JP2006036736A - Acid anhydride having phosphazene skeleton, flame retardant resin composition and flame retardant resin-molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphazene compound having a high flame retardant property (an acid anhydride having a phosphazene skeleton) without bleeding from a mixed resin composition, having a high heat resistance and having remaining property in the resin, and a flame retardant resin composition and a flame retardant resin-molded article by using the same. <P>SOLUTION: This acid anhydride obtained by bonding a cyclic phosphazene with an aromatic acid anhydride by an ester bond is provided. Also, the flame retardant resin composition is characterized by containing the acid anhydride and a thermoplastic resin and/or thermosetting resin. The flame retardant resin-molded article is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an acid anhydride having a phosphazene skeleton, a flame retardant resin composition using the acid anhydride, and a flame retardant resin molded article.

  Resins are used as materials for various products such as electric products and automobiles because of their excellent moldability, mechanical characteristics, electrical characteristics, and appearance. However, the resin has a disadvantage that it is more easily combusted than a metal material or an inorganic material. Therefore, the improvement of the flame retardance of resin is made into the subject.

  Conventionally, it is known to add a phosphazene compound to impart flame retardancy to a resin. For example, (Patent Document 1) discloses a flame retardant resin composition in which a phosphazene compound is blended with a polycarbonate resin or the like. Since the phosphazene compound is a halogen-free flame retardant, it has an advantage of less impact on the environment.

However, when a resin composition is produced using a conventional phosphazene compound, the initial excellent flame retardancy cannot be maintained over a long period of time. The main causes are that the conventional phosphazene compound bleeds from the resin composition and the heat resistance of the phosphazene compound is insufficient. For example, thermoplastic resins are used in housings and mechanism parts of various monitors or printers. In recent years, the resin molding temperature has been higher than before in order to improve functionality by thin-wall molding and productivity by shortening the molding cycle. It has been practiced to improve the fluidity of the resin at a temperature, for example, around 300 ° C. In addition, lead-free solder has been put into practical use from the viewpoint of environmental problems in thermosetting resins used for printed wiring boards and sealing materials, such as epoxy resins and phenol resins, and the associated increase in reflow temperature. (250 ° C. to 260 ° C.), heat resistance is required for resin parts used for electric / electronic parts. In such a high temperature range, a conventional phosphazene compound may cause volatilization and disappearance, and a flame retardant having a better survivability in a resin has been demanded.
JP 7-292233 A

  A phosphazene compound (acid anhydride having a phosphazene skeleton) that does not bleed from the mixed resin composition, has high heat resistance and has a residual property to the resin, and has high flame retardancy, and a flame retardant resin composition using the same And providing a flame-retardant resin molded product.

  The present invention provides an acid anhydride having the following phosphazene skeleton, a flame retardant resin composition using the acid anhydride, and a flame retardant resin molded article, thereby solving the above-described problems.

  The first of the present invention is an acid anhydride having a phosphazene skeleton. By using this acid anhydride, it is possible to obtain a resin composition having high heat resistance and high flame retardancy without bleeding from the mixed resin composition.

  The second of the present invention is the acid anhydride according to claim 1, which has a structure of the following formula (3). Since the introduced acid anhydride reacts with the mixed resin composition, it does not bleed, and a resin composition having high heat resistance and high flame retardancy can be obtained.

（式中ｍは３〜２５の整数を示す。Ｒ¹はフェニル基を示す。Ｒ²はフェニル基あるいは式（４）に示される酸無水物骨格を示し、式（３）の化合物中で式（４）に示される酸無水物骨格を１以上含む。）

(In the formula, m represents an integer of 3 to 25. R ¹ represents a phenyl group. R ² represents a phenyl group or an acid anhydride skeleton represented by the formula (4). (Including one or more acid anhydride skeletons shown in (4))

本発明の第三は、請求項１または請求項２に記載の酸無水物に加え、熱可塑性樹脂及び／または熱硬化性樹脂を含有することを特徴とする難燃性樹脂組成物である。本発明のホスファゼン骨格を有する酸無水物により、混合した熱可塑性樹脂及び／または熱硬化性樹脂に難燃性を付与することが出来る。

A third aspect of the present invention is a flame retardant resin composition containing a thermoplastic resin and / or a thermosetting resin in addition to the acid anhydride described in claim 1 or claim 2. The acid anhydride having a phosphazene skeleton of the present invention can impart flame retardancy to the mixed thermoplastic resin and / or thermosetting resin.

  A fourth aspect of the present invention is a flame retardant resin molded product obtained by molding the flame retardant resin composition according to claim 3. By molding the flame retardant resin composition of the present invention, a flame retardant resin molded product can be produced.

  High flame resistance to resin compositions and flame-retardant resin molded products mixed with phosphazene compounds (acid anhydrides having a phosphazene skeleton) that do not bleed from the mixed resin composition and have high heat resistance and resin persistence Can be granted.

  The acid anhydride having a phosphazene skeleton used in the present invention will be described.

  An acid anhydride having a phosphazene skeleton of the present invention is synthesized by reacting a phosphazene compound having a phenolic hydroxyl group with trimellitic acid or trimellitic acid chloride.

  First, the phosphazene compound having a phenolic hydroxyl group (hydroxyl group) used in the present invention will be described.

Cyclic and / or chain phosphazene compounds having a hydroxyl group (hydroxyl group) are described in, for example, (Non-patent document 1), (Non-patent document 2), (Patent document 2), (Non-patent document 3) and the like. Can be manufactured according to the method. For example, 4-methoxyphenol in which one hydroxyl group of dihydric phenol is protected with a methyl group or a benzyl group, lithium salt, sodium salt or potassium salt of 4- (benzyloxy) phenol, and phosphonitrile chloride (Patent Documents 3 to 3). 4) is reacted, and then the methyl group or benzyl group is deprotected by reaction with pyridine hydrohalide, boron tribromide or the like, and converted to a hydroxyl group. It can also be produced by reacting a lithium salt, sodium salt or potassium salt of hydroxyalkylphenol with phosphonitrile chloride. In addition, production of cyclic and / or chain phosphazene compounds having a partially substituted hydroxy-substituted phenoxy group can be achieved by producing 4-methoxyphenol in which one hydroxyl group of dihydric phenol is protected with a methyl group or a benzyl group, 4- ( Benzyloxy) Lithium salt, sodium salt or potassium salt of alcoholic or phenolic compound is used simultaneously in the reaction of lithium salt, sodium salt or potassium salt of phenol and / or hydroxyalkylphenol with phosphonitrile chloride. Can be manufactured.
Yokoyama Masaaki et al., Industrial Chemical Journal, Vol. 67, no. 9, p. 1378 (1964) Okuhashi Shinya et al., Industrial Chemical Journal, Vol. 73, no. 6, p. 1164 (1970) JP 58-219190 A Alessandro Medici, et. al. , Macromolecules, Vol. 25, no. 10, p. 2569 (1992) JP-A-54-145394 JP, 54-145395, A The specific method is explained.

  For the cyclic dichlorophosphazene compound represented by formula (5) (wherein m represents an integer of 3 to 25).

式（６）で表されるアルカリ金属フェノラート（式中Ｍはアルカリ金属を示す。）と、

An alkali metal phenolate represented by formula (6) (wherein M represents an alkali metal);

式（７）（式中Ｍはアルカリ金属を示す。）で表されるアルキルオキシ基を有するアルカリ金属フェノラートとを、

An alkali metal phenolate having an alkyloxy group represented by the formula (7) (wherein M represents an alkali metal):

反応させることにより、
式（８）で表されるメトキシフェニル基を導入した環状ホスファゼン（式中ｍは３〜２５の整数を示す。Ｒ³及びＲ⁴はフェニル基或いは基−Ｃ₆Ｈ₄ＯＣＨ₃を示す。）が生成する。

By reacting,
Cyclic phosphazene into which a methoxyphenyl group represented by the formula (8) is introduced (wherein m represents an integer of 3 to 25. R ³ and R ⁴ represent a phenyl group or a group —C ₆ H ₄ OCH ₃ ). Produces.

式（８）で表される化合物を、その後にピリジンハロゲン化水素酸塩又は三臭化ホウ素等との反応によって、メチル基又はベンジル基を脱保護し、水酸基に変えることで、
式（９）（式中ｍは３〜２５の整数を示す。Ｒ⁵及びＲ⁶はフェニル基或いは基−Ｃ₆Ｈ₄ＯＨを示す。）で示される、対応するフェノール性水酸基を有する環状ホスファゼン化合物

By deprotecting the methyl group or benzyl group by subsequent reaction with a compound represented by the formula (8), such as pyridine hydrohalide or boron tribromide, and changing to a hydroxyl group,
A cyclic phosphazene having a corresponding phenolic hydroxyl group represented by the formula (9) (wherein m represents an integer of 3 to 25; R ⁵ and R ⁶ represent a phenyl group or a group —C ₆ H ₄ OH). Compound

を製造することが出来る。

Can be manufactured.

  Next, a method for synthesizing an acid anhydride having a phosphazene skeleton of the present invention by reacting a phosphazene compound having a phenolic hydroxyl group with trimellitic acid or trimellitic acid chloride will be described.

  The reaction between the phosphazene compound having a phenolic hydroxyl group and trimellitic acid chloride can be easily synthesized by reacting in the presence of a tertiary amine such as pyridine in an organic solvent. Reaction solvents include aromatic solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and γ-butyrolactone, and acetamides such as N, N-dimethylacetamide and N, N-diethylacetamide. Various solvents can be used as long as they are aprotic solvents, such as pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, and ether solvents such as tetrahydrofuran, dioxane and dioxolane. I can do it. The reaction temperature is about −20 ° C. to 120 ° C., and the reaction is completed in several hours.

  The reaction between a phosphazene compound having a phenolic hydroxyl group and trimellitic acid is synthesized by reacting with p-toluenesulfonic acid chloride, dicyclohexylcarbodiimide or a phosphorus condensing agent in the presence of a tertiary amine such as pyridine. I can do it. Reaction solvents include aromatic solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and γ-butyrolactone, and acetamides such as N, N-dimethylacetamide and N, N-diethylacetamide. Various solvents can be used as long as they are aprotic solvents such as a system solvent, a pyrrolidone solvent such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, and an ether solvent such as tetrahydrofuran and dioxane. The reaction temperature is about 0 ° C. to 120 ° C., and the reaction is completed in several hours.

In this way, a phosphazene compound having a phenolic hydroxyl group can be reacted with trimellitic acid or trimellitic acid chloride to obtain an acid anhydride having a phosphazene skeleton of the present invention represented by the formula (10). . (In the formula, m represents an integer of 3 to 25. R ¹ represents a phenyl group and R ² represents a phenyl group or an acid anhydride skeleton represented by the formula (11). In the compound of the formula (10), the formula (11 And 1 or more acid anhydride skeletons represented by

本発明のホスファゼン骨格を有する酸無水物は、沸点が高いため各種樹脂と混合した場合においても、熱混合時に揮散しないため、高い難燃性が保持される。混合できる樹脂としては特に制限されず、公知の熱可塑性樹脂及び熱硬化性樹脂のいずれも使用できる。

Since the acid anhydride having a phosphazene skeleton of the present invention has a high boiling point, even when mixed with various resins, it does not evaporate during heat mixing, and thus high flame retardancy is maintained. The resin that can be mixed is not particularly limited, and any of known thermoplastic resins and thermosetting resins can be used.

<Acid anhydride>
As long as an acid anhydride having a phosphazene skeleton can be achieved, the acid anhydride is not particularly limited.

<Thermoplastic resin>
Specific examples of the thermoplastic resin include, for example, polyethylene, polypropylene, polyisoprene, polybutadiene, chlorinated polyethylene, polyvinyl chloride, styrene resin, impact-resistant polystyrene, acrylonitrile-styrene resin (AS resin), and acrylonitrile-butadiene-styrene. Resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), polymethyl (meth) acrylate, Polycarbonate, modified polyphenylene ether (PPE), polyamide (aliphatic and / or aromatic), polyester (polyethylene terephthalate, polybutylene tele Talate, polyethylene naphthalate, etc.), polyphenylene sulfide, polyimide, polyetheretherketone, polysulfone, polyarylate, polyetherketone, polyethernitrile, polythioethersulfone, polyethersulfone, polybenzimidazole, polycarbodiimide, polyamideimide, poly Examples thereof include, but are not limited to, ether imides, liquid crystal polymers, and composite plastics.

<Thermosetting resin>
Examples of the thermosetting resin include, but are not limited to, an epoxy compound, an isocyanate compound, a cyanate ester, a compound having a vinyl group such as acrylic, methacrylic, and vinyl.

  Examples of the epoxy compound include bisphenol resins such as Epicote 828 (manufactured by Japan Epoxy Resin Co., Ltd.), orthocresol novolac resins such as 180S65 (manufactured by Japan Epoxy Resin Co., Ltd.), 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) Novolak resin, trishydroxyphenylmethane novolak resin such as 1032H60 (made by Japan Epoxy Resin Co., Ltd.), naphthalene aralkyl novolak resin such as ESN375, tetraphenylolethane 1031S (made by Japan Epoxy Resin Co., Ltd.), YGD414S (Tohto Kasei), Tris Hydroxyphenylmethane EPPN502H (Nippon Kayaku), Special bisphenol VG3101L (Mitsui Chemicals), Special naphthol NC7000 (Nippon Kay) ), TETRAD-X, TETRAD-C (although Mitsubishi Gas Chemical Co., Ltd.) glycidylamine type resins, and the like, but is not limited thereto.

  Examples of isocyanate compounds include aliphatic, alicyclic or aromatic diisocyanates, such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5- Trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4, 4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate Ane - can be mentioned bets like, but is not limited thereto.

  Further, the isocyanate compound is derived from an aliphatic, alicyclic or aromatic isocyanate, such as isocyanurate-modified isocyanate, burette-modified isocyanate, urethane-modified isocyanate, etc. May be. In addition, the isocyanate compound used in the present invention is preferably a block isocyanate in which the isocyanate group of the isocyanate compound is blocked with a blocking agent, but is not limited thereto. Absent.

  Examples of the blocking agent include alcohol, phenol, active methylene, mercaptan, acid amide, acid imide, imidazole, urea, oxime, amine, and bisulfite. There are salts, imine-based compounds, imide-based compounds, pyridine-based compounds, and the like. These may be used alone or in combination, but are not limited thereto. Specific examples of the blocking agent include alcohols such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexyl. For example, phenol, cresol, ethyl phenol, butyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol, hydroxybenzoate, etc. As dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc., as mercaptans, butyl mercaptan, dodecyl mercaptan, etc., as acid amides, acetanilide, acetate amide, ε-caprolactam, δ-valerolactam Γ-Butylora Kutam, etc., acid imide series, succinimide, maleic imide, imidazole series, imidazole, 2-methylimidazole, urea series, urea, thiourea, ethylene urea etc., oxime series, Formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., amine type, diphenylamine, aniline, carbazole, etc., imine type, ethyleneimine, polyethyleneimine, etc., bisulfite, bisulfite soda, etc. Examples of the pyridine series include 2-hydroxypyridine and 2-hydroxyquinoline, but are not limited thereto.

  In particular, Elastron [trade name BN-P17, 4,4′-diphenylmethane diisocyanate blocked form] manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Elastron [BN-04, BN-08, BN-44, BN] -45: 3 to 5 functional groups per molecule of urethane-modified isocyanate block. Any of them can be used after drying and isolation in a water emulsion product].

  Examples of compounds having a vinyl group such as acrylic, methacrylic and vinyl include bisphenol F EO modified (n = 2-50) diacrylate, bisphenol A EO modified (n = 2-50) diacrylate, bisphenol S EO modified (n = 2-50) diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, Tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate , Ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol Cole acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane Diol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy · diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy · polyethoxy) phenyl] propane, poly Reethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2-bis [4- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy-polyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenoxy polyethylene glycol acrylate, nonyl Phenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-fur Rate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6- Mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol Diacrylate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) Enyl] propane, 2,4-diethyl-1,5-pentanediol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxy Pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloyl hexahydro-s -Triazine, triallyl-1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, tria Rilphosphate, allobarbital (5,5-diallylbarbituric acid), diallylamine, diallyldimethylsilane, diallyldisulfide, diallylether, zalylsialate, diallylisophthalate, diallylterephthalate, 1,3-dialyloxy-2-propanol, diallyl Sulfide diallyl maleate, 4,4′-isopropylidene diphenol dimethacrylate, 4,4′-isopropylidene diphenol diacrylate and the like are preferable, but not limited thereto. In order to improve the crosslink density, it is particularly desirable to use a bifunctional or higher monomer.

  The cyanate ester compound is not particularly limited as long as the cyanate ester is contained in the molecule, but can be exemplified as follows.

  As a specific chemical formula, formula (12) can be exemplified.

（Ｒ⁷ は同一でも異なってもよく、水素かアルキル基、パーフルオロアルキル基、アリール基、またはハロゲンであり、Ａは単結合、未置換メチレン基、水素原子の１つまたは２つをアルキル基、パーフルオロアルキル基、および／またはアリール基で置換した置換メチレン基、５員もしくは６員の環状脂肪族基、スルホン基、２価の硫黄、酸素、２価のカルボニル基、メチレン基が置換又は未置換のキシリレン基、フェニル基である。ｗは４である。）
その他のシアン酸エステルの例としては、１，３−ジシアネートベンゼン、１，４−ジシアネートベンゼン、１，３，５−トリシアネートベンゼン、１，３−ジシアネートナフタレン、１，４−ジシアネートナフタレン、１，６−ジシアネートナフタレン、１，８−ジシアネートナフタレン、２，６−ジシアネートナフタレン、２，７−ジシアネートナフタレン、１，３，６−トリシアネートナフタレン、２，２−ビス（３，５−ジシクロ−４−シアネートフェニル）プロパン、トリス（４−シアネートフェニル）ホスファイト、トリス（４−シアネートフェニル）ホスフェート、およびフェノール樹脂とハロゲン化シアンとの反応により得られるベンゼン多核体のポリシアネート化合物等が挙げられるが、これらに限定されるものではない。例示したシアン酸エステルを加熱してオリゴマー化したものも同様に使用することができる。

(R ⁷ may be the same or different and is hydrogen, an alkyl group, a perfluoroalkyl group, an aryl group, or a halogen, and A is a single bond, an unsubstituted methylene group, or one or two of the hydrogen atoms are alkyl groups. A substituted methylene group substituted with a perfluoroalkyl group and / or an aryl group, a 5- or 6-membered cycloaliphatic group, a sulfone group, a divalent sulfur, oxygen, a divalent carbonyl group, or a methylene group. An unsubstituted xylylene group and a phenyl group. W is 4.)
Examples of other cyanate esters include 1,3-dicyanate benzene, 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 1,3-dicyanate naphthalene, 1,4-dicyanate Naphthalene, 1,6-dicyanate naphthalene, 1,8-dicyanate naphthalene, 2,6-dicyanate naphthalene, 2,7-dicyanate naphthalene, 1,3,6-tricyanate naphthalene, 2,2-bis ( 3,5-dicyclo-4-cyanatephenyl) propane, tris (4-cyanatephenyl) phosphite, tris (4-cyanatephenyl) phosphate, and polybenzenes of benzene polynuclears obtained by reaction of phenolic resin with cyanogen halide Examples include, but are not limited to, cyanate compounds. Those obtained by oligomerizing the exemplified cyanate ester by heating can also be used.

  This cyanate ester compound is preferably blended in an amount of 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, per 100 parts by weight of the resin composition of the present invention. As the cyanate ester compound, one kind of compound may be used, or several kinds may be mixed and used.

<Resin composition>
As a preferable mixing ratio of the acid anhydride having a phosphazene skeleton of the present invention to a thermoplastic resin and a thermosetting resin, the content of the acid anhydride having a phosphazene skeleton is 0.1 to 50% by weight based on the whole. It is preferable to be in the range. If it is less than 0.1%, the flame retardancy is small, and if it is 50% or more, a decrease in adhesiveness and a decrease in mechanical properties are observed.

  Since the acid anhydride having a phosphazene skeleton of the present invention has an acid anhydride skeleton, it can react with various reactive groups. Examples of the various reactive groups include an epoxy group, an isocyanate, an amino group, and an alcoholic hydroxyl group. If these reactive groups are present in the resin, it reacts with the acid anhydride having the phosphazene skeleton of the present invention, and the acid anhydride having the phosphazene skeleton is taken into the resin, so that bleeding from the resin does not occur. These reactive groups may be hung from the side chain of the polymer, may be at the terminal of the polymer, and may be a low molecular compound or an oligomer such as the above-described epoxy compound or isocyanate compound.

  In addition to the acid anhydride having a phosphazene skeleton of the present invention, a phosphorus compound may be included. The acid anhydride having a phosphazene skeleton of the present invention has a high thermal decomposition temperature and high heat resistance. Therefore, when the decomposition temperature of the thermoplastic resin and the thermosetting resin to be mixed is lower than the acid anhydride having a phosphazene skeleton, a small amount of a phosphorus compound lower than the decomposition temperature of the thermoplastic resin and the thermosetting resin to be mixed is added. This is preferable because the flame-retardant effect is further enhanced.

  Examples of preferred phosphorus compounds include phosphorus compounds such as phosphine, phosphine oxide, phosphate ester (including condensed phosphate ester), phosphite ester, and phosphazene (not including acid anhydride structure). It is not limited to these. Of these, phosphine oxide, phosphate ester (including condensed phosphate ester), and phosphazene are particularly preferable. The phosphorus content of the phosphorus compound used as a flame retardant is preferably 5.0% by weight, more preferably 7.0% by weight or more.

  Furthermore, from the point that it can impart flame retardancy and has hydrolysis resistance, for example, SPE-100 (phosphazene compound manufactured by Otsuka Chemical), SPH-100 (phosphazene compound manufactured by Otsuka Chemical), TPP (triphenyl phosphate). ), TCP (tricresyl phosphate), TXP (trixylenyl phosphate), CDP (cresyl diphenyl phosphate), PX-110 (cresyl 2,6-xylenyl phosphate) (all manufactured by Daihachi Chemical) Non-halogen-based condensed phosphate esters such as phosphate ester, CR-733S (resinol diphosphate), CR-741, CR-747, PX-200 (all manufactured by Daihachi Chemical), Biscoat V3PA (Osaka Organic Chemical) Kogyo), MR-260 (manufactured by Daihachi Chemical), etc. And phosphites such as triphenyl phosphite, but are not limited thereto.

  These phosphorus compounds are preferably used in an amount of 100 to 10% by weight based on the amount of the acid anhydride having a phosphazene skeleton of the present invention.

<Molded product>
The molded product referred to in the present invention refers to a product obtained by molding the resin composition into a film shape, a pellet shape, a foam shape, a block shape, or the like, and is not particularly limited by the shape. The molding method includes, but is not limited to, extrusion molding, blow molding, vacuum molding, injection molding, die extrusion, and the like.

Evaluation of <Flame Retardancy> Flame retardance is evaluated based on the UL-94 test method. V-0 has high flame retardancy, and the degree of flame retardance decreases in the order of V-1 and V-2.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.

<Synthesis Example 1> (Synthesis of raw material phosphazene)
In a 5 L flask equipped with a reflux condenser, thermometer, stirrer, phosphorus trichloride dropping device and chlorine gas blowing tube, 2.5 L of chlorobenzene, 182.5 g (3.4 mol) of ammonium chloride and 2.5 g of zinc chloride Was added to obtain a mixed dispersion. The dispersion was heated to a temperature of 130 ° C., and 425.5 g of phosphorus trichloride was added dropwise at a rate of 9 g / min over 48 minutes under reflux, while 227 g of chlorine gas was supplied at a rate of 5 g / min over 46 minutes. After supplying phosphorus trichloride and chlorine gas, the reaction was completed by further refluxing (131 ° C.) for 150 minutes. Next, suction filtration was performed to remove unreacted ammonium chloride, and chlorobenzene was distilled off at 30 to 50 ° C. under a reduced pressure of 1.0 to 3.0 hPa to obtain 352 g of a reaction product. The yield of the reaction product based on phosphorus trichloride was 98.1%. Redissolved in chlorobenzene, and recrystallization gave a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene (226 g, hexachlorocyclotriphosphazene: 76%, octachlorocyclotetraphosphazene: 24%). Further, 155 g of hexachlorocyclotriphosphazene having a purity of 99.9% was obtained by recrystallizing the mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene obtained previously three times using hexane.

<Synthesis Example 2> (Synthesis of phosphazene having a hydroxy group)
In a 2 L 4-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 58 g of hexachlorocyclotriphosphazene of 99.9% purity synthesized in Synthesis Example 1 (0.5 unit mol, 1 NPCl ₂₎ Unit) and 100 mL of tetrahydrofuran (THF) were charged to obtain a solution. Next, while separately preparing a THF solution of 4-methoxyphenol sodium salt (4-methoxyphenol 149.0 g (1.2 mol), sodium 25.3 g (1.1 g-atom), THF 600 mL) while stirring, The solution was added dropwise to the THF solution of hexachlorocyclotriphosphazene over time. There was a violent exotherm until about 1/3 of the sodium salt was added, and the dropping reaction was carried out while cooling. When the remaining 2/3 amount was added, a vigorous exothermic reaction did not occur, but the reaction was carried out by appropriately cooling the reaction temperature to 30 ° C. or lower. After completion of the dropwise addition, a stirring reaction was continued at room temperature for 12 hours. Next, in order to complete the reaction, the reaction was performed for 6 hours under reflux of the solvent. After completion of the reaction, the solvent THF was distilled off under reduced pressure, and then 500 mL of toluene was added and redissolved. Further, 500 mL of water was added and the organic layer was separated in a separatory funnel. The organic layer was washed with 500 mL of 5% aqueous sodium hydroxide solution three times, further washed once with 500 mL of 5 wt% aqueous hydrochloric acid solution, once with 500 mL of 5% aqueous sodium hydrogen carbonate, and twice with 500 mL of water. The pH of the aqueous layer at this time was 7-8. The organic layer was separated, dehydrated with anhydrous magnesium sulfate, and toluene was distilled off to obtain 138.4 g (yield 95%) of hexa (4-methoxyphenoxy) cyclotriphosphazene as a yellow solid. The amount of residual chlorine was 0.02%, and the melting point was 104 ° C. (document value 103 to 104 ° C.). 130.6 g (0.45 unit mol) of hexa (4-methoxyphenoxy) cyclotriphosphazene obtained by the above method and 1040 g (9 mol) of pyridine hydrochloride were charged into a 2 L four-necked flask, and gradually The temperature was raised and the reaction was carried out at 205-210 ° C. for 1 hour. After cooling at room temperature, 300 mL of water was added to dissolve the reaction product and excess pyridine hydrochloride, and a reaction solution was prepared to pH 6-7 with a 20% aqueous sodium hydroxide solution. Next, extraction was performed 4 times with 500 mL of ethyl acetate, and the combined extracts were washed 4 times with 500 mL of saturated aqueous sodium sulfate solution. The organic layer was separated, dehydrated with anhydrous magnesium sulfate, and then subjected to reduced pressure. The ethyl acetate was distilled off. Next, the step of dissolving the concentrate in 200 mL of methanol and adding it to 1.5 L of water to precipitate the crystals was repeated three times. The obtained crystals were dried under reduced pressure, and 94.8 g of light yellow crystals (yield 80). %). The residual chlorine content of the product is 0.01% or less, and the hydroxyl group (OH, OH, acetylation method with acetic anhydride and pyridine described in Analytical Chemistry Handbook (edited by the Japan Society for Analytical Chemistry), Organics, page 316 is used. %) Was 12.9% (theoretical value 12.9%, composition formula N ₃ P ₃ (OC ₆ H ₄ OH) ₆ hydroxyl group equivalent 131.8). Further, ¹ H- and ³¹ P-NMR analyzes were performed to confirm the synthesis.

<Synthesis Example 3> Hydroxyl equivalent weight 363 (synthesis of phosphazene partially having a hydroxyl group)
In a 2 L four-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 58 g of hexachlorocyclotriphosphazene having a purity of 99.9% (0.5 unit mol, NPCl ₂ as one unit), THF 100 mL Was added to obtain a solution. Next, a separately prepared THF solution of 4-methoxyphenol Na salt (4-methoxyphenol 43.4 (0.35 mol), sodium 7.6 g (0.33 g-atom)) and THF 200 mL were stirred for 1 hour. The solution was dropped into the above THF solution of hexachlorocyclotriphosphazene over a period of time, and since it was a vigorous exothermic reaction, the reaction was carried out with appropriate cooling so that the reaction temperature did not exceed 30 ° C. After completion of the dropping, the reaction was continued at 60 ° C. for 6 hours. The residual chlorine content of the partially substituted product obtained by the reaction was 27.11%, and the estimated structure was N ₃ P ₃ Cl _4.0 (OC ₆ H ₄ OCH ₃ ) _2.0 . Next, separately prepared sodium phenolate in THF (phenol 79.1 g (0.85 mol), sodium 18.4 g (0.8 g-atom), THF 200 m Was added dropwise over 1 hour under cooling control so that the reaction temperature was 30 ° C. or less, and then the reaction was completed at room temperature for 5 hours and at reflux temperature for 3 hours. Was distilled off under reduced pressure, and then 500 mL of toluene was added to redissolve the product, and 300 mL of water was further added and the solution was washed with water, and the organic layer was washed with 5% aqueous sodium hydroxide solution and 2% sodium hydroxide. Washing with an aqueous solution was performed once, followed by washing once with a 5% by weight aqueous hydrochloric acid solution, washing once with 5% aqueous sodium hydrogen carbonate, and further washing twice with water to neutralize the aqueous layer. The organic layer was separated and dried over anhydrous magnesium sulfate, and toluene was distilled off to obtain 110.0 g (yield 91%) of a pale yellow oily product with a residual chlorine content of 0.01% or less. 4-methoxyphene obtained by the above method. 96.8 g (0.40 unit mol) of cyclotriphosphazene mixed with xy group and phenoxy group and 583.6 g (5.05 mol) of pyridine hydrochloride were charged into a 2 L 4-necked flask and gradually heated. The reaction was carried out for 1 hour at 205 to 210 ° C. The subsequent operation was carried out in the same manner as in Synthesis Example 2 to obtain 75.0 g (yield 77.5%) of a yellow solid having a residual chlorine content of 0.01. %, And the hydroxyl group content was 4.7% (theoretical value: 4.7%, composition formula: N ₃ P ₃ (OPh) _4.0 (OC ₆ H ₄ OH) _2.0 , hydroxide equivalent 363)
(Example 1) Synthesis of an acid anhydride having a phosphazene skeleton In a reaction vessel equipped with a stirrer and a dropping funnel, 21.06 g (100 mmol) of trimellitic acid chloride and 50 g of methyl ethyl ketone are taken and stirred at room temperature. 36.3 g (100 mmol based on OH) of phosphazene having a partially hydroxyl group (composition formula N ₃ P ₃ (OPh) _4.0 (OC ₆ H ₄ OH) _2.0 ) synthesized in Synthesis Example 3 was added to 50 g of methyl ethyl ketone and 9.5 g of pyridine. The solution was added dropwise to the reaction solution at room temperature and stirred for 1 hour at room temperature. Thereafter, the mixture was stirred for 2 hours under reflux. The reaction vessel was then cooled with ice water for 30 minutes. All previous reactions were carried out under a nitrogen stream.

The precipitated hydrochloride of pyridine was filtered off, the filtrate was concentrated, and 30 g of acetone was added to the concentrated solution to dissolve the concentrate. This solution was poured into 200 g of distilled water and stirring was continued for 1 hour. The deposited viscous liquid was taken out and dried in a vacuum oven (120 ° C. for 2 hours) to obtain 46.5 g of an acid anhydride. This acid anhydride was dissolved in 60 g of acetic anhydride, heated at 140 ° C. for 2 hours, and then dried in a vacuum oven (120 ° C. for 2 hours) to obtain 46.5 g of the desired acid anhydride. (Yield 86.6%) This is referred to as Compound A. ¹ H-NMR: Measurement conditions Gemini 300 manufactured by Varian, operating frequency 300 Hz, solvent DMSO-d ₆ , (1) trimellitic acid-derived aromatic ring δ7.8-8.6, 6H, (2) other aromatic ring δ6. 9-7.5, 28H.

(Example 2) Synthesis of acid anhydride having phosphazene skeleton 31.6 g (150 mmol) of trimellitic acid chloride prepared in Example 1, phosphazene having a hydroxy group synthesized in Synthesis Example 2 (composition formula N ₃ P ₃ (OC ₆ H ₄ OH) ₆ hydroxyl group equivalent 131.8) 19.8 g (150 mmol on the basis of OH) and 14.2 g of pyridine were reacted in the same manner to obtain 36.7 g of acid anhydride. (Yield 80%) This is designated as Compound B. ¹ H-NMR: Measurement conditions Gemini300 manufactured by Varian, operating frequency 300 Hz, solvent DMSO-d ₆ , (1) trimellitic acid-derived aromatic ring δ7.8-8.6, 18H, (2) other aromatic rings δ6 .9-7.5, 24H.

(Example 3)
15 parts of Compound A produced in Example 1 and 0.2 part of PTFE were added to a resin composed of 75 parts (parts by weight) of an aromatic polycarbonate resin and 25 parts of ABS resin, mixed with a mixer, and then used with a lab plast mill. And kneaded to obtain a flame retardant resin composition.

  A test piece having a thickness of 1/8 inch was prepared from this composition by a hot press, and the flame retardant evaluation based on the UL-94 test method and the measurement of the heat distortion temperature according to ASTM D-648 were performed. It was. As a result, the flame retardancy was V-0, the heat distortion temperature was 108 ° C., and juicing was not observed during molding. This represents the excellent remaining performance of the resin composition comprising the compound having a phosphazene skeleton of the present invention on the resin molded body. Since there is no juicing at the time of molding, the mold or the like is not soiled, which is preferable.

Example 4
Using Compound B produced in Example 2, sample preparation and evaluation were carried out in the same manner as in Example 3. As a result, the flame retardancy was V-0, the heat distortion temperature was 111 ° C., and juicing was not observed during molding.

(Example 5)
In the formulation of Example 3, a sample was prepared without adding PTFE, and the flame retardancy and the heat distortion temperature were evaluated. As a result, the flame retardancy was V-0 and the heat distortion temperature was 109 ° C., and juicing was not observed during molding.

(Comparative Example 1)
Sample preparation and evaluation were carried out in the same manner as in Example 1 except that trixylyl phosphate was used in place of Compound A produced in Example 1. As a result, the flame retardancy was V-2, the heat distortion temperature was 82 ° C., and juicing was observed during molding.

(Reference Example 1)
A stirring bar, a condenser, a dropping funnel and a flask equipped with a thermometer were charged with 460 g (3 mol) of phosphorus oxychloride, 110 g (2 mol) of resorcin, 94.1 g (1 mol) of phenol and 9 g of aluminum chloride (catalyst) at 150 ° C. The reaction was continued until 564.6 g (6 mol) of phenol was added. After the reaction mixture was washed with water, triphenyl phosphate was distilled off under high temperature vacuum to obtain 515 g of condensed phosphoric acid diphenyl ester crosslinked with resorcinol.

  Quality of this condensed phosphoric acid diphenyl ester: yellow liquid, average molecular weight = 540,% P = 10.6, acid value 2.2.

(Comparative Example 2)
Sample preparation and evaluation were performed in the same manner as in Example 1 except that condensed phosphoric acid diphenyl ester crosslinked with resorcinol (obtained in Reference Example 1) was used in place of Compound A produced in Example 1. As a result, the flame retardancy was V-2, the heat distortion temperature was 89 ° C., and juicing was observed during molding.

(Comparative Example 3)
When a sample was prepared and evaluated in the same manner as in Example 1 without adding a flame retardant, the test piece burned and showed no flame retardancy. The heat distortion temperature was 111 ° C.

(Example 6)
70 parts of polycarbonate, 15 parts of epoxy compound (Epicoat 1004, manufactured by Japan Epoxy Resin Co., Ltd.), 15 parts of Compound A synthesized in Example 1 were dissolved in methylene chloride, and 18 μm thick copper foil (3EC-VLP made by Mitsui Kinzoku) After coating, the film was dried at 40 ° C. for 5 minutes, 60 ° C. for 5 minutes and 80 ° C. for 5 minutes, then heated at 160 ° C. for 1 hour, and the copper foil was removed by etching to obtain a 25 μm thick film. This film was VTM-0 as a result of evaluation of flame retardancy based on the UL-94 test method.

(Comparative Example 4)
The obtained film was burned as a result of the evaluation of flame retardancy based on the UL-94 test method.

Claims (4)

An acid anhydride having a phosphazene skeleton. The acid anhydride of Claim 1 which has a structure of following formula (1).

(In the formula, m represents an integer of 3 to 25. R ¹ represents a phenyl group. R ² represents a phenyl group or an acid anhydride skeleton represented by the formula (2). (Including one or more acid anhydride skeletons shown in (2))

A flame retardant resin composition comprising a thermoplastic resin and / or a thermosetting resin in addition to the acid anhydride according to claim 1 or 2. A flame-retardant resin molded product obtained by molding the flame-retardant resin composition according to claim 3.