WO2004024844A1 - Phosphazene composition

Info

Publication number: WO2004024844A1
Application number: PCT/JP2003/010773
Authority: WO
Inventors: Fumiki Murakami; Jun-Ichi Nakahashi; Atsushi Nanasawa; Tomoyuki Fujita
Original assignee: Asahi Kasei Chemicals Corporation
Priority date: 2002-09-13
Filing date: 2003-08-26
Publication date: 2004-03-25
Also published as: CN1681906A; JPWO2004024844A1; KR100634927B1; DE10393198T5; JP3923497B2; DE10393198B4; CN1308418C; KR20050042810A; AU2003261725A1

Abstract

A phosphazene composition whose volatile matter content at heating at 200ºC for 2 hr is in the range of 0.02 to 1.0 wt.%. This phosphazene composition is excellent in hydrolysis resistance and when added to a resin, can provide a resin composition that retains highly desirable balance among hydrolysis resistance, flame retardancy and electrical characteristic stability at high-frequency region of 1 GHz or over.

Description

Description Phosphazene composition Technical field

The present invention relates to a phosphazene composition having excellent hydrolysis resistance, and a flame retardant and a flame retardant resin composition containing the phosphazene composition as an effective component.

Background art

Since phosphazene compositions have excellent properties, they have been studied in various fields and are widely and suitably used. Examples include flame retardants for polymer materials, rubber, lubricants, lithium ion batteries, solar cells, fuel cells, non-combustible electrolytes, battery cases, release agents, release films, roughened surface forming materials, water repellent It has been proposed for a variety of uses, including pharmaceuticals such as fertilizers, anticancer agents, AIDS inhibitors, and dental materials.

Regarding flame retardants, the method of adding flame retardants to flame-retardant resins by adding chlorine compounds, bromine compounds, antimony trioxide, etc. to the resins has been used. However, these are said to be unfavorable from the viewpoint of environmental protection, toxicity, and the like, and there has been a demand for an improvement in flame-retardant methods. Therefore, the use of phosphorus-based flame retardants as alternative flame retardants that do not contain chlorine, bromine or metal oxides is being studied for flame retardancy. Conventionally, red phosphorus, phosphate esters, condensed phosphate esters, and the like have been used as phosphorus-based flame retardants. However, red phosphorus has problems such as hydrolysis and mold corrosion due to generation of corrosive phosphoric acid. Phosphate esters and condensed phosphate esters need to be added in large amounts due to their relatively low phosphorus concentration, which deteriorates their mechanical and thermal properties, and increases the cost due to the increase in the amount added. There was a problem. Also, when added to the resin, the glass transition temperature was greatly reduced and the heat resistance was poor. Furthermore, when used for electrical and electronic equipment, the hydrolysis resistance was poor.

On the other hand, phosphazene compounds are attracting attention because of their high phosphorus content, relatively good heat resistance and hydrolysis resistance, and excellent flame retardancy. In recent years, there have been several techniques for flame retarding resin compositions using phosphazene compounds. Some suggestions have been made. As an example, Japanese Patent Application Laid-Open No. 08-302124 discloses a flame-retardant resin composition comprising a thermoplastic resin composition containing a styrene resin, a phosphazene compound and a polyphenol compound. Japanese Unexamined Patent Publication No. Hei 10-2599292 discloses a flame-retardant epoxy composition in which phenoxyphosphazene is added to an epoxy resin. These proposals are effective from the viewpoint of imparting flame retardancy. However, these proposals could not be said to be sufficient when used in fields where properties such as hydrolysis resistance and excellent stability of electrical properties are also required. Further, Japanese Patent No. 3,053,617 describes the JIS-K2246 standard, that is, a phosphazene composition having a low volatile content after heating in a boiling water bath for 2 hours. However, there is no mention of the effect of the content of volatile components on flame retardancy, hydrolysis resistance, and stability of electrical properties, and the phosphazene composition obtained by the method is not used. In any case, it is difficult to say that it is sufficient in terms of hydrolysis resistance and electrical characteristics stability! / Was the thing.

From these prior arts, there is no reading about the effect of the volatile components contained in the phosphazene composition found by the present inventors as disclosed below. That is, the surprising effect of the volatile component contained in the phosphazene composition on the flame retardancy, hydrolysis resistance, and electrical property stability of the composition cannot be inferred from the prior art. This has been clarified for the first time by the present invention.

Disclosure of the invention

The present invention provides a phosphazene composition which does not contain chlorine and bromine compounds, and is excellent in moisture resistance, flame retardancy, and electrical property stability in a high frequency region of 1 gigahertz (GHz) or higher.

The present inventors have intensively studied a technique for achieving the above object, and as a result, it has been found that a phosphazene composition having a volatile content at a high temperature of 200 ° C. within a specific range is, surprisingly, resistant to moisture absorption. It has been found that when added to a resin composition, a resin composition excellent in stability of electrical properties and flame retardancy is provided.

That is, the present invention

(1) A phosphazene composition containing at least one phosphazene compound, wherein a volatile content from the phosphazene composition is 0 .0% based on the total weight of the phosphazene composition when heated at 200 for 2 hours. 0 2 wt ^_0/0 or more, 1.0 wt ^_0/0 or more The phosphazene yarn composition below.

(2) The volatilization from the phosphazene composition is carried out from the reaction solvent, the raw material, and the by-product generated from the reaction solvent and / or the raw material in the synthesis of the phosphazene compound remaining in the phosphazene composition. The phosphazene composition according to the above (1), containing at least one selected from the group consisting of:

(3) The phosphazene composition according to the above (1) or (2), wherein the water content measured by the Karl Fisher method at 150 ° C. is 100 Oppm or less.

(4) The phosphazene composition according to the above (1) or (2), wherein the water content measured by the Karl Fischer method at 150 ° C. is 650 ppm or less. (5) The phosphazene composition according to any one of the above (1) to (4), which contains 95% by weight or more of the cyclic phosphazene compound based on the total weight of the phosphazene composition.

(6) The content of one or more metal elements based on the total weight of the phosphazene composition is 20 ppm or less, respectively, and the content of the compound having a P—OH bond is 1% by weight. The phosphazene composition according to any one of (1) to (5) above, wherein the phosphazene composition has a chlorine content of 1,000 ppm or less.

(7) When the content of one or more kinds of metal elements based on the total weight of the phosphazene composition is 50 ppm or less, respectively, and the content of the compound having a P-OH bond is 1% by weight or less. The phosphazene composition according to any one of (1) to (5) above, wherein the phosphazene composition has a chlorine content of 500 ppm or less.

(8) Out of all the substituents in the phosphazene compound, 90% or more of the substituents are phenoxy groups, and the phosphorus content is 13.0 to 14.4 based on the total weight of the phosphazene composition. 5 by weight ^_0/0, (1) to (7) phosphazene composition according to any one of clauses.

(9) When heated from room temperature to 600 ° C at a heating rate of 10 ° C / min under an inert gas atmosphere by TGA, the weight retention at 500 ° C is 15% by weight or less. The phosphazene composition according to any one of the above (1) to (8).

(10) When heated from normal temperature to 600 ° C at a heating rate of 10 ° C / min under an inert gas atmosphere with TGA, the weight retention at 500 ° C is 10% by weight or less. The phosphazene composition according to any one of the above (1) to (8).

(11) The phosphazene composition according to any one of (1) to (10) above, wherein the phosphazene composition has a bulk density of 0.45 gZ cm ³ or more.

(12) A flame-retardant resin composition comprising a resin and the phosphazene composition according to any one of the above (1) to (11).

(13) The resin is an unsaturated polyester resin, vinyl ester resin, diaryl phthalate resin, epoxy resin, cyanate resin, xylene resin, triazine resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, urethane resin, ketone resin The flame-retardant resin composition according to the above (12), comprising at least one curable resin selected from the group consisting of alkyd resin, furan resin, styrylpyridine resin, silicone resin and synthetic rubber.

(14) The resin is selected from the group consisting of polycarbonate, poly (phenylene ether), poly (phenylene sanololefide), polypropylene, polyethylene, polystyrene, ABS resin, polyalkylene terephthalate, polyamide, thermotropic liquid crystal, and polystyrene containing elastomer. The flame-retardant resin composition according to the above (12), comprising at least one thermoplastic resin.

(15) Any one of the above items (12) to (14), wherein the phosphorus atom concentration is from 0.5% by weight to 8.0% by weight based on the total weight of the flame-retardant resin composition. Flame-retardant resin composition.

(16) The flame-retardant resin composition according to any one of the above (12) to (15), which is used for electrical or electronic equipment parts or housings used in a high frequency range of 1 gigahertz or more. object.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

In general, flame retardants such as phosphazene compositions are protected from the outside air to some extent, for example, paper bags with polyethylene inner bags, paper bags with aluminum inner bags, polyethylene inner bags, etc. are packaged in drums or flexible containers. Transported and stored at However, depending on the conditions of transportation and storage, it is often handled in an environment that can be hot and humid. The Zen composition has a problem that it absorbs moisture and causes quality deterioration. In other words, storage stability is poor. A resin composition using the absorbed phosphazene composition as a raw material is inferior in hydrolysis resistance and electrical property stability.

In general, flame retardants are not limited to phosphazene compounds and preferably do not contain volatile components. On the other hand, in the present invention, the volatile component specified in the present application is an essential component for stabilizing the quality, and the weight change rate when heated at 200 ° C. for 2 hours (to the content of the volatile component). 0.02% by weight or more and 1.0% by weight or less, preferably 0.02% by weight or more, 0.8% by weight or less, and more preferably 0.04% by weight or more. It has been found that the phosphazene composition having a content of 0.8% by weight or less has excellent moisture absorption resistance even under high temperature and high humidity conditions, and accordingly, has excellent electrical property stability, that is, excellent storage stability. The phosphazene composition of the present invention does not absorb moisture even when stored for a long time under high temperature and high humidity, and is stable in quality. When the amount of volatile components is less than 0.02% by weight, the water absorption at the time of moisture absorption becomes high, and the stability of electric characteristics is poor. On the other hand, when the content exceeds 1.0% by weight, the stability of the electrical properties and the flame retardancy are inferior, which is not preferable. There is a tendency.

Generally, a phosphazene compound is obtained by reacting a phosphorus halide with ammonium chloride in an organic solvent to obtain a halogenated phosphazene oligomer, and further reacting the alkali metal salt of the hydroxy conjugate in an organic solvent. Can be. The organic solvent suitably used for the synthesis reaction of the phosphazene compound is not particularly limited, but examples thereof include ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as tolylene, xylene, trimethinolebenzene, ethynolebenzene, and propynolebenzene. Examples include aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents such as monochlorobenzene and dichlorobenzene, and amide solvents such as dimethylformamide and getylformamide. In this synthesis reaction, various low-boiling by-products may be produced depending on the reaction solvent and reaction conditions used, and these may remain as volatile components in the final product.

The volatile matter from the phosphazene composition in the present invention includes a reaction solvent in the synthesis of the phosphazene compound remaining in the composition, phenols, alcohols, and the like. Low boiling point residual raw materials. The type of solvent remaining naturally depends on the reaction solvent used. In addition, examples of volatile components include low-boiling-point impurities with an unknown structure, which are by-produced from the substance used or the solvent used, or produced by the reaction between the solvent used and the raw material used. Examples of by-products from the raw materials used include phosphoric acid-based compounds generated from phosphorus halides, and multimeric compounds such as raw phenols and dimeric compounds produced as by-products from alcohols. Further, as an example of a by-product derived from the solvent used, a compound obtained by a ring-opening reaction when an ether-based solvent is used, and the like can be mentioned. Examples of by-products of the reaction between the solvent used and the raw materials used include raw phenols, ethers obtained by reacting alcohols with the solvent, and the like.

The amount of water contained in the phosphazene composition of the present invention is 1000 ppm or less, preferably 800 ppm or less, more preferably 650 ppm or less, further 500 ppm or less, more preferably 30 ppm or less. Is desirable. If it exceeds 1000 ppm, the stability of the electrical properties and the hydrolysis resistance are poor, which is not preferable.

The phosphazene compound used in the present invention is described in, for example, "Inorganic Polymers" Pretice-Hall by James E. Mark, Harry R. Allcock, Robert West.

International, Inc., 1992, p61-pl40. For example, general formula (1)

(1)

A cyclic phosphazene compound represented by the formula and Z or a general formula (2)

And a chain phosphazene compound represented by the formula:

Here, n in the formula is an integer of 3 to 25, m is an integer of 3 to 10000, and the substituents X ¹ and X ² are each independently an alkyl group having 1 to 6 carbon atoms, and To 1 1 aryl group, fluorine atom, or the following general formula (3)

Aryloxy group having a substituent represented by (wherein R ^A , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group having 1 to 5 carbon atoms) , Or at least one substituent selected from the group consisting of phenyl), or a naphthyloxy group, or a substituent represented by an alkoxy group having 1 to 6 carbon atoms or an alkoxy-substituted alkoxy group And at least one type of substituent, and hydrogen on the substituent may be partially or entirely substituted with fluorine. In the formula, Y represents -N = P (0) (X ² ) or -N = P (X ² ) ₃ , and Z represents -Ρ (Ρ) ₄ or -Ρ (0) (Χ ² ) ₂ Represents

As an example of the substituents X ¹ and X ^2, a methyl group, Echiru group, .eta. propyl group, an isopropyl group, _eta _ butyl, s- butyl group, tert- heptyl group, n- Amiru group, such as isoamyl group Alkyl group, phenyl group, 2-methylphenyl group, 3-methynolephenyl group, 4-methynolephenyl group, 2,6-dimethinolephenyl group, 3,5-dimethylphenyl group, 2,5-dimethylphenyl group, Aryl groups such as 2,4-dimethinolephenyl group, 3,4-dimethylphenyl group, 4-tert-butyltinphenyl group, 2-methyl-4-tert-butylphenyl group, methoxy group, ethoxy group, n-propyloxy group , Isopropyloxy, n-butyloxy, tert-butyloxy, s-butyl Alkoxy group, n-amyloxy group, isoamyloxy group, tert-amyloxy group, n-hexyloxy group, etc., alkoxy group, methoxy methoxy group, methoxy ethoxy group, methoxy ethoxy methoxy group, methoxy ethoxy ethoxy group Group, alkoxy-substituted alkoxy group such as methoxypropyloxy group, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,5-dimethyl Phenoxy, 2,4-dimethylphenoxy, 3,5-dimethylphenoxy, 3,4-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,4-dimethylphenoxy 3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 3,4,5-trimethylphenoxy, 2-ethylphenoxy, 3-ethylphenoxy, 4-ethylphenoxy, 2,6-getylphenoxy, 2,5-getylphenoxy, 2,4-Getyl phenoxy group, 3,5-Getyl phenoxy group, 3,4-Jetinolephenoxy group, 41-n-Propinolephenoxy group, 4-Isopropylphenoxy group, 4- Alkyl-substituted phenoxy groups such as tert-butynolephenoxy group, 2-methynoleic 4-tert-butynolephenoxy group, 2-phenyl-2-enophenoxy group, 3-phenylphenoxy group, and 4-phenylphenoxy group And aryl-substituted phenoxy, naphthyl, and naphthyloxy groups. Some or all of the hydrogens in these groups may be replaced by fluorine.

In the phosphazene composition of the present invention, the phosphazene compound may be used singly or as a mixture of two or more types. However, the phosphazene compound may be used as a general formula (1) based on the total weight of the phosphazene composition. It is preferable to contain 95% by weight or more having the structure of (2).

One of the factors that determine flame retardancy is the concentration of phosphorus atoms contained in the molecule of the phosphazene compound. Among the phosphazene compounds, the chain phosphazene compound having a chain structure has a substituent at the molecular terminal, and therefore has a lower phosphorus content than the cyclic phosphazene compound. Therefore, when the same amount is added, the cyclic phosphazene compound is more effective in imparting flame retardancy than the chain phosphazene compound. Therefore, in the present invention, a compound containing 95% by weight or more of the cyclic phosphazene compound based on the total weight of the phosphazene composition is preferable. In consideration of the balance between heat resistance and flame retardancy, it is preferred that 90% or more of all the substituents in the phosphazene compound are phenoxy groups. Furthermore, these phosphazene compounds can be prepared by the technique disclosed in International Publication No. 00/09518 pamphlet by using a phenylene group, a biphenylene group, and a group shown below (4)

(Four)

(Wherein R ° is one C (CH ₃₎ 2 one, -S0 ₂ _, _S-, or a O-, and 1 represents 0 or 1) it is cross-linked by a cross-linking group selected from the group consisting of May be. These phosphazene compounds having a crosslinked structure are specifically produced by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These metal salts are added to the dichlorophosphazene oligomer in a slightly excessive amount over the stoichiometric amount.

Further, the phosphazene compound is a mixture of compounds having different structures such as a cyclic body such as a cyclic trimer and a cyclic tetramer and a chain phosphazene compound, but the processability of the flame-retardant resin composition is a cyclic trimer. The higher the content of the cyclic tetramer, the more preferable it is. Specifically, a phosphazene compound containing at least 80% by weight of a cyclic trimer and / or a cyclic tetramer compound is preferred. More preferably, it contains at least 7% by weight of the cyclic trimer, and more preferably at least 80% by weight of the cyclic trimer.

The phosphazene compound can take various forms such as liquid, waxy, and solid depending on the type and structure of the substituent, but any form may be used as long as the effect of the present invention is not impaired. But it doesn't matter. In the case of a solid state, the bulk density is preferably 0.45 g / cm ³ or more and 0.75 gZ cm ³ or less. If the bulk density is less than 0.45 g / cmu, include many particles with small particle size Therefore, it is not preferable because the possibility of dust explosion also appears.

Alkali metal components such as sodium and potassium contained in the phosphazene compound are each 200 ppm or less, more preferably 50 ppm or less, and more preferably 50 ppm or less, based on the total weight of the phosphazene composition. The metallic component is less than 5 Oppm. Also, based on the total weight of the phosphazene composition, the general formula

In (1), the content of the phosphazene compound in which at least one of the substituents X ¹ is a hydroxyl group, that is, the content of the phosphazene compound containing a P—OH bond is preferably less than 1% by weight, and chlorine It is desirable that the content be 1000 ppm or less, preferably 500 ppm or less, and more preferably 300 ppm or less. Based on the total weight of the phosphazene composition, if the alkali metal component exceeds 200 ppm, the hydroxyl-containing phosphazene compound is 1% by weight or more, and the chlorine content exceeds 100 Oppm, The resin composition containing the phosphazene composition has problems such as inferior flame retardancy and hydrolysis resistance, and deteriorates electrical characteristics. Further, when such a phosphazene composition is added to a resin which is easily decomposed by an acid, the resin itself may be decomposed by phosphoric acid traces derived from P-OH, and the mechanical properties of the resin composition may be deteriorated. .

Table have a cyclic structure represented by the general formula (1), and phosphazene compound in which at least one of the substituents X ¹ is a hydroxyl group, the general formula (5) (wherein, a a + b = n) In some cases, such an oxo compound has a oxo structure, but it is desirable that such an oxo compound be less than 1% by weight based on the total weight of the phosphazene composition, as in the case of the hydroxyl group-containing phosphazene compound. The same applies to the phosphazene compound having a chain structure represented by the general formula (2).

(Five)

The volatile matter content of the present invention when heated at 200 ° C for 2 hours is 0.02% by weight or more, The method for producing the phosphazene composition of not more than% by weight is not particularly limited as long as a phosphazene composition satisfying such requirements can be obtained. The phosphazene yarn composition of the present invention can be suitably obtained, for example, by the following method.

In the process of synthesizing the phosphazene compound, it is not necessary to control by-products to a high degree, and rather, some by-products are suitable in the phosphazene composition of the present invention. For example, a phosphazene composition containing an appropriate amount of by-product can be obtained by appropriately controlling the water concentration in the reaction system, the purity of the raw materials, the reaction temperature, the reaction time, and the like. ·

In the purification step, it is necessary to appropriately control the solvent used for the purification, the temperature, the time, and in the drying step, the type of the drying apparatus, the drying temperature, the time, the degree of vacuum, the surface area of the phosphazene compound, and the like. The phosphazene composition of the present invention can be obtained only by controlling the conditions of all these steps.

The phosphazene composition of the present invention can be suitably used in a wide range, and the method of use and the field of use are not particularly limited. Examples of suitable use include flame retardants, rubbers, lubricants, lithium ion batteries, solar cells, fuel cells, non-combustible electrolytes, battery cases, release agents, release films, and roughened surfaces. Materials, water repellents, and other uses such as fertilizers, anti-cancer agents, AIDS inhibitors, and dental materials, etc., have been proposed, all of which are suitably used. It is suitably used as a fuel, a lubricant, a lithium ion battery, a fuel cell, a solar cell, a non-combustible electrolyte, a battery case, and a release film. When the phosphazene composition of the present invention is used, a conventionally known non-halogen or non-antimony flame retardant can be used in addition to the phosphazene compound of the present invention as long as the effects of the present invention can be achieved. Illustrative examples include triphenyl phosphate, tricresyl phosphate, trixyleninophosphate, cresinoresifinolephosphophosphate, xyleninolefinophosphate, dixyleninolephenophosphate, and resinoresinoinophosphate bisphosphate. Phosphoric acid esters such as bisphenol A bisphosphate, metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium aluminate, nitrogen compounds such as triazine compounds, melamine, melamine cyanurate, melamine resins, guanidine compounds, etc. Zinc borate Compounds, zinc stannate compounds, inorganic silicon compounds such as silica, kaolin clay and talc, and silicon-containing organic compounds.

When using the phosphazene composition of the present invention, other additives such as a plasticizer, an antioxidant, and the like are added as long as the effects of the present invention are not impaired in order to impart other characteristics such as rigidity and dimensional stability. And stabilizers such as ultraviolet absorbers, curing agents, curing accelerators, antistatic agents, stress relaxation agents, release agents, flow regulators, dyes, sensitizers, coloring pigments, rubber polymers, and high conductivity. Molecules and the like can be added in advance.

The phosphazene composition of the present invention can be used in combination with a conventionally known resin. The resin that can be used is not limited at all, and known curable resins and plastic resins are preferably used. As an example, the plastic resins include polycarbonate, polyphenylene ether, polyphenylene phenol, polypropylene, polyethylene, polystyrene, high-impact polystyrene, elastomer-containing polystyrene, syndiotactic polystyrene, ABS resin, and polycarbonate. Examples include alloys of ABS resin, polyalkylene terephthalate such as polyethylene terephthalate, polyethylene terephthalate, and polypropylene terephthalate, polyamides, thermopick liquid crystals, and the like. Alloys with polyphenylene ether and polyamide, alloys with polyphenylene ether and liquid crystal with thermopic opening Porifue two ether and Borifue two Rensarufuai de and Aroi of is preferably used.

Curable resins include unsaturated polyester resins, vinyl ester resins, diaryl phthalate resins, epoxy resins, cyanate resins, xylene resins, triazine resins, phenolic resins, urea resins, melamine resins, benzoguanamine resins, urethane resins, There are ketone resins, alkyd resins, furan resins, styrylpyridin resins, silicone resins, and synthetic rubbers, and they are particularly suitable for epoxy resins.

These plastic resins and curable resins may be used alone or in a polymer alloy containing two or more kinds, or a polymer alloy of these resins and a rubber-like polymer. You may use as.

The epoxy resin suitably used in the present invention may be a compound having at least two epoxy groups in a molecule, and is not particularly limited. Examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, resorcinol epoxy resin, novolak epoxy resin, biphenyl epoxy resin, and multifunctional epoxy resin. These epoxy resins can be used alone or in combination of two or more.

In the present invention, as the polyphenylene ether resin suitably used, a homopolymer or a copolymer having a repeating unit represented by the general formula (6) and / or (7) is used (where, ^{^{^{R 7, R 8, R 9}}} , R 1 0, R丄^1, R ^{1 2} is independently an alkyl group having a carbon 1 to 4, Ariru group, a halogen, a hydrogen. However, R ^{¹ 1} R ¹ ² is Not hydrogen at the same time).

(7) Representative examples of homopolymers of polyphenylene ether resins include poly (6-dimethyl-1,4-phenylene) ether and poly (2-methylenol 6) Cyl-1,4-phenylene ether, poly (2,6-tetraquinone 1,4-phenylene) ether, poly (2-ethynole 6-n-propyl-1,4-phenylene) Athenole, poly ( 2,6-di-n-propynolee 1,4-phenylene ether, poly (2-methyl-1-6-n-butynolee 1,4-phenylene) ether, poly (2-ethyl-6-isopropynolee 1,4) And homopolymers such as poly (2-methyl-6-hydroxy-6-hydroxy-1,4-phenylene) ether.

Among them, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (di-dimethyl) ether described in JP-A-63-301222 is preferred. Alkylaminomethinole)-6-methinolephenylene ether unit 2-(N-alkynole N-phenylaminomethinole)-Polyphenylene ether containing, as a partial structure, 6-methinolephenylene etherene unit Is particularly preferred.

Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main unit unit. Examples include copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and o-cresolone, or copolymers of 2,6-dimethylphenol and 2,6-dimethylphenol. , 3, 6-trimethylphenol and copolymers with o-cresol.

In the present invention, a modified polyphenylene ether resin obtained by modifying a part or all of the polyphenylene ether resin with a group containing a carboxy group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, or a silyl group is used. These may be used alone or in combination of two or more. The method for producing the functionalized modified polyphenylene ether resin is described in, for example, Japanese Patent Publication No. Sho 63-503332, Japanese Patent Publication No. 7-51818, and Japanese Patent Publication No. 3-61885. Japanese Patent Publication No. JP-A-2001-302738, Japanese Patent Publication No. 2000-309270, Japanese Patent No. 328997, Japanese Patent It is produced by the method described in Japanese Patent No. 3109735, Japanese Patent No. 3401179, Japanese Patent No. 3490935 and the like.

In the resin composition using the phosphazene composition of the present invention, the effect of the present invention is To the extent achievable, conventionally known non-halogen and non-antimony flame retardants can be used in addition to the phosphazene compound of the present invention. For example, triphenyl phosphate, tricresinole phosphate, trixyleninole phosphate, cresyl diphenyl phosphate, xylen diphenyl phosphate, dixylinolefeninophosphate, bisphenolinorebisphosphate, bisphenoleno A Phosphate esters such as phosphates, metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium aluminate, triazine compounds, nitrogen-containing compounds such as melamine, melamine cyanurate, melamine resin, guanidine compounds, etc. And silicon compounds.

In the resin composition using the phosphazene composition of the present invention, when it is necessary to further improve the rigidity and dimensional stability of the resin composition, an inorganic filler can be added. The filler type can be selected arbitrarily according to the purpose, but glass fiber, potassium titanate fiber, glass cloth, glass flake, carbon fiber, myriki, talc, silica, zircon, alumina, quartz, magnetite, graphite, and graphite Laren, gypsum, kaolin, silicon carbide, calcium carbonate, iron powder, copper powder and the like are generally used.

In the resin composition using the phosphazene composition of the present invention, other properties such as dimensional stability are further imparted, and other additives such as a plasticizer and an antioxidant are provided as long as the effects of the present invention are not impaired. And stabilizers such as UV absorbers, curing agents, curing accelerators, antistatic agents, stress relief agents, release agents, flow regulators, dyes, sensitizers, coloring pigments, rubber polymers, etc. Can be added. In addition, various known flame retardants and flame retardant auxiliaries, for example, alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing water of crystallization, and zinc borate compounds It is also possible to further improve the flame retardancy by adding an inorganic silicon compound such as silica, kaolin clay, and talc, and a zinc stannate compound.

The method of mixing the phosphazene composition and the resin in the present invention is not particularly limited as long as the effects of the present invention can be achieved. The phosphazene composition and the resin, and the additives to be added as necessary, may be mixed at the same time, or the phosphazene composition and the additives may be mixed in advance into the resin after being previously mixed. Also, each The components can be blended sequentially.

The method of blending the phosphazene composition and the thermoplastic resin in the present invention is not particularly limited as long as the effects of the present invention can be achieved. For example, kneading and manufacturing can be performed using a kneading machine such as an extruder, a heating roll, a kneader, and a bumper mixer. Among them, kneading with an extruder is preferable in terms of productivity. The kneading temperature may be in accordance with the preferred processing temperature of the base resin, and is in the range of 200 to 360 ° C, preferably in the range of 240 to 320 ° C.

In addition, when compounding with a curable resin, the components for producing the resin composition are mixed without solvent or, if necessary, using a solvent that can be mixed uniformly, and then the solvent is removed. A method in which a resin mixture is obtained, cast into a mold, cured, cooled, and removed from the mold to obtain a molded product. It can also be cast in a mold and cured by hot pressing. The solvent for dissolving each component is not particularly limited as long as it can uniformly mix various materials and does not impair the effects of the present invention when used. Examples include toluene, xylene, acetone, methylethylketone, getinoleketone, cyclopentanone, cyclohexanone, dimethinoleformamide, methinoreserosonolev, methanole, ethanolanole, n-prononoone, iso. —Professional. Examples thereof include nonole, n-butanol, n-pentanole, n-hexanol, cyclohexanol, n-hexane, and n-pentane.

Also, as an example, a method of kneading and manufacturing using a kneading machine such as a heating roll, an eder, a bread palli mixer, an extruder, and the like, cooling, pulverizing, and further performing molding by transfer molding, injection molding, compression molding, or the like. be able to. The curing method varies depending on the curing agent used, but is not particularly limited. Examples include thermal curing, light curing, curing by pressure, curing by moisture, and the like, but are not limited as long as the curing method can achieve the effects of the present invention. The order of mixing the components is not particularly limited as long as the effects of the present invention can be achieved. A preferred method of producing the resin composition can be used depending on the suitability of each resin.

The resin composition using the phosphazene composition of the present invention comprises: a coil bobbin; Electrical components such as power transformers, connectors, polarizing yokes, printed wiring boards, printed circuit boards, encapsulants, electrical insulating materials, electrical coatings, laminates, high-speed arithmetic varnishes, advanced composite materials, electric wires, Applications for electrical and electronic materials such as antenna agents, cables, high-performance molding materials, paints, adhesives, coating materials, tableware, buttons, textiles, paper treatment agents, decorative boards, UV curable inks, sealants, synthetic leather, Insulation buffering materials, waterproof coatings, anticorrosive linings, binders for molds, lacquers, paints, ink modifiers, resin modifiers, aircraft interior agents, composite materials matrix, household goods, OA equipment, AV equipment It is optimally used for battery cases, lighting equipment, automotive parts applications, housing applications, ETC, ITC, mobile phones, etc. Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.

1) Volatile content measurement

5 g of the phosphazene composition was weighed into a glass bottle, heated at 200 ° C. for 2 hours, and the change in weight before and after heating was measured to determine the amount of volatile matter.

2) Water content measurement of phosphazene composition

The measurement was carried out at a set temperature of 150 ° C. by the force fisher method.

3) Measurement of water content after absorption of phosphazene composition

In advance, the phosphazene composition is sifted through a sieve having an opening of 7 10 μππι, and 10 g of the sifted phosphazene composition is taken in a petri dish, and the temperature and the relative humidity are 95 ° C and 95 ° C, respectively, in a thermo-hygrostat. Humidification was carried out for 6 hours under the condition of% Rh, and the water content before and after the humidification was measured by the Karl Fisher method at a set temperature of 150 ° C.

4) Bulk density of phosphazene composition

Loose apparent specific gravity (Aerated Bulk Density) was measured using a powder tester manufactured by Hosokawa Micron Corp. to determine the bulk density.

5) Electrical characteristics (electrical stability)

The relative dielectric constant and the relative dielectric loss tangent were measured at a frequency of 4 GHz by a cylindrical cavity resonator method using a molded piece of about 120 mm in thickness and about 2 mm in thickness.

In addition, it absorbs moisture for 48 hours in a thermo-hygrostat set at 90 ° C and a relative humidity of 95% Rh. After that, the relative permittivity and relative tangent of the molded piece were measured at a frequency of 4 GHz using a cylindrical cavity resonator.

6 Li T¾JA (Thermogravime ric Analysis)

When 1 Omg of the phosphazene yarn and the product was heated to 600 ° C at a rate of 10 ° CZmin in a nitrogen flow of 3 Om1Zmin using a Thermal Analysis System 7 Series manufactured by Perkin Enorema Co., Ltd., 500 The value obtained by dividing the weight at 100 ° C by the weight at 100 ° C and multiplying by 100 was defined as the weight retention at 500 ° C.

7) Flame retardant

Based on the UL-94 vertical combustion test, measurements were made using an injection-molded test specimen having a thickness of 1Z16 inch, and the average burning time after 10 times of flame contact and the presence or absence of absorbent cotton ignition by dripping during burning were evaluated.

8) MFR (Melt Flow Rate)

It was measured at 250 ° C. under a load of 10 kg based on JISK 7210.

9) Metal content measurement

Concentrated sulfuric acid was added to the sample for incineration, and after dissolution in diluted nitric acid, quantitative analysis of lithium and sodium was performed using an atomic absorption spectrometer.

10) Phosphorus content measurement

Approximately lO Omg of the sample was weighed, concentrated sulfuric acid was added for incineration, and dissolved in dilute nitric acid. Then, quantitative analysis of phosphorus was performed by the ICP-AES method.

1 1) Chlorine content measurement

The measurement was performed by one method of ion chromatography.

1 2) Moisture resistance

A molded piece with a thickness of about 2 mm and 50 x 5 Omm is humidified in a constant temperature and humidity chamber at a set temperature of 85 ° C and a relative humidity of 95% Rh for 56 hours, and the difference in weight before and after humidification is measured. By doing so, the water absorption rate was obtained. In addition, the color change of the test piece was visually observed.A color change was hardly observed before and after moisture absorption, and a color change was confirmed as X. confirmed.

The components used in the examples and comparative examples are as follows.

(1) Polyphenylene ether (PPE) Poly 1,2,6-dimethinole 1,4-phenylene 1,0 with a spr / c of 0.54 measured in a 30 ° C black-mouthed form solution.

(2) Rubber reinforced polystyrene (HIPS)

Rubber content 9% by weight, 30. C, matrix polystyrene measured in toluene solution? Rubber reinforced polystyrene with a sp / c of 0.74 and a volume average rubber particle diameter of 1.5 // m.

(3) Epoxy resin: ''

AER 250 (manufactured by Asahi Kasei Epoxy Co.); epoxy equivalent: 184-186.

(4) Curing agent

m-xylene-α α, Jiamine (manufactured by Wako Pure Chemical Industries, Ltd.).

The phosphazene compositions were synthesized by the methods of Examples 1 to 6 and Comparative Examples 1 to 3.

[Example 1]

FR 1: In a 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth type cooling tube, a dropping funnel, a thermometer and a stirrer, 160.2 g of phenol, solid potassium hydroxide 1 1 2 .2 g and 500 ml of xylene were charged, and heated to reflux at an oil bath temperature of 145 ° C. under a nitrogen stream. The generated water was taken out of the system by azeotropy with xylene, and only xylene was returned to the system. The mixture was heated and refluxed until distillation of the generated water was completed, and it took four hours to complete the reaction. Place the reaction vessel in an ice bath, cool the reaction solution to 10 ° C or less, and keep the reaction solution at 10 ° C or less, and add 72.1 g of chlorophosphazene oligomer (95% trimer, tetramer). A mixed solution of 4%, 1% of other components) and 250 ml of xylene was added dropwise using a dropping funnel over 30 minutes. After the dropwise addition, the reaction solution was heated again, and heated and refluxed at an oil bath temperature of 145 ° C for 7 hours. The end point of the reaction was followed by ³¹ PN MR, and the reaction was performed until no signal derived from the halogen-substituted phosphazene compound was observed. After completion of the reaction, cool the reaction solution to 80 ° C, maintain the temperature at 0 to 85 ° C, wash twice with 10% aqueous sodium hydroxide solution, and then wash with dilute hydrochloric acid once and water four times. went. The reaction solution was dried over anhydrous magnesium sulfate, magnesium sulfate was filtered off, and the solvent was distilled off at 80 ° C and 1 OmmHg or less. The product was dried under reduced pressure at 1 mmHg or less for 5 hours in an open at a set temperature of 105 ° C. to obtain 132.5 g of a phenoxyphosphazene mixture. The obtained massive phosphazene composition was ground using a Henschel mixer. The composition of the obtained phosphazene was determined by "丄 PNMR. Trimer: 96%, tetramer 3%, other phosphazene compounds: 1%. K content: 23 ppm, Na content; 1 13.4% Phosphorus content: 13.4% Chlorine content: 30ppm 500 ° C residue: 2.2% by weight Volatile content: 0.174% by weight Bulk density: 0 46 gZ cm ^3. [Example 2]

FR 2: In a 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth-type cooling tube, a dropping funnel, a thermometer and a stirrer, phenol 1.55.1 g, solid potassium hydroxide 1 33.6 g and 500 ml of xylene were charged and heated to reflux at an oil bath temperature of 145 ° C. under a nitrogen stream. The generated water was taken out of the system by azeotropy with xylene, and only xylene was returned to the system. The mixture was heated and refluxed until distillation of the generated water was completed, and it took four hours to complete the reaction. Place the reaction vessel in an ice bath, cool the reaction solution to 10 ° C or less, and keep the reaction solution at 10 ° C or less, and add a mixed solution of 70.Og of chlorophosphazene oligomer and 25 Om1 of xylene. The solution was dropped using a dropping funnel over 30 minutes. After the dropwise addition, the reaction solution was heated again, and heated under reflux at an oil bath temperature of 145 ° C for 7 hours. The end point of the reaction was followed by ¹ PNMR, and the reaction was continued until no signal derived from the halogen-substituted phosphazene compound was observed. After completion of the reaction, the reaction solution was cooled to 80 ° C., washed twice with a 10% aqueous sodium hydroxide solution while maintaining the temperature at 70 to 85 ° C., and further washed once with dilute hydrochloric acid and four times with water. The reaction solution is dried with anhydrous magnesium sulfate, and the magnesium sulfate is separated by filtration.The solvent is distilled off at 80 ° C and below 10 mmHg, and then dried in an oven at a set temperature of 105 ° C and below ImmHg for 5 hours under reduced pressure. As a result, 126.3 g of a phosphazene composition containing a mixture of phenoxyphosphazene compounds was obtained. The obtained massive phosphazene composition was pulverized using a Henschel mixer. The composition of the resulting phosphazene was more determined in ^{3 1} PNMR. Trimer: 88%, tetramer 8%, other phosphazene compounds 4%.

K content; 20 ppm; Na content; 11 ppm. Phosphorus content: 13.7 weight %, Chlorine content: 82 ppm. 500 ° C residue: 6.3 weight ¹ ½. Volatile content is 0.

It was 225% by weight. The bulk density was 0.47 g / cm ³ .

[Embodiment 3]

FR3: In a 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth-type cooling tube, a dropping funnel, a thermometer and a stirrer, 158.0 g of phenol, solid lithium hydroxide 11 1 0.0 g of benzene and 500 ml of benzene were charged and heated to reflux at an oil bath temperature of 145 ° C. under a nitrogen stream. The generated water was taken out of the system by azeotropic distillation with benzene, and only benzene was returned to the system. Heating and refluxing until the distillation of the generated water was completed, took 6 hours to complete the reaction.

Place the reaction vessel in an ice bath, cool the reaction solution to 1o ° C or less, and keep the reaction solution at 10 ° C or less, and add a mixed solution of 72.1 g of chlorophosphazene oligomer and 250 ml of chlorobenzene. The solution was dropped over 30 minutes using a dropping funnel. After the dropwise addition, the reaction solution was heated again, and heated to reflux at an oil bath temperature of 145 ° C for 7 hours. The end point of the reaction was followed by ^{3 1} PNMR, the reaction was carried out until a signal from the halogen-substituted Hosufaze emission compound is not observed. After completion of the reaction, the reaction solution was cooled to 80 ° C., washed twice with a 10% aqueous sodium hydroxide solution while maintaining the temperature at 70 to 85 ° C., and further washed once with dilute hydrochloric acid and four times with water. The reaction solution is dried over anhydrous magnesium sulfate, magnesium sulfate is filtered off, the solvent is distilled off at 80 ° C and 1 OmmHg or less, and then dried under reduced pressure at 1 mmHg or less in an oven at a set temperature of 105 ° C for 5 hours. As a result, 211.8 g of a phosphazene composition containing a mixture of phenoxyphosphazene compounds was obtained. The obtained massive phosphazene composition was pulverized using a Henschel mixer. The composition of the obtained phosphazene was determined by P-band R. Trimer: 84%, tetramer 14%, other phosphazene compounds: 2%. K content; 30 ppm; Na content; 15 ppm. Phosphorus content; 13.5%. Chlorine content: 65 ppm. 500 ° C residue: 7.1% by weight. The amount of volatiles was 0.586% by weight. The bulk density was 0.55 g / cm ³ . [Example 4]

FR4: Dissolve FR 1 in toluene / methanol = 10/90 mixed solvent After recrystallization, the obtained crystal was dried under reduced pressure of ImmHg or less for 4 hours in an open at a set temperature of 105 ° C, and the obtained massive phosphazene composition was ground using a Henschel mixer. did. Trimer: 97%, tetramer: 2%, other phosphazene compounds: 1 o / ₀ . K content; 8 ppm, Na content; 10 ppm. Phosphorus content; 13.4% by weight; Chlorine content: 10 ppm or less; Residue at 500 ° C: 2.1% by weight. The volatile content was 0.125% by weight. The bulk density was 0.57 g / cm.

[Example 5]

FR5: A 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth-type cooling tube, a dropping funnel, a thermometer and a stirrer was charged with 500.0 g of phenol and 1000.1 solid potassium hydroxide. g and xylene 50 Om 1 were charged, and heated to reflux at an oil bath temperature of 145 ° C under a nitrogen stream. The generated water was taken out of the system by azeotropy with xylene, and only xylene was returned to the system. The mixture was heated and refluxed until distillation of the generated water was completed, and it took four hours to complete the reaction. Place the reaction vessel in an ice bath, cool the reaction solution to 10 ° C or less, and keep the reaction solution at 10 ° C or less, and mix a solution of 70.3 g of chlorophosphazene oligomer and 25 Om1 of xylene. Was added dropwise using a dropping funnel over 30 minutes. After the dropwise addition, the reaction solution was heated again, and refluxed with heating at an oil bath temperature of 145 ° C for 6 hours. The end point of the reaction was followed by ³¹ PNMR, and the reaction was carried out until no signal derived from the halogen-substituted phosphazene compound was observed. After the completion of the reaction, the reaction solution was cooled to 80 ° C and maintained at a temperature of 70 to 85 ° C. /. The mixture was washed twice with an aqueous sodium hydroxide solution, and once with dilute hydrochloric acid and four times with water. The reaction solution was dried with anhydrous magnesium sulfate, magnesium sulfate was separated by filtration, and the solvent was distilled off at 80 ° C and below 10 mmHg. The obtained crude crystals are washed with methanol (10 Om1), and then dried in an oven at a set temperature of 105 ° C under reduced pressure of not more than ImmHg for 5 hours to obtain a mixture of the phenoxyphosphazene compound. The obtained phosphazene composition 1 18.1 g was obtained. The obtained massive phosphazene composition was pulverized using a Henschel mixer. The composition of the obtained phosphazene is: 93.6% trimer, 4.0% tetramer, 2.4% other phosphazene compounds. K content; 28 ppm, Na content; 10 ppm. Phosphorus content: 13.5% by weight, chlorine content: 102 ppm. 500 ° C residue: 4.3% by weight. The volatile content is 0.088% by weight and the bulk density is 0.49 g / cm. Met.

[Example 6]

FR6: In a 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth-type cooling tube, a dropping funnel, a thermometer and a stirrer, 555.1 g of phenol and 100.0 g of solid potassium hydroxide And xylene 50 Om1 were charged and heated to reflux at an oil bath temperature of 145 ° C. The generated water was taken out of the system by azeotropy with xylene, and only xylene was returned to the system. The reaction was completed by heating and refluxing until the distilling of the generated water was completed. It took four hours.

Place the reaction vessel in an ice bath, cool the reaction solution to 1 ° C or less, and keep the reaction solution at 10 ° C or less, and add a mixed solution of 72.2 g of chlorophosphazene oligomer and 25 Oml of xylene. The solution was dropped using a dropping funnel over 30 minutes. After the dropwise addition, the reaction solution was heated again, and refluxed with heating at an oil bath temperature of 145 ° C for 6 hours. The end point of the reaction was followed by ³¹ PNMR. After completion of the reaction, the reaction solution was cooled to 80 ° C, washed twice with a 10% aqueous sodium hydroxide solution at a temperature of 70 to 85 ° C, and further washed once with dilute hydrochloric acid and four times with water. The reaction solution was dried over anhydrous magnesium sulfate, and the magnesium sulfate was filtered off.The solvent was distilled off at 80 ° C and below 10 mmHg. Drying yielded 24.1 g of a phosphazene composition containing a mixture of phenoxyphosphazene compounds. The obtained massive phosphazene composition was pulverized using a Hensil mixer. The composition of the obtained phosphazene is as follows: trimer: 90.3%, tetramer: 4.3%, phosphazene trimer compound having one hydroxyl group in the molecule: 0.1%, monochrome pentaphenoki Cyphosphazene trimer: 0.4%, other phosphazene compounds 4.9%. K content; 35 ppm; Na content; 13 ppm. Phosphorus content: 14.1%, chlorine content: 290 ppm. 500 ° C residue: 8.6% by weight. The volatile content was 0.451% by weight and the bulk density was 0.57 g / cm.

[Comparative Example 1] FR 7: A 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth-type cooling tube, a dropping funnel, a thermometer and a stirrer was charged with 177.0 g of phenol and 75 OmL of xylene. Below, the oil bath temperature was set to 145 ° C. A solution prepared by dissolving 120.2 g of potassium hydroxide in purified water to form a 40% aqueous solution was added dropwise over 4 hours using a dropping funnel, and the water in the system was azeotropically mixed with xylene. It was sequentially removed from the system. After the dropwise addition of the aqueous potassium hydroxide solution, the mixture was heated under reflux until the distilling of the generated water was completed, and it took 90 minutes to complete the reaction.

Place the reaction vessel in an ice bath, cool the reaction solution to 10 ° C or less, and while maintaining the reaction solution at 10 ° C or less, mix a mixed solution of 85.lg of chlorophosphazene oligomer and 25 Om1 of xylene with The solution was dropped using a dropping funnel over 30 minutes. After the dropwise addition, the reaction solution was heated again, and heated under reflux at an oil bath temperature of 145 ° C for 7 hours. The end point of the reaction was followed by ³¹ PNMR. After completion of the reaction, the reaction solution is cooled to 40 ° C or lower, washed twice with a 10% aqueous solution of sodium hydroxide / methanol = 7: 3, and further diluted with hydrochloric acid once, and a solution of water / methanol = 7: 3. Cleaning was performed three times. The reaction solution was dried over anhydrous magnesium sulfate, magnesium sulfate was separated by filtration, and the solvent was distilled off at 80 ° C and 1 OmmHg or less. It was dried under reduced pressure to obtain 154 g of a phosphazene composition containing a mixture of phenoxyphosphazene compounds. The composition of the obtained phosphazene was determined by PNMR above. Trimer: 87%, tetramer: 10%, other phosphazene compounds: 3%. K content; 10 ppm, Na content; 10 ppm. 500 ° C residue: 7.8% by weight. The volatile content was 0.017% by weight. The bulk density was 0. 42 g / cm ^3.

[Comparative Example 2]

FR8: Purification of 167.0 g of phenol and 100.lg of potassium hydroxide in a 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth condenser, a dropping funnel, a thermometer and a stirrer. A 40% aqueous solution of oxidizing water dissolved in water and 500 ml of xylene were charged, and heated and refluxed at an oil bath temperature of 145 ° C under a nitrogen stream. The water in the system and the water formed are azeotropic with xylene It was taken out of the system, and only xylene was returned to the system. The mixture was heated and refluxed until the distillation of the generated water was completed, and it took 8 hours to complete the reaction.

Place the reaction vessel in an ice bath, cool the reaction solution to 10 ° C or less, and drop a mixed solution of 80.lg of chlorophosphazene oligomer and 250 ml of xylene while keeping the reaction solution at 10 ° C or less. The solution was added dropwise using a funnel over 30 minutes. After the dropwise addition, the reaction solution was heated again, and refluxed with heating at an oil bath temperature of 145 ° C for 6 hours. The end point of the reaction was followed by ^{3 1} PNMR. After the completion of the reaction, the reaction solution was cooled to 40 ° C. or lower, neutralized with dilute hydrochloric acid, and washed three times with water. The reaction solution is dried over anhydrous magnesium sulfate, magnesium sulfate is filtered off, the solvent is distilled off at 80 ° C and less than 10 mmHg, and then dried under reduced pressure at 1 mmHg or less in an oven at a set temperature of 80 ° C for 3 hours. As a result, 151 g of a phosphazene composition containing a mixture of phenoxyphosphazene compounds was obtained. The composition of the resulting phosphazene was obtained by ^{3 1} PNMR. Trimer: 81%, tetramer: 12%, phosphazene compound having one hydroxyl group in the molecule: 1%, monochrome-opening pentaphenoxyphosphazene trimer: 2%, other phosphazene compounds 4% . K content; 212 ppm, Na content: 38 ppm. Phosphorus content; 14.6% by weight; chlorine content; 2200 ppm. 500 ° C residue: 15.1% by weight. The volatile content was 5.12% by weight. ₀ The bulk density was 0. 76 g / cm

[Comparative Example 3]

FR 9: In a 2 L four-necked flask equipped with a Dean-Stark tube equipped with a Dimroth condenser, a dropping funnel, a thermometer and a stirrer, 555.1 g of phenol, 100.1 g of potassium hydroxide, purification 25 ml of water and 500 ml of benzene with a monochrome mouth were charged, and heated and refluxed at an oil bath temperature of 145 ° C. The generated water was taken out of the system by azeotropy with monochlorobenzene, and only the benzene with monochrome mouth was returned to the system. The mixture was heated and refluxed until the distillation of the generated water was completed, and it took 7 hours to complete the reaction.

Place the reaction vessel in an ice bath, cool the reaction solution to 10 ° C or lower, and keep the reaction solution at 10 ° C or lower, and mix a 72.2 g chlorophosphazene oligomer and 250 ml monochlorobenzene. Over 30 minutes using a dropping funnel It was dropped. After the dropwise addition, the reaction solution was heated again, and heated and refluxed at an oil bath temperature of 145 ° C for 6 hours. The end point of the reaction was followed by ³¹ PNMR. After the completion of the reaction, the reaction solution was cooled to 50 ° C. or lower, washed twice with a 10% aqueous sodium hydroxide solution, and further washed once with dilute hydrochloric acid and three times with water. The reaction solution was dried over anhydrous magnesium sulfate, magnesium sulfate was filtered off, the solvent was distilled off at 80 ° C and 1 OmmHg or less, and then dried under reduced pressure at 95 ° C and 1 mmHg or less for 5 hours to obtain phenoxyphosphazene. A phosphazene composition containing a mixture of compounds was obtained in a yield of 121. 1 g. The composition of the obtained phosphazene is as follows: trimer: 62.1%, tetramer: 26.4%, phosphazene trimer compound having one hydroxyl group in the molecule: 0.8%, monochrome-opened pentaphenoxyphosphazene Trimer: 1.2%, other phosphazene compounds 9.5%. K content; 126 ppm; Na content; 31 ppm. Phosphorus content: 14.3%, chlorine content: 1 270 ppm. 500 ° C residue: 18.2% by weight. The volatile content was 1.24% by weight, and the bulk density was 0.62 g / cm "" ¹ .

[Application example]

[Examples 7 to 10, Comparative Examples 4 and 5]

The water content of each of the phosphazene compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was measured before and after moisture absorption, and the results shown in Table 1 were obtained. Table 1 also shows the volatile content of these phosphazene compositions.

In addition, 11% by weight of the phosphazene composition obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and 39% by weight of HIPS / ⁰ . , PPE mixed at a ratio of 50% by weight, and supplied to a twin screw extruder with a screw diameter of 25 mm where the maximum temperature of the heated cylinder was set to 300 ° C, and melted and mixed at a screw rotation speed of 300 rpm. Then, the strand was cooled and cut to obtain a resin composition pellet. Next, the obtained resin composition pellets were molded into a UL-94 test specimen and an electrical property measurement specimen at a cylinder set temperature of 280 ° C and a mold temperature of 80 ° C by injection molding. A physical property test was performed by the test method, and the results in Table 1 were obtained. 【table 1】

Example Example Example Example Example Comparative example Comparative example

7 8 9 1 0 4 5

[Phosphazene composition] FR 1 FR2 FR 3 FR4 FR7 F R 8 Volatile content / ^ / o 0.174 0.225 0.586 0.125 0.017 5.12 Before moisture absorption (A) / ppm 101 180 155 75 37 326

After moisture absorption (B) / ppm 499 452 612 540 1498 862

Change (B-A) 398 272 457 465 1461 536

[Resin composition]

Before moisture absorption 2.64 2.64 2.65 2.64 2.63 2.67 Dielectric constant After moisture absorption 2.66 2.66 2.67 2.66 2.69 2.69

A 0.02 0.02 0.02 0.02 0.06 0.02 Before moisture absorption 0.0027 0.0028 0.0029 0.0027 0.0027 0.003 Dielectric loss tangent After moisture absorption 0.0037 0.0036 0.0038 0.0035 0.00340.0064

A 0.001 0.0008 0.0009 0.0008 0.00070.0034 Flame retardant [UL 94] V- 0 V- 0 V- 0 V- 0 V- 0 V— 1 From the results in Table 1, those with a volatile content within the range indicated in this application are moisture-absorbing. It can be seen that the change in electrical characteristics before and after is small, and that good flame retardancy is exhibited.

[Examples 11 to 15]

The phosphazene composition (FR2) obtained in Example 2 was pulverized using a Henschel mixer, and the pulverization time was changed to obtain phosphazene yarns having different bulk densities. The obtained phosphazene composition was absorbed for 6 hours in the same manner as in Examples 7 to 10, and the water content before and after the absorption was measured.

[Table 2]

Example embodiment Example embodiment Example

1 1 1 2 1 3 1 4 1 5

¾ Density g / cm 0.47 0.53 0.45 0.61 0.33

Before moisture absorption (A) / ppm 180 176 188 170 163

After moisture absorption (B) / ppm 452 488 486 522 769

From the change amount (BA) 272 312 298 352 606 Table 2 results, the bulk density is 0. 45 g Z cm ³ or more ones, moisture absorption resistance is particularly It turns out that it is high.

[Example 16-22, Comparative Examples 6-8]

The phosphazene compositions obtained in Examples 1, 2, 5, and 6 and Comparative Examples 2 and 3 were each measured for water content and weight retention before and after moisture absorption, and the results in Tables 3 and 4 were obtained. . Tables 3 and 4 also show the volatile content and bulk density of these phosphazene compositions.

Furthermore, each component was mixed in the ratio shown below, and fed to a twin screw extruder with a screw diameter of 25 mm with the maximum temperature of the heating cylinder set at 300 ° C, and melt-mixed at a screw rotation speed of 300 rpm. Then, the strand was cooled and cut to obtain a resin composition pellet. Next, physical properties test pieces were molded from the obtained resin composition pellets at a cylinder setting temperature of 240 to 290 ° C by injection molding, and physical properties tests were performed by the above-described test methods, and the results in Tables 3 and 4 were obtained. Got.

[Table 3]

Example Example Example Example Comparative example

16 1 7 18 19 6

[Phosphazene composition] FR 1 FR 2 FR 5 FR6 FR8 Volatile content wt% 0.174 0.225 0.088 0.451 5.12 Before moisture absorption (A) ppm 101 180 127 178 326 After moisture absorption (B) P m 499 452 433 584 586 862 Change (B- A) ppm 398 272 306 406 536

Bulk density g / cm 0.47 0.53 0.49 0.57 0.76 Weight retention w t% 2.2 6.3 4.3 8.6 15.1

[Resin composition]

Flame retardant [UL-94] V- 0 V- 0 V- 0 V- 0 V- 1

MF R g Z lOmin 8.8 8.1 8.2 7.9 6.2 Resin composition: PPE / HIP SZ phosphazene composition = 55/33/12 (% by weight) Table 4]

Example Example Example Comparative example Comparative example

20 21 22 7 8

[Phosphazene composition] FR 1 FR 2 FR 5 FR 9 FR 8 Volatile content t% 0.174 0.225 0.088 1.24 5.12 Before moisture absorption (A) ppm 101 180 127 289 326 After moisture absorption (B) ppm 499 452 433 769 862 Change (B -A) ppm 398 272 306 480.536

g / / cm 3 0.47 0.53 0.49 0.62 0.76 Weight retention t% 2.2 6.3 4.3 18.2 15.1

[Resin composition]

Flame retardant [UL--94] V- 0 V- 0 V- 0 V- 1 V- 2

MFR .30.2 29 28.9 23.4 20.6 Resin composition: PPE / HIPS / phosphine-fazene yarn = 40/45/15

%)

From the results shown in Tables 3 and 4, it can be seen that TGA having a low residue at 500 ° C exhibits particularly good heat flowability and flame retardancy.

[Examples 23 to 26, Comparative examples 9 to: I 2]

The water content of each of the phosphazene compositions obtained in Examples 1, 2, 4, 5 and Comparative Examples 1 to 3 was measured before and after moisture absorption, and the results in Tables 5 and 6 were obtained. Tables 5 and 6 also show the volatile content of these phosphazene compositions.

Furthermore, AER 250 71. ◦ weight ^_0/0及Pi phosphazene composition 1 6.0 wt. /. Was melted at 110 ° C., a curing agent (13.0% by weight) was added at 110 ° C., the mixture was heated with stirring for 90 seconds, and then poured into a mold.

Then, 2 minutes at 100 ° C / 0 kgf / cm , 100 ° CZ 10 kgf do in 2 minutes, 30 minutes m ² N 100 ° CZ40 kgf, and cured in a hot press molding piece for moisture measurements Obtained. Tables 5 and 6 show the measurement results of the moisture resistance.

[Comparative Example 12]

AE R250 84.5% by weight was kept at 110 ° C, 15.5% by weight of a curing agent was added thereto, heated with stirring for 90 seconds, and then poured into a mold. Then 100 at 100 ° C / 0 kgf / cm ² for 2 minutes. CZl 0 kgf / cm ² for 2 minutes, 1 00 ° CZ40 kgf / cm 2 in 30 minutes and cured in a hot press to obtain a molding piece for moisture measurements. Table 6 shows the results of the moisture resistance measurement.

[Table 5]

Example Example Example Comparative example

23 24 25 26 9

[Phosphazene composition] FR 1 FR 2 FR4 FR 5 FR 9

Volatile content /% 0.174 0.225 0.125 0.088 1.24

Before moisture absorption (A) / ppm 101 180 75 127 289

After moisture absorption (B) / ppm 499 452 540 433 769

Change (B-A) 398 272 465 306 480

[Resin composition]

Water absorption ^ / o 1.69 1.65 1.71 1.66 1.72

Color stability 〇〇〇〇 X

[Table 6]

Comparative example Comparative example Comparative example

10 1 1 1 2

[Phosphazene composition] FR 7 FR8-Volatile content /% 0.017 5.12-Before moisture absorption (A) / ppm 37 326

After moisture absorption (B) / ppm 1498 862-Change (B-A) 1461 536-

[Resin composition]

Water absorption /% 1.92 1.81 2.06

Color stability 〇 ■ 'X 産業 Industrial applicability

The phosphazene composition having a volatile content of 0.02% by weight or more and 1.0% by weight or less when heated at 200 ° C for 2 hours contains no chlorine-based compound or bromine-based compound, and is added to the resin. hydrolysis resistance when it is possible to provide a resin composition which can be highly hold the balance of electrical properties stability in flame retardancy and 1 GH _Z or more high-frequency region.

Claims

The scope of the claims

1. A phosphazene composition containing at least one phosphazene compound, wherein volatile matter from the phosphazene composition is 0.02 with respect to the total weight of the phosphazene composition when heated at 200 ° C. for 2 hours. The phosphazene or composition as described above, which is not less than 1.0% by weight and not more than 1.0% by weight.

2. The volatile matter from the phosphazene composition is selected from the reaction solvent, raw material, and the reaction solvent and z or by-products generated from the raw material in the synthesis of the phosphazene compound remaining in the phosphazene composition. The phosphazene or composition according to claim 1, comprising at least one.

3. The phosphazene composition according to claim 1, wherein the water content measured by the Karl Fischer method at 150 ° C. is 1000 ppm or less.

4. The phosphazene composition according to claim 1, wherein the water content measured by the Karl Fischer method at 150 ° C. is 650 ppm or less.

5. The phosphazene composition according to any one of claims 1 to 4, comprising at least 95% by weight of the cyclic phosphazene compound based on the total weight of the phosphazene composition.

6. The content of one or more metal elements based on the total weight of the phosphazene composition is 20 Oppm or less, respectively, and the content of the compound having a P-OH bond is 1% by weight or less. The phosphazene composition according to any one of claims 1 to 5, wherein the phosphazene composition has a chlorine content of 1,000 ppm or less.

7. The content of one or more kinds of metal elements based on the total weight of the phosphazene composition is 5 Oppm or less, respectively, and the content of the compound having a P-OH bond is 1% by weight or less, The phosphazene composition according to any one of claims 1 to 5, wherein the chlorine content is 500 ppm or less.

8. 90% or more of all the substituents in the phosphazene compound are phenoxy groups, and the phosphorus content is 13.0 to 14.5% by weight based on the total weight of the phosphazene composition. The phosphazene composition according to any one of claims 1 to 7, wherein

9. The weight retention rate at 500 ° C when heated from room temperature to 600 ° C at a temperature rising rate of 10 ° C under an inert gas atmosphere by TGA is 15% by weight or less. 9. The phosphazene composition according to any one of items 1 to 8.

10. The weight retention rate at 500 ° C when heated from room temperature to 600 ° C in a temperature rising rate of 10 ° CZ under an inert gas atmosphere by TGA under an inert gas atmosphere is 10% by weight or less. 9. The phosphazene composition according to any one of items 1 to 8.

1 1. The bulk density is 0.45 gZcm ³ or more. 11. The phosphazene composition according to any one of items 10 to 10.

1 2. A flame-retardant resin composition comprising a resin and the phosphazene composition according to any one of claims 1 to 11.

1 3. Resins are unsaturated polyester resin, butyl ester resin, diaryl phthalate resin, epoxy resin, cyanate resin, xylene resin, triazine resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, urethane resin, ketone resin, alkyd 13. The flame-retardant resin composition according to claim 12, comprising at least one curable resin selected from the group consisting of a resin, a furan resin, a styrylpyridine resin, a silicone resin, and a synthetic rubber.

14. The resin is a group consisting of polycarbonate, polyphenylene ether, polypropylene phenol, polyethylene, polyethylene, polystyrene, ABS resin, polyalkylene terephthalate, polyamide, thermopic liquid crystal and elastomer-containing polystyrene. 13. The flame-retardant resin composition according to claim 12, comprising at least one thermoplastic resin selected from the group consisting of:

15. The flame retardancy according to any one of claims 12 to 14, wherein the phosphorus atom concentration is 0.5% to 8.0% by weight based on the total weight of the flame retardant resin composition. Resin composition.

16. The flame-retardant lumber composition according to any one of claims 12 to 15, which is used for an electric or electronic device part or a casing used in a high-frequency region of 1 gigahertz or more.