JP2019163404A - Flame-retardant resin composition - Google Patents

Abstract

To provide a resin molding which exhibits good dielectric properties and has excellent flame retardancy and heat resistance.SOLUTION: There is provided a composition used as a production raw material for a resin molding which comprises a specific aryloxy cyclic phosphazene compound and a resin component. The specific aryloxy cyclic phosphazene compound used here has, for example, a structure in which in the following formula (1), n is 3 and all of R is a phenoxy phenoxy group, an ethenylphenoxy group or a benzylphenoxy group and satisfies the conditions that the weight retention rate at 500°C when heated from normal temperature to 600°C at a temperature-raising rate of 10°C/min in an inert gas atmosphere in a thermogravimetric analysis is 50% or more, the specific dielectric constant at a frequency of 1GHz at 25°C is 2.6 or less and the dielectric loss is 0.002.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, in particular, a flame retardant resin composition.

  Automotive, ITS (Intelligent Transport Systems), IoT (Internet of Things), M2M (Machine to Machine), D2D (Device to Device) and 5th generation mobile communication systems (5G) Practical use of high-frequency signal handling systems and more advanced practical plans are in progress. Accordingly, high frequency transmission signals are required for electrical and electronic devices indispensable in these industrial fields, for example, electronic components typified by semiconductors and printed wiring boards on which these are mounted.

  In response to this demand, there is a demand for a resin material for realizing a substrate with low transmission loss in the high frequency band and excellent dielectric characteristics, and development and practical application of the resin material in response to this demand are also progressing. Such a resin material is required to have the above-described electrical characteristics, and at the same time, is required to have flame retardancy when processed into a thin film suitable for itself or a substrate. Consider the use of flame retardants.

  In general, flame retardants used for resin materials are roughly classified into inorganic flame retardants and organic flame retardants. Examples of the inorganic flame retardant include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, nitrogen compounds such as melamine cyanurate, phosphorus compounds such as red phosphorus, phosphoric acid amide, ammonium polyphosphate, and aluminum phosphinate. , Antimony compounds such as antimony trioxide and antimony pentoxide, and boron compounds. On the other hand, examples of the organic flame retardant include halogenated compounds such as chlorinated paraffin, bis (pentabromophenyl) ethane, brominated polystyrene and tetrabromobisphenol A, triphenyl phosphate (TPP), tricresyl phosphate (TCP ) And bisphenol A bis-diphenyl phosphate (BDP), and phosphorus halide compounds such as tris (chloroethyl) phosphate (TCEP) and tris (β-chloropropyl) phosphate (TCPP).

  Inorganic flame retardants have excellent dielectric properties and are not likely to impair the electrical properties of the resin material. However, since they exhibit water absorption and hydrolyzability, the mechanical properties and electrical properties of the resin molded products can be reduced by their use. As a flame retardant for resin materials used for electrical and electronic equipment that require long-term reliability, it is liable to cause deterioration of mechanical characteristics over time. On the other hand, the use of organic flame retardants is being restricted from the viewpoint that halogen-based compounds are required to be environmentally friendly with halogen-free, and phosphorous compounds have plasticity, so the amount added to resin materials is increased. If the flame retardancy is increased, the mechanical strength of the resin molded body may be impaired. Also, since it shows hydrolyzability, its use will deteriorate over time in the mechanical and electrical characteristics of the resin molded body. It is easy to invite.

  Thus, phosphazene compounds, which are organic / inorganic hybrid materials, have attracted attention as flame retardants used for resin materials. Since the phosphazene compound is a phosphorus-containing compound and has a higher phosphorus content than the organic phosphorus compound, the amount of addition to the resin material can be suppressed, and the required flame retardancy can be imparted to the resin molded body. Since the plasticity and hydrolyzability are small, the mechanical properties and electrical properties of the resin molded body are unlikely to deteriorate over time.

  Patent Document 1 discloses a flame retardant containing a composition containing a phenoxyphosphazene compound as an active ingredient, and by using such a flame retardant, a resin molded article having excellent electrical property stability in a high frequency region can be obtained. It is said. However, this flame retardant has a weight retention of not more than 15% by weight at 500 ° C. when the composition is heated from room temperature to 600 ° C. at a temperature rising temperature of 10 ° C./min in an inert gas atmosphere by TGA. Therefore, a resin molded body using the same lacks thermal stability at high temperatures.

Japanese Patent No. 3923497

  This invention makes it a subject to implement | achieve the resin molding which shows a favorable dielectric characteristic, and was excellent in the flame retardance and thermal stability.

  The flame retardant resin composition according to the present invention includes a specific aryloxy cyclic phosphazene compound and a resin component. Here, the specific aryloxy cyclic phosphazene compound is represented by the following formula (1), and when heated at a heating rate of 10 ° C./min from normal temperature to 600 ° C. in an inert gas atmosphere in thermogravimetric analysis. The weight retention at 500 ° C. is 50% or more, the relative dielectric constant at a frequency of 1 GHz at a temperature of 25 ° C. is 2.6 or less, and the dielectric loss is 0.002 or less.

In formula (1), n shows the integer of 3-8, R shows the following R-1 group or R-2 group each independently, and at least one is R-2 group.
R-1 group: An aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
R-2 group: a substituted aryloxy group represented by the following formula (2).

In the formula (2), R ¹ represents a single bond, an oxygen atom, a sulfur atom, a methylene group, an oxymethylene group or a sulfonyl group, and R ² represents a hydrogen atom or a characteristic group having a molar polarization per molar volume of 0.4 or less. Each of R ³ independently represents a hydrogen atom, an alkyl or alkenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent, p and q Each independently represents an integer of 1 to 4, and r represents 0 or 1. However, R ² when r is 0 is not a hydrogen atom or a methyl group.

  The aryloxy cyclic phosphazene compound used in the present invention is usually 95% by weight in which n in the formula (1) is 3 or 4 or n in the formula (1) is 3 and 4 An aryloxy cyclic phosphazene compound mixture containing the above.

  The aryloxy cyclic phosphazene compound used in the present invention preferably has an acid value of 0.05 mgKOH / g or less.

  Furthermore, the aryloxy cyclic phosphazene compound used in the present invention preferably has a water content of 100 mg / kg or less as measured by the Karl Fischer method.

  The resin component used in the present invention includes, for example, polyarylate resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyethersulfone resin, polyimide resin, polyetheretherketone resin, polyphenylene ether resin, bismaleimide resin, It is selected from the group consisting of phenyl sulfone resin, polyphthalamide resin, polyphenylene sulfide resin, cyanate ester resin, bismaleimide-cyanate ester resin, styrene-butadiene resin, styrene-maleic acid resin and their modified resins. is there.

The aryloxy cyclic phosphazene compound used in one embodiment of the present invention has a polymerization-reactive characteristic group having a molar polarization per molar volume of 0.4 or less as R ² in the formula (2). The flame retardant resin composition of the present invention according to this embodiment may further contain a polymerizable material capable of undergoing a polymerization reaction with the polymerizable reactive characteristic group of the aryloxy cyclic phosphazene compound. The flame retardant resin composition of this form uses an aryloxy cyclic phosphazene compound having an alkenyl group as the polymerizable reactive characteristic group, and a vinyl compound, vinylidene compound, diene compound, acrylic compound, epoxy as the polymerizable material. A compound using at least one selected from the group consisting of a series compound and a cyclic compound selected from the group consisting of lactones, lactams and cyclic ethers is preferred.

  This invention which concerns on another viewpoint is related with the resin molding, and this resin molding consists of the flame-retardant resin composition of this invention.

  The present invention according to still another aspect relates to an electric / electronic component, and the electric / electronic component includes the resin molded body of the present invention.

  Since the flame-retardant resin composition according to the present invention uses a specific aryloxy cyclic phosphazene compound, it is possible to form a resin molded article that exhibits good dielectric properties and is excellent in flame retardancy and thermal stability. is there.

  Since the resin molded body according to the present invention is composed of the flame retardant resin composition of the present invention, it exhibits good dielectric properties and is excellent in flame retardancy and thermal stability.

  Since the electrical / electronic component according to the present invention includes the resin molded body of the present invention, it exhibits good dielectric properties and is excellent in flame retardancy and thermal stability.

  The flame retardant resin composition of the present invention contains a specific aryloxy cyclic phosphazene compound and a resin component.

  The structure of the aryloxy cyclic phosphazene compound used in the composition of the present invention is represented by the following formula (1).

  In formula (1), n shows the integer of 3-8. Therefore, the aryloxy cyclic phosphazene compound represented by the formula (1) includes an aryloxycyclotriphosphazene compound (trimer) in which n is 3 and an aryloxycyclotetraphosphazene compound (tetramer) in which n is 4 , N is 5 aryloxycyclopentaphosphazene compound (pentamer), n is 6 aryloxycyclohexaphosphazene compound (hexamer), n is 7 aryloxycycloheptaphosphazene compound (7mer) Or an aryloxycyclooctaphosphazene compound (octamer) in which n is 8.

  When these aryloxy cyclic phosphazene compounds are used in the composition of the present invention, those having a small n are easy to realize a resin molded article having excellent dielectric properties. And those having n of 3 or 4 are particularly preferred. In addition, the aryloxy cyclic phosphazene compound may be a mixture of two or more kinds having different n, but this mixture has a higher content of the aryloxy cyclic phosphazene compound having a small n. When used in the above, it is easy to realize a resin molded article having excellent dielectric characteristics. Accordingly, the mixture of aryloxy cyclic phosphazene compounds having different n is preferably a mixture containing 95% or more by weight of cyclic phosphazene compounds having n of 3 to 6, and 95% by weight of cyclic phosphazene compounds having n of 3 and 4. A mixture containing at least% is particularly preferred.

  R in Formula (1) represents the following R-1 group or R-2 group, at least one of which is an R-2 group.

R-1 group:
An aryloxy group having 6 to 20 carbon atoms, wherein at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  Examples of such aryloxy groups include phenoxy group, methylphenoxy group, dimethylphenoxy group, ethylphenoxy group, ethylmethylphenoxy group, diethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, isopropylmethylphenoxy group, Isopropylethylphenoxy group, diisopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-pentylphenoxy group, n-hexylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, n-propoxy group Phenoxy group, iso-propoxyphenoxy group, n-butoxyphenoxy group, tert-butoxyphenoxy group, 4-methoxy-3-methylphenoxy group, 4-ethoxy-3-methyl Ruphenoxy group, 4-n-propoxyphenoxy group, 4-iso-propoxy-3-methylphenoxy group, 4-n-butoxy-3-methylphenoxy group, 4-tert-butoxy-3-methylphenoxy group, phenylphenoxy Group, naphthyloxy group, anthryloxy group, phenanthryloxy group and the like. Of these, phenoxy group, methylphenoxy group, dimethylphenoxy group, diethylphenoxy group, methoxyphenoxy group, phenylphenoxy group and naphthyloxy group are preferable, and phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthyloxy group are particularly preferable.

R-2 group:
A substituted aryloxy group represented by the following formula (2).

In the formula (2), R ¹ represents a single bond, an oxygen atom (O), a sulfur atom (S), a methylene group (CH ₂ ), an oxymethylene group (OCH ₂ ) or a sulfonyl group (SO ₂ ). R ² represents a hydrogen atom or a characteristic group having a molar polarization per molar volume of 0.4 or less. R ³ each independently represents a hydrogen atom, an alkyl group or alkenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent. p and q each independently represent an integer of 1 to 4, and r represents 0 or 1. However, when r is 0 in the formula (2), R ² is not a hydrogen atom or a methyl group.

Molar polarization 0.4 following characteristics groups per molar volume is an option of R ² (hereinafter, sometimes referred to as "R ² Characteristics group".) "Molar polarization per mole volume", the following Clausius -Defined by the Mossotti equation.

_Where P _LL is molar polarization and V is molar volume. ε is a relative dielectric constant of an atomic group (molecule) constituting the R ² characteristic group.

The above-mentioned characteristic groups P _LL and V are obtained by the sum of P _LL and V of atomic groups constituting the characteristic group. In order to achieve a low dielectric constant in the resin molded body made of the composition of the present invention, it is preferable to use an atomic group having a smaller molar polarization per molar volume as the R ² characteristic group.

  The numerical value of molar polarization per molar volume of the characteristic group and the calculation method are described in, for example, the following documents 1 to 4.

Reference 1: Electrical properties of polymer, Kanamaru K., Kyoritsu Publishing Co., Ltd. Reference 2: Electronic materials, 31 [10] 84-87 (1992)
Reference 3: Circuit Technology, Vol8, No. 2 (1993)
Reference 4: Properties of Polymers, D.M. W. Van Krevelen, 2009, Elsevier

The R ² characteristic group can be classified into a non-reactive type having no reactivity such as polymerization activity and a reactive type having a polymerization activity reactivity.

Non-reactive R ² characteristic groups include, for example, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group, fluoro group, monofluoromethyl group, difluoromethyl group, trifluoro group. Fluoroalkyl groups such as methyl group, pentafluoroethyl group and heptafluoropropyl group, alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group and n-butoxy group, and methylthio group, ethylthio group, Examples thereof include alkylthio groups such as propylthio group, isopropylthio group and butylthio group, but are not limited to these as long as the molar polarizability per molar volume satisfies the condition of 0.4 or less. .

Examples of the reactive R ² characteristic group include alkenyl groups such as ethenyl group, methylethenyl group, ethylethenyl group, propylethenyl group, isopropylethenyl group, butylethenyl group, 1-propenyl group and allyl group, and Examples thereof include alkoxyethenyl groups such as methoxyethenyl group, ethoxyethenyl group, propoxyethenyl group, isopropoxyethenyl group and butoxyethenyl group, provided that the molar polarizability per molar volume is 0.4 or less. However, the present invention is not limited to these as long as the above is satisfied. Preferred as the reactive R ² characteristic group are ethenyl group, methylethenyl group and ethylethenyl group because of good reactivity.

Specific examples of the R-2 group in which R ² is hydrogen include a phenylphenoxy group, a phenoxyphenoxy group, and a benzylphenoxy group.

Specific examples of the R-2 group in which R ² is a non-reactive characteristic group include 4-methylphenylphenoxy group, 3-methylphenylphenoxy group, 2-methylphenylphenoxy group, 4-ethylphenylphenoxy group, 3 -Ethylphenylphenoxy group, 2-ethylphenylphenoxy group, 4- (n-propyl) phenylphenoxy group, 3- (n-propyl) phenylphenoxy group, 2- (n-propyl) phenylphenoxy group, 4-isopropylphenyl Phenoxy group, 3-isopropylphenylphenoxy group, 2-isopropylphenylphenoxy group, 4- (n-butyl) phenylphenoxy group, 3- (n-butyl) phenylphenoxy group, 2- (n-butyl) phenylphenoxy group, 4-fluorophenylphenoxy group, 3-fluorophenylpheno group Xyl group, 2-fluorophenylphenoxy group, 4- (monofluoromethyl) phenylphenoxy group, 3- (monofluoromethyl) phenylphenoxy group, 2- (monofluoromethyl) phenylphenoxy group, 4- (difluoromethyl) phenyl Phenoxy group, 3- (difluoromethyl) phenylphenoxy group, 2- (difluoromethyl) phenylphenoxy group, 4- (trifluoromethyl) phenylphenoxy group, 3- (trifluoromethyl) phenylphenoxy group, 2- (trifluoro Methyl) phenylphenoxy group, 4- (pentafluoroethyl) phenylphenoxy group, 3- (pentafluoroethyl) phenylphenoxy group, 2- (pentafluoroethyl) phenylphenoxy group, 4- (heptafluoropropyl) phenylphenoxy 3- (heptafluoropropyl) phenylphenoxy group, 2- (heptafluoropropyl) phenylphenoxy group, 4-methoxyphenylphenoxy group, 3-methoxyphenylphenoxy group, 2-methoxyphenylphenoxy group, 4-ethoxyphenylphenoxy group 3-ethoxyphenylphenoxy group, 2-ethoxyphenylphenoxy group, 4- (n-propoxy) phenylphenoxy group, 3- (n-propoxy) phenylphenoxy group, 2- (n-propoxy) phenylphenoxy group, 4- (Isopropoxy) phenylphenoxy group, 3- (isopropoxy) phenylphenoxy group, 2- (isopropoxy) phenylphenoxy group, 4- (n-butoxy) phenylphenoxy group, 3- (n-butoxy) phenylphenoxy group, 2- ( -Butoxy) phenylphenoxy group, 4-methylthiophenylphenoxy group, 3-methylthiophenylphenoxy group, 2-methylthiophenylphenoxy group, 4-ethylthiophenylphenoxy group, 3-ethylthiophenylphenoxy group, 2-ethylthiophenylphenoxy group Group, 4- (n-propylthio) phenylphenoxy group, 3- (n-propylthio) phenylphenoxy group, 2- (n-propylthio) phenylphenoxy group, 4- (isopropylthio) phenylphenoxy group, 3- (isopropylthio) ) Phenylphenoxy group, 2- (isopropylthio) phenylphenoxy group, 4- (n-butylthio) phenylphenoxy group, 3- (n-butylthio) phenylphenoxy group, 2- (n-butylthio) phenylphenoxy group, 4- Mechi Ruphenoxyphenoxy group, 3-methylphenoxyphenoxy group, 2-methylphenoxyphenoxy group, 4-ethylphenoxyphenoxy group, 3-ethylphenoxyphenoxy group, 2-ethylphenoxyphenoxy group, 4- (n-propyl) phenoxyphenoxy group 3- (n-propyl) phenoxyphenoxy group, 2- (n-propyl) phenoxyphenoxy group, 4-isopropylphenoxyphenoxy group, 3-isopropylphenoxyphenoxy group, 2-isopropylphenoxyphenoxy group, 4- (n-butyl) ) Phenoxyphenoxy group, 3- (n-butyl) phenoxyphenoxy group, 2- (n-butyl) phenoxyphenoxy group, 4-fluorophenoxyphenoxy group, 3-fluorophenoxyphenoxy group, 2-fluorophenoxy group Phenoxy group, 4- (monofluoromethyl) phenoxyphenoxy group, 3- (monofluoromethyl) phenoxyphenoxy group, 2- (monofluoromethyl) phenoxyphenoxy group, 4- (difluoromethyl) phenoxyphenoxy group, 3- (difluoro Methyl) phenoxyphenoxy group, 2- (difluoromethyl) phenoxyphenoxy group, 4- (trifluoromethyl) phenoxyphenoxy group, 3- (trifluoromethyl) phenoxyphenoxy group, 2- (trifluoromethyl) phenoxyphenoxy group, 4 -(Pentafluoroethyl) phenoxyphenoxy group, 3- (pentafluoroethyl) phenoxyphenoxy group, 2- (pentafluoroethyl) phenoxyphenoxy group, 4- (heptafluoropropyl) phenoxyphenoxy group 3- (heptafluoropropyl) phenoxyphenoxy group, 2- (heptafluoropropyl) phenoxyphenoxy group, 4-methoxyphenoxyphenoxy group, 3-methoxyphenoxyphenoxy group, 2-methoxyphenoxyphenoxy group, 4-ethoxyphenoxyphenoxy group 3-ethoxyphenoxyphenoxy group, 2-ethoxyphenoxyphenoxy group, 4- (n-propoxy) phenoxyphenoxy group, 3- (n-propoxy) phenoxyphenoxy group, 2- (n-propoxy) phenoxyphenoxy group, 4- (Isopropoxy) phenoxyphenoxy group, 3- (isopropoxy) phenoxyphenoxy group, 2- (isopropoxy) phenoxyphenoxy group, 4- (n-butoxy) phenoxyphenoxy group, 3- (n-butoxy) Phenoxyphenoxy group, 2- (n-butoxy) phenoxyphenoxy group, 4-methylthiophenoxyphenoxy group, 3-methylthiophenoxyphenoxy group, 2-methylthiophenoxyphenoxy group, 4-ethylthiophenoxyphenoxy group, 3-ethylthiophenoxyphenoxy group Group, 2-ethylthiophenoxyphenoxy group, 4- (n-propylthio) phenoxyphenoxy group, 3- (n-propylthio) phenoxyphenoxy group, 2- (n-propylthio) phenoxyphenoxy group, 4- (isopropylthio) phenoxy Phenoxy group, 3- (isopropylthio) phenoxyphenoxy group, 2- (isopropylthio) phenoxyphenoxy group, 4- (n-butylthio) phenoxyphenoxy group, 3- (n-butylthio) phenoxyphe Xyl group, 2- (n-butylthio) phenoxyphenoxy group, 4-methylbenzylphenoxy group, 3-methylbenzylphenoxy group, 2-methylbenzylphenoxy group, 4-ethylbenzylphenoxy group, 3-ethylbenzylphenoxy group, 2 -Ethylbenzylphenoxy group, 4- (n-propyl) benzylphenoxy group, 3- (n-propyl) benzylphenoxy group, 2- (n-propyl) benzylphenoxy group, 4-isopropylbenzylphenoxy group, 3-isopropylbenzyl Phenoxy group, 2-isopropylbenzylphenoxy group, 4- (n-butyl) benzylphenoxy group, 3- (n-butyl) benzylphenoxy group, 2- (n-butyl) benzylphenoxy group, 4-fluorobenzylphenoxy group, 3-Fluorobenzyl Fe Xyl group, 2-fluorobenzylphenoxy group, 4- (monofluoromethyl) benzylphenoxy group, 3- (monofluoromethyl) benzylphenoxy group, 2- (monofluoromethyl) benzylphenoxy group, 4- (difluoromethyl) benzyl Phenoxy group, 3- (difluoromethyl) benzylphenoxy group, 2- (difluoromethyl) benzylphenoxy group, 4- (trifluoromethyl) benzylphenoxy group, 3- (trifluoromethyl) benzylphenoxy group, 2- (trifluoro Methyl) benzylphenoxy group, 4- (pentafluoroethyl) benzylphenoxy group, 3- (pentafluoroethyl) benzylphenoxy group, 2- (pentafluoroethyl) benzylphenoxy group, 4- (heptafluoropropyl) benzylphenoxy group Group, 3- (heptafluoropropyl) benzylphenoxy group, 2- (heptafluoropropyl) benzylphenoxy group, 4-methoxybenzylphenoxy group, 3-methoxybenzylphenoxy group, 2-methoxybenzylphenoxy group, 4-ethoxybenzylphenoxy group Group, 3-ethoxybenzylphenoxy group, 2-ethoxybenzylphenoxy group, 4- (n-propoxy) benzylphenoxy group, 3- (n-propoxy) benzylphenoxy group, 2- (n-propoxy) benzylphenoxy group, 4 -(Isopropoxy) benzylphenoxy group, 3- (isopropoxy) benzylphenoxy group, 2- (isopropoxy) benzylphenoxy group, 4- (n-butoxy) benzylphenoxy group, 3- (n-butoxy) benzylphenoxy group , 2- ( -Butoxy) benzylphenoxy group, 4-methylthiobenzylphenoxy group, 3-methylthiobenzylphenoxy group, 2-methylthiobenzylphenoxy group, 4-ethylthiobenzylphenoxy group, 3-ethylthiobenzylphenoxy group, 2-ethylthiobenzylphenoxy group Group, 4- (n-propylthio) benzylphenoxy group, 3- (n-propylthio) benzylphenoxy group, 2- (n-propylthio) benzylphenoxy group, 4- (isopropylthio) benzylphenoxy group, 3- (isopropylthio) ) Benzylphenoxy group, 2- (isopropylthio) benzylphenoxy group, 4- (n-butylthio) benzylphenoxy group, 3- (n-butylthio) benzylphenoxy group and 2- (n-butylthio) benzylphenoxy group. Rukoto can.

Specific examples of the R-2 group in which R ² is a reactive characteristic group include 4-ethenylphenoxy group, 3-ethenylphenoxy group, 2-ethenylphenoxy group, 4- (methylethenyl) phenoxy group, 3 -(Methylethenyl) phenoxy group, 2- (methylethenyl) phenoxy group, 4- (ethylethenyl) phenoxy group, 3- (ethylethenyl) phenoxy group, 2- (ethylethenyl) phenoxy group, 4- (n-propylethenyl) phenoxy group 3- (n-propylethenyl) phenoxy group, 2- (n-propylethenyl) phenoxy group, 4- (isopropylethenyl) phenoxy group, 3- (isopropylethenyl) phenoxy group, 2- (isopropylethene) Tenenyl) phenoxy, 4- (n-butylethenyl) phenoxy, 3- (n-butylethenyl) Enoxy group, 2- (n-butylethenyl) phenoxy group, 4- (methoxyethenyl) phenoxy group, 3- (methoxyethenyl) phenoxy group, 2- (methoxyethenyl) phenoxy group, 4- (ethoxyethenyl) Phenoxy group, 3- (ethoxyethenyl) phenoxy group, 2- (ethoxyethenyl) phenoxy group, 4- (n-propoxyethenyl) phenoxy group, 3- (n-propoxyethenyl) phenoxy group, 2- ( n-propoxyethenyl) phenoxy group, 4- (isopropoxyethenyl) phenoxy group, 3- (isopropoxyethenyl) phenoxy group, 2- (isopropoxyethenyl) phenoxy group, 4- (n-butoxyethenyl) phenoxy group Group, 3- (n-butoxyethenyl) phenoxy group, 2- (n-butoxyethenyl) phenoxy group 4- (1-propenyl) phenoxy group, 3- (1-propenyl) phenoxy group, 2- (1-propenyl) phenoxy group, 4-ethenylphenylphenoxy group, 3-ethenylphenyl Phenoxy group, 2-ethenylphenylphenoxy group, 4- (methylethenyl) phenylphenoxy group, 3- (methylethenyl) phenylphenoxy group, 2- (methylethenyl) phenylphenoxy group, 4- (ethylethenyl) phenylphenoxy group, 3- ( Ethylethenyl) phenylphenoxy group, 2- (ethylethenyl) phenylphenoxy group, 4- (n-propylethenyl) phenylphenoxy group, 3- (n-propylethenyl) phenylphenoxy group, 2- (n-propylethenyl) Phenylphenoxy group, 4- (isopropylethenyl) phenyl Nonoxy group, 3- (isopropylethenyl) phenylphenoxy group, 2- (isopropylethenyl) phenylphenoxy group, 4- (n-butylethenyl) phenylphenoxy group, 3- (n-butylethenyl) phenylphenoxy group, 2- ( n-butylethenyl) phenylphenoxy group, 4- (methoxyethenyl) phenylphenoxy group, 3- (methoxyethenyl) phenylphenoxy group, 2- (methoxyethenyl) phenylphenoxy group, 4- (ethoxyethenyl) phenylphenoxy group Group, 3- (ethoxyethenyl) phenylphenoxy group, 2- (ethoxyethenyl) phenylphenoxy group, 4- (n-propoxyethenyl) phenylphenoxy group, 3- (n-propoxyethenyl) phenylphenoxy group, 2- (n-propoxyethenyl) fur Enylphenoxy group, 4- (isopropoxyethenyl) phenylphenoxy group, 3- (isopropoxyethenyl) phenylphenoxy group, 2- (isopropoxyethenyl) phenylphenoxy group, 4- (n-butoxyethenyl) phenylphenoxy group , 3- (n-butoxyethenyl) phenylphenoxy group, 2- (n-butoxyethenyl) phenylphenoxy group, 4- (1-propenyl) phenylphenoxy group, 3- (1-propenyl) phenylphenoxy group, 2- (1- Propenyl) phenylphenoxy group, 4-ethenylphenoxyphenoxy group, 3-ethenylphenoxyphenoxy group, 2-ethenylphenoxyphenoxy group, 4- (methylethenyl) phenoxyphenoxy group, 3- (methylethenyl) phenoxyphenoxy group, 2- (Me Ruethenyl) phenoxyphenoxy group, 4- (ethylethenyl) phenoxyphenoxy group, 3- (ethylethenyl) phenoxyphenoxy group, 2- (ethylethenyl) phenoxyphenoxy group, 4- (n-propylethenyl) phenoxyphenoxy group, 3- (n -Propylethenyl) phenoxyphenoxy group, 2- (n-propylethenyl) phenoxyphenoxy group, 4- (isopropylethenyl) phenoxyphenoxy group, 3- (isopropylethenyl) phenoxyphenoxy group, 2- (isopropylethenyl) ) Phenoxyphenoxy group, 4- (n-butylethenyl) phenoxyphenoxy group, 3- (n-butylethenyl) phenoxyphenoxy group, 2- (n-butylethenyl) phenoxyphenoxy group, 4- (methoxyethenyl) phene Xyphenoxy group, 3- (methoxyethenyl) phenoxyphenoxy group, 2- (methoxyethenyl) phenoxyphenoxy group, 4- (ethoxyethenyl) phenoxyphenoxy group, 3- (ethoxyethenyl) phenoxyphenoxy group, 2- (Ethoxyethenyl) phenoxyphenoxy group, 4- (n-propoxyethenyl) phenoxyphenoxy group, 3- (n-propoxyethenyl) phenoxyphenoxy group, 2- (n-propoxyethenyl) phenoxyphenoxy group, 4- (Isopropoxyethenyl) phenoxyphenoxy group, 3- (isopropoxyethenyl) phenoxyphenoxy group, 2- (isopropoxyethenyl) phenoxyphenoxy group, 4- (n-butoxyethenyl) phenoxyphenoxy group, 3- (n- Butoxyethenyl) fe Noxyphenoxy group, 2- (n-butoxyethenyl) phenoxyphenoxy group, 4- (1-propenyl) phenoxyphenoxy group, 3- (1-propenyl) phenoxyphenoxy group, 2- (1-propenyl) phenoxyphenoxy group, 4 -Ethenylbenzylphenoxy group, 3-ethenylbenzylphenoxy group, 2-ethenylbenzylphenoxy group, 4- (methylethenyl) benzylphenoxy group, 3- (methylethenyl) benzylphenoxy group, 2- (methylethenyl) benzylphenoxy group, 4- (ethylethenyl) benzylphenoxy group, 3- (ethylethenyl) benzylphenoxy group, 2- (ethylethenyl) benzylphenoxy group, 4- (n-propylethenyl) benzylphenoxy group, 3- (n-propylethenyl) benzylphenoxy group Xyl group, 2- (n-propylethenyl) benzylphenoxy group, 4- (isopropylethenyl) benzylphenoxy group, 3- (isopropylethenyl) benzylphenoxy group, 2- (isopropylethenyl) benzylphenoxy group, 4 -(N-butylethenyl) benzylphenoxy group, 3- (n-butylethenyl) benzylphenoxy group, 2- (n-butylethenyl) benzylphenoxy group, 4- (methoxyethenyl) benzylphenoxy group, 3- (methoxyethenyl) Benzylphenoxy group, 2- (methoxyethenyl) benzylphenoxy group, 4- (ethoxyethenyl) benzylphenoxy group, 3- (ethoxyethenyl) benzylphenoxy group, 2- (ethoxyethenyl) benzylphenoxy group, 4- (N-propoxyethenyl) benzi Phenoxy group, 3- (n-propoxyethenyl) benzylphenoxy group, 2- (n-propoxyethenyl) benzylphenoxy group, 4- (isopropoxyethenyl) benzylphenoxy group, 3- (isopropoxyethenyl) benzyl Phenoxy group, 2- (isopropoxyethenyl) benzylphenoxy group, 4- (n-butoxyethenyl) benzylphenoxy group, 3- (n-butoxyethenyl) benzylphenoxy group, 2- (n-butoxyethenyl) benzylphenoxy group, 4- Mention may be made of (1-propenyl) benzylphenoxy, 3- (1-propenyl) benzylphenoxy and 2- (1-propenyl) benzylphenoxy.

Preferred as the R-2 group are groups in which R ² is hydrogen, particularly phenylphenoxy group, phenoxyphenoxy group and benzylphenoxy group, R ² is methyl group, ethyl group, fluoro group, monofluoromethyl group, Groups that are non-reactive characteristic groups selected from the group consisting of a fluoromethyl group, a methoxy group, and an ethoxy group, in particular, a 4-methylphenylphenoxy group, a 3-methylphenylphenoxy group, and a 2-methylphenylphenoxy group 4-ethylphenylphenoxy group, 3-ethylphenylphenoxy group, 2-ethylphenylphenoxy group, 4-fluorophenylphenoxy group, 3-fluorophenylphenoxy group, 2-fluorophenylphenoxy group, 4- (monofluoromethyl) Phenylphenoxy group, 3- (monofluoromethyl L) phenylphenoxy group, 2- (monofluoromethyl) phenylphenoxy group, 4- (trifluoromethyl) phenylphenoxy group, 3- (trifluoromethyl) phenylphenoxy group, 2- (trifluoromethyl) phenylphenoxy group, 4-methoxyphenylphenoxy group, 3-methoxyphenylphenoxy group, 2-methoxyphenylphenoxy group, 4-ethoxyphenylphenoxy group, 3-ethoxyphenylphenoxy group, 2-ethoxyphenylphenoxy group, 4-methylphenoxyphenoxy group, 3 -Methylphenoxyphenoxy group, 2-methylphenoxyphenoxy group, 4-ethylphenoxyphenoxy group, 3-ethylphenoxyphenoxy group, 2-ethylphenoxyphenoxy group, 4-fluorophenoxyphenoxy group, 3- Fluorophenoxyphenoxy group, 2-fluorophenoxyphenoxy group, 4- (monofluoromethyl) phenoxyphenoxy group, 3- (monofluoromethyl) phenoxyphenoxy group, 2- (monofluoromethyl) phenoxyphenoxy group, 4- (trifluoro Methyl) phenoxyphenoxy group, 3- (trifluoromethyl) phenoxyphenoxy group, 2- (trifluoromethyl) phenoxyphenoxy group, 4-methoxyphenoxyphenoxy group, 3-methoxyphenoxyphenoxy group, 2-methoxyphenoxyphenoxy group, 4 -Ethoxyphenoxyphenoxy group, 3-ethoxyphenoxyphenoxy group, 2-ethoxyphenoxyphenoxy group, 4-methylbenzylphenoxy group, 3-methylbenzylphenoxy group, 2-methylbenzyl Enoxy group, 4-ethylbenzylphenoxy group, 3-ethylbenzylphenoxy group, 2-ethylbenzylphenoxy group, 4-fluorobenzylphenoxy group, 3-fluorobenzylphenoxy group, 2-fluorobenzylphenoxy group, 4- (monofluoro Methyl) benzylphenoxy group, 3- (monofluoromethyl) benzylphenoxy group, 2- (monofluoromethyl) benzylphenoxy group, 4- (trifluoromethyl) benzylphenoxy group, 3- (trifluoromethyl) benzylphenoxy group, 2- (trifluoromethyl) benzylphenoxy group, 4-methoxybenzylphenoxy group, 3-methoxybenzylphenoxy group, 2-methoxybenzylphenoxy group, 4-ethoxybenzylphenoxy group, 3-ethoxybenzylphenoxy group And 2-ethoxybenzylphenoxy group, especially 4-fluorophenylphenoxy group, 3-fluorophenylphenoxy group, 2-fluorophenylphenoxy group, 4-methoxyphenylphenoxy group, 3-methoxyphenylphenoxy group, 2-methoxyphenyl Phenoxy group, 4-fluorophenoxyphenoxy group, 3-fluorophenoxyphenoxy group, 2-fluorophenoxyphenoxy group, 4-methoxyphenoxyphenoxy group, 3-methoxyphenoxyphenoxy group, 2-methoxyphenoxyphenoxy group, 4-fluorobenzylphenoxy group Group, 3-fluorobenzylphenoxy group, 2-fluorobenzylphenoxy group, 4-methoxybenzylphenoxy group, 3-methoxybenzylphenoxy group and 2-methoxybenzylpheno group A group in which R ² is a reactive characteristic group selected from the group consisting of an ethenyl group, a methylethenyl group, a methoxyethenyl group and an ethoxyethenyl group, in particular, a 4-ethenylphenoxy group, a 3- Ethenylphenoxy group, 2-ethenylphenoxy group, 4- (methylethenyl) phenoxy group, 3- (methylethenyl) phenoxy group, 2- (methylethenyl) phenoxy group, 4- (methoxyethenyl) phenoxy group, 3- (methoxy Ethenyl) phenoxy group, 2- (methoxyethenyl) phenoxy group, 4- (ethoxyethenyl) phenoxy group, 3- (ethoxyethenyl) phenoxy group, 2- (ethoxyethenyl) phenoxy group, 4-ethenyl Phenylphenoxy group, 3-ethenylphenylphenoxy group, 2-ethenylphenylphenoxy group, 4- ( Methylethenyl) phenylphenoxy group, 3- (methylethenyl) phenylphenoxy group, 2- (methylethenyl) phenylphenoxy group, 4- (methoxyethenyl) phenylphenoxy group, 3- (methoxyethenyl) phenylphenoxy group, 2- (methoxy) Ethenyl) phenylphenoxy group, 4- (ethoxyethenyl) phenylphenoxy group, 3- (ethoxyethenyl) phenylphenoxy group, 2- (ethoxyethenyl) phenylphenoxy group, 4-ethenylphenoxyphenoxy group, 3- Ethenylphenoxyphenoxy group, 2-ethenylphenoxyphenoxy group, 4- (methylethenyl) phenoxyphenoxy group, 3- (methylethenyl) phenoxyphenoxy group, 2- (methylethenyl) phenoxyphenoxy group, 4- (methoxyethene) L) Phenoxyphenoxy group, 3- (methoxyethenyl) phenoxyphenoxy group, 2- (methoxyethenyl) phenoxyphenoxy group, 4- (ethoxyethenyl) phenoxyphenoxy group, 3- (ethoxyethenyl) phenoxyphenoxy group, 2- (ethoxyethenyl) phenoxyphenoxy group, 4-ethenylbenzylphenoxy group, 3-ethenylbenzylphenoxy group, 2-ethenylbenzylphenoxy group, 4- (methylethenyl) benzylphenoxy group, 3 -(Methylethenyl) benzylphenoxy group, 2- (methylethenyl) benzylphenoxy group, 4- (methoxyethenyl) benzylphenoxy group, 3- (methoxyethenyl) benzylphenoxy group, 2- ( Methoxyethenyl) benzylphenoxy group, 4- (ethoxyethenyl) Benzylphenoxy group, 3- (ethoxyethenyl) benzylphenoxy group and 2- (ethoxyethenyl) benzylphenoxy group, especially 4-ethenylphenoxy group, 3-ethenylphenoxy group, 2-ethenylphenoxy group 4-ethenylphenylphenoxy group, 3-ethenylphenylphenoxy group, 2-ethenylphenylphenoxy group, 4-ethenylphenoxyphenoxy group, 3-ethenylphenoxyphenoxy group, 2-ethenylphenoxyphenoxy group, 4 -Ethenylbenzylphenoxy group, 3-ethenylbenzylphenoxy group, 2-ethenylbenzylphenoxy group, 4- (methylethenyl) phenoxy group, 3- (methylethenyl) phenoxy group, 2- (methylethenyl) phenoxy group, 4- ( Methylethenyl) phenylphenoxy group, 3 -(Methylethenyl) phenylphenoxy group, 2- (methylethenyl) phenylphenoxy group, 4- (methylethenyl) phenoxyphenoxy group, 3- (methylethenyl) phenoxyphenoxy group, 2- (methylethenyl) phenoxyphenoxy group, 4- (methylethenyl) benzyl Mention may be made of phenoxy, 3- (methylethenyl) benzylphenoxy and 2- (methylethenyl) benzylphenoxy.

  In the formula (1), 2n of R are contained, at least one of which is an R-2 group. In view of the R-2 group, the aryloxy cyclic phosphazene compound represented by the formula (1) can be classified into the following forms.

[Form 1]
All 2n R's are R-2 groups. In this case, all R may be the same R-2 group, or two or more R-2 groups. Preferred in this form are aryloxycyclotriphosphazene compounds in which n in formula (1) is 3, aryloxycyclotetraphosphazene compounds in which n in formula (1) is 4, n in formula (1) is An aryloxycyclopentaphosphazene compound of 5 or an aryloxycyclohexaphosphazene compound of formula (1) in which n is 6, or any mixture thereof.

The R-2 group in the cyclic phosphazene compound of this form is preferably a phenylphenoxy group, a phenoxyphenoxy group or a benzylphenoxy group as R ² is a hydrogen atom, and has a non-reactive R ² characteristic group as 4- Fluorophenylphenoxy group, 3-fluorophenylphenoxy group, 2-fluorophenylphenoxy group, 4-methoxyphenylphenoxy group, 3-methoxyphenylphenoxy group, 2-methoxyphenylphenoxy group, 4-fluorophenoxyphenoxy group, 3-fluoro Phenoxyphenoxy group, 2-fluorophenoxyphenoxy group, 4-methoxyphenoxyphenoxy group, 3-methoxyphenoxyphenoxy group, 2-methoxyphenoxyphenoxy group, 4-fluorobenzylphenoxy group, 3-full B benzyl phenoxy group, 2-fluorobenzyl phenoxy group, 4-methoxybenzyl phenoxy group, 3-methoxybenzyl phenoxy group or a 2-methoxybenzyl phenoxy groups are preferred, 4-ethenyl as having a reaction type R ² characteristic groups Phenoxy group, 3-ethenylphenoxy group, 2-ethenylphenoxy group, 4-ethenylphenylphenoxy group, 3-ethenylphenylphenoxy group, 2-ethenylphenylphenoxy group, 4-ethenylphenoxyphenoxy group, 3 -Ethenylphenoxyphenoxy group, 2-ethenylphenoxyphenoxy group, 4-ethenylbenzylphenoxy group, 3-ethenylbenzylphenoxy group, 2-ethenylbenzylphenoxy group, 4- (methylethenyl) phenoxy group, 3- ( Methylethenyl) pheno Si group, 2- (methylethenyl) phenoxy group, 4- (methylethenyl) phenylphenoxy group, 3- (methylethenyl) phenylphenoxy group, 2- (methylethenyl) phenylphenoxy group, 4- (methylethenyl) phenoxyphenoxy group, 3- ( A methylethenyl) phenoxyphenoxy group, 2- (methylethenyl) phenoxyphenoxy group, 4- (methylethenyl) benzylphenoxy group, 3- (methylethenyl) benzylphenoxy group or 2- (methylethenyl) benzylphenoxy group is preferred. The aryloxy cyclic phosphazene compound of this embodiment having such a preferred R-2 group is a resin that is more excellent in thermal stability and dielectric properties than the aryloxy cyclic phosphazene compound of this embodiment having another R-2 group. This is advantageous in that a molded body can be realized.

[Form 2]
A part (that is, at least one) of 2n Rs is an R-2 group, and the other Rs are R-1 groups. Here, when there are two or more R-2 groups, all the R-2 groups may be the same R-2 group, or two or more R-2 groups may be mixed. Good. Moreover, when there are two or more R-1 groups, all of the R-1 groups may be the same R-1 group, or two or more R-1 groups may be mixed. .

  Preferred in this form is aryloxycyclotriphosphazene wherein n in formula (1) is 3 wherein 1 to (2n-1) of 2n R are R-2 groups Compound, aryloxycyclotetraphosphazene compound in which n in formula (1) is 4, aryloxycyclopentaphosphazene compound in which n is 5 in formula (1), or aryloxycyclohexahexane in which n in formula (1) is 6 A phosphazene compound or any mixture thereof.

  In addition, it is confirmed by TOF-MS analysis of an aryloxy cyclic phosphazene compound or an intermediate in its production process whether 1 to (2n-1) of 2n R are R-2 groups or not. I can do it.

  Specific examples of the aryloxy cyclic phosphazene compound of this form include an aryloxycyclotriphosphazene compound in which n is 3 in the formula (1), an aryloxycyclotetraphosphazene compound in which n in the formula (1) is 4, An aryloxycyclopentaphosphazene compound in which n of 1) is 5 or an aryloxycyclohexaphosphazene compound in which n of formula (1) is 6, and the following can be mentioned.

R is a combination of a phenoxy group that is an R-1 group and a phenylphenoxy group that is an R-2 group, and a phenoxy group that is an R-1 group and a 3-fluorophenylphenoxy group that is an R-2 group. A combination of R-1 group phenoxy group and R-2 group 4-methoxyphenylphenoxy group, R-1 group phenoxy group and R-2 group 2-methoxy A combination of phenylphenoxy group, a combination of R-1 group phenoxy group and R-2 group 4-fluoro-2methylphenylphenoxy group, R-1 group phenoxy group and R- A combination of two phenoxyphenoxy groups, a combination of R-1 phenoxy and R-2 4-fluorophenoxyphenoxy. A combination of a phenoxy group that is an R-1 group and a 3-methoxyphenoxyphenoxy group that is an R-2 group, a phenoxy group that is an R-1 group, and a 2-methoxyphenoxyphenoxy group that is an R-2 group; A combination of R-1 group phenoxy group and R-2 group 3-ethyl-5-fluorophenylphenoxy group, R-1 group phenoxy group and benzylphenoxy group Combination, R-1 group phenoxy group and R-2 group 3-fluorobenzylphenoxy group combination, R-1 group phenoxy group and R-2 group 4-methoxy Combination of benzylphenoxy group and combination of R-1 group phenoxy group and R-2 group 2-methoxybenzylphenoxy group Those of the combination of 4-ethyl-2-fluorobenzyl phenoxy group is phenoxy group and R-2 group is R-1 group.

R is a combination of a methylphenoxy group which is an R-1 group and a phenylphenoxy group which is an R-2 group, a 4-fluorophenylphenoxy group which is a methylphenoxy group which is an R-1 group and an R-2 group A combination of a methylphenoxy group which is an R-1 group and a 3-methoxyphenylphenoxy group which is an R-2 group, a methylphenoxy group which is an R-1 group and an R-2 group A combination of 2-methoxyphenylphenoxy group, a combination of methylphenoxy group as R-1 group and 3-methyl-4-methoxyphenylphenoxy group as R-2 group, R-1 group Combination of methylphenoxy group and R-2 group phenoxyphenoxy group, R-1 group methylphenoxy group and R-2 group 3-fluoro Combination of phenoxyphenoxy group, combination of R-1 group methylphenoxy group and R-2 group 4-methoxyphenoxyphenoxy group, R-1 group methylphenoxy group and R-2 In combination with 2-methoxyphenoxyphenoxy group which is a group, in combination with methylphenoxy group which is R-1 group and 2-ethyl-5-methoxyphenoxyphenoxy group which is R-2 group, R-1 A combination of a methylphenoxy group as a group and a benzylphenoxy group as an R-2 group, a combination of a methylphenoxy group as an R-1 group and a 4-fluorobenzylphenoxy group as an R-2 group, A combination of a methylphenoxy group which is an R-1 group and a 3-methoxybenzylphenoxy group which is an R-2 group, R A combination of a methylphenoxy group that is one group and a 2-methoxybenzylphenoxy group that is an R-2 group, a methylphenoxy group that is an R-1 group, and a 2-fluoro-3-methylbenzyl that is an R-2 group Combination with phenoxy group.

R is a combination of a dimethylphenoxy group which is an R-1 group and a phenylphenoxy group which is an R-2 group, a dimethylphenoxy group which is an R-1 group and a 3-fluorophenylphenoxy group which is an R-2 group A combination of dimethylphenoxy group which is R-1 group and 4-methoxyphenylphenoxy group which is R-2 group, dimethylphenoxy group and R-2 group which are R-1 groups A combination of 2-methoxyphenylphenoxy group, a combination of R-1 group dimethylphenoxy group and R-2 group 3-ethyl-4-fluorophenylphenoxy group, R-1 group Combination of dimethylphenoxy group and R-2 group phenoxyphenoxy group, R-1 group dimethylphenoxy group and R-2 group In combination with 4-fluorophenoxyphenoxy group, in combination with dimethylphenoxy group as R-1 group and 3-methoxyphenoxyphenoxy group as R-2 group, dimethylphenoxy group as R-1 group In combination with 2-methoxyphenoxyphenoxy group as R-2 group, in combination with dimethylphenoxy group as R-1 group and 2-methyl-5-fluorophenoxyphenoxy group as R-2 group A combination of a dimethylphenoxy group that is an R-1 group and a benzylphenoxy group that is an R-2 group, a dimethylphenoxy group that is an R-1 group, and a 3-fluorobenzylphenoxy group that is an R-2 group Combination, dimethylphenoxy group which is R-1 group and 4-methoxybenzylphenoxy which is R-2 group A combination of dimethylphenoxy group which is R-1 group and 2-methoxybenzylphenoxy group which is R-2 group, dimethylphenoxy group and R-2 group which are R-1 groups Combination with 2-fluoro-4-methylbenzylphenoxy group.

R is a combination of a naphthyloxy group which is an R-1 group and a phenylphenoxy group which is an R-2 group, a 4-naphthyloxy group which is an R-1 group and a 4-fluorophenylphenoxy group which is an R-2 group A combination of a naphthyloxy group that is an R-1 group and a 3-methoxyphenylphenoxy group that is an R-2 group, a naphthyloxy group that is an R-1 group, and an R-2 group. In combination with 2-methoxyphenylphenoxy group, in combination with naphthyloxy group as R-1 group and 2-ethyl-4-methoxymethoxyphenylphenoxy group as R-2 group, in R-1 group A combination of a certain naphthyloxy group and an R-2 group phenoxyphenoxy group, an R-1 group naphthyloxy group and an R-2 group 3-fluorophene A combination with a xyphenoxy group, a combination of a naphthyloxy group which is an R-1 group and a 4-methoxyphenoxyphenoxy group which is an R-2 group, a naphthyloxy group which is an R-1 group and an R-2 group A combination with a 2-methoxyphenoxyphenoxy group which is a group, a combination of a naphthyloxy group which is an R-1 group and a 5-methyl-3-methoxyphenoxyphenoxy group which is an R-2 group, R-1 A combination of a naphthyloxy group as a group and a benzylphenoxy group as an R-2 group, a combination of a naphthyloxy group as an R-1 group and a 4-fluorobenzylphenoxy group as an R-2 group, Combination of naphthyloxy group as R-1 group and 3-methoxybenzylphenoxy group as R-2 group, naphthy as R-1 group Those of the combination of 2-methoxybenzyl phenoxy an oxy group and R-2 group.

R is a combination of a phenoxy group that is an R-1 group and a 4-ethenylphenoxy group that is an R-2 group, a 3-phenenylphenoxy that is a phenoxy group that is an R-1 group and an R-2 group A combination of a phenoxy group as an R-1 group and a 2-ethenylphenoxy group as an R-2 group, a phenoxy group as an R-1 group, and an R-2 group. -In combination with methyl-4-ethenylphenoxy group, in combination with phenoxy group as R-1 group and 6-methyl-2-ethenylphenoxy group as R-2 group, R-1 group A combination of a phenoxy group that is R-2 and a 4-ethenylphenylphenoxy group that is an R-2 group, a combination of a phenoxy group that is an R-1 group and a 3-ethenylphenoxyphenoxy group that is an R-2 group Things, R A combination of a phenoxy group as one group and a 2-ethenylbenzyl phenoxy group as a R-2 group, a phenoxy group as a R-1 group and a 4- (methylethenyl) phenoxy group as a R-2 group; A combination of R-1 group phenoxy group and R-2 group 3- (methylethenyl) phenoxy group, R-1 group phenoxy group and R-2 group 2- Combination of (methylethenyl) phenoxy group, combination of phenoxy group as R-1 group and 1-methyl-4- (methylethenyl) phenoxy group as R-2 group, phenoxy as R-1 group In combination with a 3- (methylethenyl) phenylphenoxy group which is an R-2 group, 4- (methylethenyl) which is a phenoxy group which is an R-1 group and an R-2 group Those combinations of phenoxyphenoxybenzoic group, a phenoxy group and the R-2 group is R-1 group 2 (methylethenyl) that in combination with benzyl phenoxy group.

R is a combination of a methylphenoxy group that is an R-1 group and a 4-ethenylphenoxy group that is an R-2 group, or a 3-phenone that is a methylphenoxy group that is an R-1 group and an R-2 group. A combination of a tenenylphenoxy group, a combination of a methylphenoxy group as an R-1 group and a 2-ethenylphenoxy group as an R-2 group, a methylphenoxy group and an R-2 as an R-1 group A combination of a 3-ethenylphenylphenoxy group that is a group, a combination of a methylphenoxy group that is an R-1 group and a 4-ethenylphenoxyphenoxy group that is an R-2 group, and an R-1 group Combination of methylphenoxy group and R-2 group 2-ethenylbenzyl phenoxy group, R-1 group methylphenoxy group and R-2 group 4- (methylethenyl) A combination with a nonoxy group, a combination of a methylphenoxy group that is an R-1 group and a 3- (methylethenyl) phenoxy group that is an R-2 group, a methylphenoxy group that is an R-1 group and an R-2 group In combination with 2- (methylethenyl) phenoxy group being a group, in combination with methylphenoxy group being R-1 group and 2- (methylethenyl) phenylphenoxy group being R-2 group, R-1 group A combination of a methylphenoxy group which is R and a 3- (methylethenyl) phenoxyphenoxy group which is an R-2 group, a methylphenoxy group which is an R-1 group and a 4- (methylethenyl) benzylphenoxy group which is an R-2 group In combination with R-1 group methylphenoxy group and R-2 group 3-methyl-4- (methylethenyl) pheny Combination of phenoxy group, combination of methylphenoxy group as R-1 group and 4-methyl-3-ethenylphenoxyphenoxy group as R-2 group, methylphenoxy group as R-1 group In combination with 4-methyl-2-ethenylphenoxyphenoxy group which is R-2 group.

R is a combination of a dimethylphenoxy group that is an R-1 group and a 4-ethenylphenoxy group that is an R-2 group, a 3-dimethyl group that is a dimethylphenoxy group that is an R-1 group, and an R-2 group. A combination with a tenenylphenoxy group, a combination of a dimethylphenoxy group which is an R-1 group and a 2-ethenylphenoxy group which is an R-2 group, a dimethylphenoxy group which is an R-1 group and an R-2 group In combination with 4-ethenylphenylphenoxy group which is a group, in combination with dimethylphenoxy group which is R-1 group and 2-ethenylphenoxyphenoxy group which is R-2 group, in R-1 group A combination of a certain dimethylphenoxy group and an R-2 group, 3-ethenylbenzyloxy group, an R-1, dimethylphenoxy group and an R-2 group, 4- (me Ruethenyl) in combination with phenoxy group, R-1 group in combination with dimethylphenoxy group and R-2 group in 3- (methylethenyl) phenoxy group, R-1 group in dimethylphenoxy group and R-1 A combination of 2- (methylethenyl) phenoxy group which is -2 group, a combination of dimethylphenoxy group which is R-1 group and 4- (methylethenyl) phenylphenoxy group which is R-2 group, R- Combination of dimethylphenoxy group as one group and 2- (methylethenyl) phenoxyphenoxy group as R-2 group, dimethylphenoxy group as R-1 group and 3- (methylethenyl) benzyl as R-2 group Combination with phenoxy group.

R is a combination of a naphthyloxy group which is an R-1 group and a 4-ethenylphenoxy group which is an R-2 group, or a 3-naphthyloxy group which is an R-1 group and an R-2 group. A combination with a tenenylphenoxy group, a combination of a naphthyloxy group as an R-1 group and a 2-ethenylphenoxy group as an R-2 group, a naphthyloxy group and an R-2 as an R-1 group In combination with 4-ethenylphenylphenoxy group which is a group, in combination with naphthyloxy group which is R-1 group and 3-ethenylphenoxyphenoxy group which is R-2 group, in R-1 group A combination of a certain naphthyloxy group and an R-2 group 2-ethenylbenzyl phenoxy group, an R-1 group naphthyloxy group and an R-2 group 4- (methylethenyl) phenoxy group; Combination, naphthyloxy group as R-1 group and 3- (methylethenyl) phenoxy group as R-2 group, naphthyloxy group as R-1 group and 2 as R-2 group -In combination with-(methylethenyl) phenoxy group, in combination with naphthyloxy group which is R-1 group and 3- (methylethenyl) phenylphenoxy group which is R-2 group, naphthyloxy which is R-1 group In combination with a 4- (methylethenyl) phenoxyphenoxy group that is an R-2 group and a 2- (methylethenyl) benzylphenoxy group that is an R-2 group with a naphthyloxy group that is an R-1 group A combination.

A mixture of any selected from aryloxy cyclic phosphazene compounds according to the above specific examples.

  The aryloxy cyclic phosphazene compound used in the composition of the present invention satisfies a specific characteristic condition among the structures represented by the formula (1), that is, normal temperature in an inert gas atmosphere in thermogravimetric analysis. When heated from 10 to 600 ° C. at a heating rate of 10 ° C./min, the weight retention at 500 ° C. is 50% or more, the relative dielectric constant at a frequency of 1 GHz at a temperature of 25 ° C. is 2.6 or less, and the dielectric loss is 0. It satisfies the condition of 0.002 or less. The measuring method of each characteristic is as described in the examples described later.

  The acid value of the aryloxy cyclic phosphazene compound used in the composition of the present invention is preferably 0.05 mgKOH / g or less, more preferably 0.03 mgKOH / g or less, and particularly preferably 0.01 mgKOH / g or less. Even if the aryloxy cyclic phosphazene compound represented by the formula (1) satisfies the required characteristic conditions, if the acid value exceeds 0.05 mgKOH / g, the dielectric characteristics, particularly the dielectric loss may be impaired. There is.

  The above acid value of the aryloxy cyclic phosphazene compound is measured according to JIS K0070 “Testing method of acid value, saponification value, esterification, iodine value, hydroxyl value and unsaponified product of chemical products”, for example, A cyclic phosphazene compound containing a unit represented by the following formula (3) is an acid value component to be measured. In Formula (3), R is the same as Formula (1).

  The water content of the aryloxy cyclic phosphazene compound used in the composition of the present invention is preferably 100 mg / kg or less, more preferably 50 mg / kg or less, and particularly preferably 30 mg / kg or less. Even if the aryloxy cyclic phosphazene compound represented by the formula (1) satisfies the required characteristic conditions, if the water content exceeds 100 mg / kg, the dielectric characteristics, particularly the dielectric loss may be impaired. is there.

  The above-mentioned water content of the aryloxy cyclic phosphazene compound is measured by the Karl Fischer method according to JIS K0068 “Method of measuring water content of chemical products”.

  In the composition of the present invention, two or more of the above-mentioned aryloxy cyclic phosphazene compounds may be used in combination.

  The resin component used in the composition of the present invention is not particularly limited as long as it is usually used as a material for producing a resin molded body. For example, polyarylate resin, polyamide resin, polyamideimide resin, polyetherimide Resins, polyethersulfone resins, polyimide resins, polyetheretherketone resins, polyphenylene ether resins, bismaleimide resins, polyphenylsulfone resins, polyphthalamide resins, polyphenylene sulfide resins, cyanate ester resins, bismaleimide-cyanate ester resins Styrene-butadiene resin, styrene-maleic acid resin or modified resins thereof. Two or more of these resin components may be used in combination. Moreover, these resin components can also be used by mixing the following thermoplastic resins or thermosetting resins. At this time, the thermoplastic resin and the thermosetting resin may be used in combination.

  Specific examples of thermoplastic resins that can be mixed are polyethylene resin, polyisoprene resin, polybutadiene resin, chlorinated polyethylene resin, polyvinyl chloride resin, polystyrene resin, high impact polystyrene resin, acrylonitrile-styrene resin (AS resin). , 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 acrylate resin, polymethyl methacrylate resin, polyketone resin, polycarbonate resin, modified polyphenylene ether resin, polyester resin, polysulfone resin, polyester Terunitoriru resins, polythioether sulfone resin and liquid crystal polymer. As the modified polyphenylene ether resin, for example, a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and an anhydrous dicarboxyl group may be added to some or all of the polyphenylene ether by some method such as graft reaction or copolymerization. The introduced one is used. Examples of polyester resins include polyethylene terephthalate (PET) resin, polypropylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin. Two or more thermoplastic resins may be used in combination.

  When the composition of the present invention is used as a molding material used in an electronic device, it is preferable to use a polyester resin, an ABS resin, a polycarbonate resin, a modified polyphenylene ether resin, a polybutadiene resin, or a polyisoprene resin as the thermoplastic resin.

  Specific examples of thermosetting resins that can be mixed include polyurethane resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, benzoxazine resin, polybenzimidazole resin, polyesterimide resin And polycarbodiimide resins and maleimide resins. Among these, polyimide resins such as polyesterimide resin, polycarbodiimide resin, and maleimide resin may be provided with thermoplasticity and solvent solubility in order to improve their handling processability and adhesiveness. Two or more thermosetting resins may be used in combination.

  The composition of the present invention can be prepared by uniformly mixing the above aryloxy cyclic phosphazene compound and the above resin component. The content of the aryloxy cyclic phosphazene compound in the composition of the present invention can be appropriately set according to various conditions such as the type of the resin component and the use of the composition of the present invention. It is preferable to set to 0.1-200 weight part with respect to 100 weight part of resin components, it is more preferable to set to 0.5-100 weight part, and it is especially preferable to set to 1-50 weight part. When the content of the aryloxy cyclic phosphazene compound is less than 0.1 parts by weight, it may be difficult to obtain a resin molded article exhibiting sufficient flame retardancy. Conversely, if the content of the aryloxy cyclic phosphazene compound exceeds 200 parts by weight, the original properties of the resin component are impaired, and it may be difficult to obtain a resin molded product exhibiting the properties due to the resin component.

The composition of the present invention may further contain a polymerizable material capable of undergoing a polymerization reaction with the characteristic group when the aryloxy cyclic phosphazene compound having a reactive R ² characteristic group is used. Examples of the polymerizable material include vinyl compounds, vinylidene compounds, diene compounds, acrylic compounds, epoxy compounds, and cyclic compounds selected from the group consisting of lactones, lactams, and cyclic ethers.

  Specific examples of such polymerizable materials include vinyl chloride, butadiene, isoprene, styrene, high impact polystyrene precursor, acrylonitrile-styrene resin (AS resin) precursor, acrylonitrile-butadiene-styrene resin (ABS resin) precursor. Body, methyl methacrylate-butadiene-styrene resin (MBS resin) precursor, methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin) precursor, acrylonitrile-acrylic rubber-styrene resin (AAS resin) precursor, methyl (meth) Acrylate, epoxy acrylate resin precursor, epoxidized oil acrylate resin precursor, urethane acrylate resin precursor, polyester acrylate resin precursor, polyether acrylate resin precursor, acrylic acrylate Resin precursor, unsaturated polyester resin precursor, vinyl / acrylate resin precursor, vinyl ether resin precursor, polyene / thiol resin precursor, silicon acrylate resin precursor, polybutadiene acrylate resin precursor, polystyryl (ethyl) methacrylate resin precursor Body, polycarbonate acrylate resin precursor, photocurable or thermosetting polyimide resin precursor, photocurable or thermosetting polyphenylene ether resin precursor, photocurable or thermosetting silicon-containing resin precursor, light Examples thereof include curable or thermosetting epoxy resin precursors, alicyclic epoxy resin precursors, and glycidyl ether epoxy resin precursors. Of these, butadiene, isoprene, styrene, epoxy acrylate resin precursor, urethane acrylate resin precursor and polyester acrylate resin precursor are preferred.

  Two or more kinds of polymerizable materials may be used in combination.

It is preferable that the composition of the present invention containing a polymerizable material further contains a polymerization initiator. The kind of the polymerization initiator can be selected by a method in which an aryloxy cyclic phosphazene compound having a reactive R ² characteristic group and a polymerizable material are subjected to a polymerization reaction. When polymerizing by heating, examples of usable polymerization initiators include peroxides such as benzoyl peroxide, dicumyl peroxide and diisopropyl peroxydicarbonate, 2,2-azobisisobutyronitrile (AIBN), Azo compounds such as azobis-2,4-dimethylvaleronitrile, azobiscyclohexylnitrile, azobiscyanovaleric acid and 2,2-azobis (2-methylbutyronitrile), and acid generators such as aromatic sulfonates be able to.

  Examples of usable polymerization initiators when polymerizing by irradiation with energy rays include acetophenone photopolymerization initiators, benzophenone photopolymerization initiators, benzoin photopolymerization initiators, thioxanthone photopolymerization initiators, sulfoniums. -Based photopolymerization initiators and iodonium-based photopolymerization initiators. In this case, a sensitizer such as a tertiary amine can be used in combination as necessary.

  The composition of this invention may contain the reactive diluent as needed. The reactive diluent that can be used is not particularly limited. For example, an aliphatic alkyl glycidyl ether such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, or allyl glycidyl ether, glycidyl methacrylate, or tertiary carboxylic acid glycidyl ester. And alkyl glycidyl esters such as styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether and nonylphenyl glycidyl ether. Two or more reactive diluents may be used in combination.

  The composition of the present invention can be blended with various additives in a range that does not impair the intended physical properties, depending on the application, the type of resin component, and the like. Examples of available additives include natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, zinc borate, zinc stannate, oxidation Titanium, zinc oxide, molybdenum oxide, zinc molybdate, natural mica, synthetic mica, aerosil, kaolin, clay, talc, calcined kaolin, calcined clay, calcined talc, wollastonite, short glass fiber, glass fine powder, hollow glass and Surface treatment agent for fillers such as inorganic fillers such as potassium titanate fiber, nanocarbon tubes, nanocarbons such as graphene and fullerene, organic fibers such as aramid fiber and polyparaphenylenebenzbisoxazole fiber, silane coupling agent , Waxes, fat And metal salts thereof, release agents such as acid amides and paraffin, chlorinated paraffin, phosphate ester, condensed phosphate ester, phosphate amide, phosphate amide ester, phosphinate, phosphinate salt, ammonium phosphate and red phosphorus Phosphorus flame retardant, melamine, melamine cyanurate, nitrogen flame retardant such as melam, melem, melon and succinoguanamine, flame retardant such as silicone flame retardant and bromine flame retardant, flame retardant aid such as antimony trioxide Agents, anti-dripping agents such as polytetrafluoroethylene (PTFE), ultraviolet absorbers such as benzotriazole, antioxidants such as hindered phenol and styrenated phenol, photopolymerization initiators such as thioxanthone, stilbene derivatives, etc. Optical brightener, curing agent, dye, pigment, colorant, light stability , Photosensitizers, thickeners, lubricants, defoamers, leveling agents, gloss agents, polymerization inhibitors, thixotropic agents, may be mentioned plasticizers and antistatic agents.

The composition of the present invention can be molded by various molding methods, and can be used as a material for producing a resin molded body. Here, when the composition of the present invention includes an aryloxy cyclic phosphazene compound having a reactive R ² characteristic group and a polymerizable material, it is heated during molding, or energy rays such as light and radiation. , The polymerization reaction between the aryloxy cyclic phosphazene compound and the polymerizable material can be advanced.

  The resin molded body formed using the composition of the present invention is excellent in flame retardancy and thermal stability at high temperatures, and therefore used for various applications and purposes in various industrial fields. Can do. In particular, this resin molded article has excellent dielectric characteristics because of its low relative dielectric constant and dielectric loss, and is useful in electrical and electronic parts. For example, this resin molding is used for semiconductor sealing and circuit board applications (particularly metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, printed wiring board insulating properties). Electrical / electronic components including circuit protective film, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, circuit protective agent, coverlay film or cover ink) have low relative permittivity and dielectric loss, and transmission signal It is possible to cope with higher frequency.

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples.

In the following, “unit” in “unit mol” means the smallest structural unit of a cyclic phosphazene compound, for example, (NPR ₂ ) for formula (1). In the case of a chlorocyclophosphazene compound, “unit” is (NPCl ₂ ), and ₁ unit mol thereof is 115.87 g. In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

Phosphorus flame retardants used in Examples etc. Phosphorus flame retardants used in Examples etc. are as follows. Various cyclic phosphazene compounds as phosphorus-based flame retardants produced for Examples and the like were identified based on the results of ¹ H-NMR, ³¹ P-NMR and TOF-MS.

  Table 1 shows the dielectric properties and thermal stability measured for each phosphorus-based flame retardant. The dielectric characteristics were measured by using a powder measurement cavity resonator manufactured by AET Co., Ltd., and measuring the relative dielectric constant and dielectric loss at a temperature of 25 ° C. and a frequency of 1 GHz. In addition, the thermal stability is measured when a temperature range from room temperature to 600 ° C. is heated at 10 ° C./min in a nitrogen atmosphere using a differential thermothermal gravimetric simultaneous measurement device (model number “STA7200” manufactured by Hitachi High-Technology Corporation). The weight retention (%) at 500 ° C. was measured. The higher the weight retention, the better the thermal stability.

<Phosphorus flame retardant A: Phenoxy group fully substituted cyclic phosphazene compound>
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. A white solid hexaphenoxycyclotriphosphazene ([N = P (OC ₆ H ₅ ) ₂ ] ₃ ) is produced from hexachlorocyclotriphosphazene according to the method described in ALLCOCK, 1972, page 151, ACADEMIC PRESS. This was used as phosphorus flame retardant A.

<Phosphorus flame retardant B: Cyclic phosphazene compound containing allylphenoxy group>
In a 1-liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, 200 mL of tetrahydrofuran and 52.8 g (1.32 mol) of sodium hydride (60%, liquid paraffin-dispersed powder) under a nitrogen stream Then, 69.5 g (0.60 unit mol) of hexachlorocyclotriphosphazene was charged, and a phenol solution (dissolved in 62.1 g (0.66 mol) of phenol in 60 mL of tetrahydrofuran) was added dropwise. After aging at 50 ° C. for 1 hour, a 2-allylphenol solution (80.5 g (0.6 mol) of 2-allylphenol dissolved in 80 mL of tetrahydrofuran) was added dropwise to the reaction solution, followed by aging at 50 ° C. for 24 hours. The reaction mixture was cooled to room temperature and diluted with 500 mL of toluene. The diluted solution was washed twice with 500 mL of ion-exchanged water, neutralized with dilute nitric acid, and further washed with water. The toluene layer of the solution after washing with water was concentrated under reduced pressure to obtain 154.0 g of product (yield: 94.6%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
3.3 (6H), 4.8 to 5.1 (6H), 5.7 to 6.0 (3H), 6.8 to 7.3 (27H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
9.0-9.3 Trimer (P = N) ₃
◎ TOF-MS:
774, 814, 854

From the above analysis results, the product _{[N 3 P 3 (OC 6} H 4 CH 2 CH = CH 2) 2 (OC 6 H 5) 4], [[N 3 P 3 (OC 6 H 4 CH 2 CH = CH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ] and [N ₃ P ₃ (OC ₆ H ₄ CH ₂ CH═CH ₂ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is It was confirmed to be an allylphenoxy group-containing cyclic phosphazene compound of [[N ₃ P ₃ (OC ₆ H ₄ CH ₂ CH═CH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ]. This product was used as phosphorus flame retardant B.

<Phosphorus flame retardant C: Phosphinic acid metal salt>
A trade name “Exolit OP935” of Clariant, which is a metal salt of phosphinic acid, was obtained and used as phosphorus flame retardant C.

<Phosphorus flame retardant D: Cyclic phosphazene compound containing phenoxyphenoxy group>
In a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, under a nitrogen stream, hexachlorocyclotriphosphazene solution (700 mL of tetrahydrofuran, 173.8 g of hexachlorocyclotriphosphazene (1.50 unit mol)) was added. In this solution, a sodium salt solution of phenoxyphenol prepared in advance (dissolved 725.9 g (3.47 mol) of sodium salt of phenoxyphenol in 1,000 mL of tetrahydrofuran) was added dropwise over 1 hour. Refluxed for 3 hours. The reaction mixture was cooled to room temperature and concentrated by distilling off the solvent. Toluene (1,000 mL) and 5% aqueous sodium hydroxide solution (500 mL) were added, and the mixture was transferred to a separatory funnel. The toluene layer separated from the aqueous layer was washed with 500 mL of 5% aqueous sodium hydroxide solution, neutralized with dilute nitric acid, and further washed with water. The toluene layer was concentrated under reduced pressure to obtain 560.7 g of product (yield: 90.0%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.9-7.2 (54H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
10.0 Trimer (P = N) ₃
◎ TOF-MS (m / z):
1245

From the above analysis results, this product was confirmed to be a phenoxyphenoxy group-containing cyclic phosphazene compound having a structure of [N ₃ P ₃ (OC ₆ H ₄ OC ₆ H ₅ ) ₆ ]. This product was used as phosphorus flame retardant D.

<Phosphorus flame retardant E: benzylphenoxy group-containing cyclic phosphazene compound>
In a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, under a nitrogen stream, hexachlorocyclotriphosphazene solution (700 mL of tetrahydrofuran, 173.8 g of hexachlorocyclotriphosphazene (1.50 unit mol)) was added. A sodium salt solution of benzylphenol (715.6 g (3.47 mol) of sodium benzylphenol dissolved in 1,000 mL of tetrahydrofuran) was added dropwise to the solution over 1 hour. Refluxed for 3 hours. The reaction mixture was cooled to room temperature and concentrated by distilling off the solvent. Toluene (1,000 mL) and 5% aqueous sodium hydroxide solution (500 mL) were added, and the mixture was transferred to a separatory funnel. The toluene layer separated from the aqueous layer was washed with 500 mL of 5% aqueous sodium hydroxide solution, neutralized with dilute nitric acid, and further washed with water. The toluene layer was concentrated under reduced pressure to obtain 570.9 g of product (yield: 92.5%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
3.8 (12H), 6.7 to 7.4 (54H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
9.3 Trimer (P = N) ₃
◎ TOF-MS (m / z):
1234

From the above analysis results, this product was confirmed to be a benzylphenoxy group-containing cyclic phosphazene compound having a structure of [N ₃ P ₃ (OC ₆ H ₄ CH ₂ C ₆ H ₅ ) ₆ ]. This product was used as phosphorus flame retardant E.

<Phosphorus Flame Retardant F: Cyclic Phosphazene Compound Containing Ethenylphenoxy Group>
In a 5-liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, 750 mL of tetrahydrofuran and sodium hydride (60%, liquid paraffin dispersion powder) 158.3 g (3.96 mol) under a nitrogen stream And 208.6 g (1.80 unit mol) of hexachlorocyclotriphosphazene were charged. The solution was cooled to 0 to 5 ° C., a 4- (methylethenyl) phenol solution (523.3 g (3.9 mol) of 4- (methylethenyl) phenol dissolved in 750 mL of tetrahydrofuran) was added dropwise, and the temperature was raised to 50 ° C. For 24 hours. After confirming the completion of the reaction, 2,000 mL of toluene was added to the reaction solution for dilution, and this diluted solution was added to 2,000 mL of ion-exchanged water. This was washed twice with 2,000 mL of ion-exchanged water and then further washed with 1,000 mL of saturated saline. Then, after the organic layer was concentrated, the residue was diluted with diethyl ether and applied to a silica gel column chromatograph. The obtained fraction was concentrated to obtain 411.5 g of a product (yield 85.7%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.1 (18H), 5.1 (6H), 5.3 (6H), 6.8 to 7.3 (24H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
9.5 to 10.5 Trimer (P = N) ₃
◎ TOF-MS:
933

From the above analysis results, this product was confirmed to be an ethenylphenoxy group-containing cyclic phosphazene compound having a structure of [N ₃ P ₃ (OC ₆ H ₄ C (CH ₃ ) ═CH ₂ ) ₆ ]. This product was used as phosphorus flame retardant F.

<Phosphorus flame retardant G: Cyclic phosphazene compound containing ethenylphenoxy group>
In a 1-liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, 200 mL of tetrahydrofuran and 52.8 g (1.32 mol) of sodium hydride (60%, liquid paraffin-dispersed powder) under a nitrogen stream And 69.5 g (0.60 unit mol) of hexachlorocyclotriphosphazene were charged. To this was added dropwise a phenol solution (dissolved in 56.5 g (0.60 mol) of phenol in 60 mL of tetrahydrofuran) and aged at 50 ° C. for 1 hour. Thereafter, a 4- (methylethenyl) phenol solution (93.9 g (0.7 mol) of 4- (methylethenyl) phenol dissolved in 100 mL of tetrahydrofuran) was added dropwise to the reaction solution, followed by aging at 50 ° C. for 24 hours. The reaction mixture was cooled to room temperature and diluted with 500 mL of toluene. The diluted solution was washed twice with 500 mL of ion exchange water, neutralized with dilute nitric acid, and further washed with water. The toluene layer was concentrated under reduced pressure to obtain 159.6 g of product (yield: 98.1%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.1 (9H), 5.0 to 5.3 (6H), 6.8 to 7.4 (27H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
9.5 to 10.5 Trimer (P = N) ₃
◎ TOF-MS:
774, 814, 853

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₄ CH (CH ₃ ) ═CH ₂ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₄ CH (CH ₃ ) ═CH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ] and [N ₃ P ₃ (OC ₆ H ₄ CH (CH ₃ ) ═CH ₂ ) ₄ (OC ₆ H ₅ ) ₂ ] The average composition was confirmed to be an ethenylphenoxy group-containing cyclic phosphazene compound of [N ₃ P ₃ (OC ₆ H ₄ CH (CH ₃ ) ═CH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ]. This product was used as phosphorus flame retardant G.

<Phosphorus Flame Retardant H: Cyclic Phosphazene Compound Containing Ethenylphenoxy Group>
In a 1 liter four-necked flask equipped with a thermometer, stirrer, condenser, and dropping funnel, 200 mL of tetrahydrofuran and sodium hydride (60%, liquid paraffin dispersion powder) 55.5 g (1.39 mol) under a nitrogen stream And 73.0 g (0.63 unit mol) of hexachlorocyclotriphosphazene were charged. To this was added dropwise a phenol solution (98.8 g (1.05 mol) of phenol dissolved in 100 mL of tetrahydrofuran), and aged at 50 ° C. for 1 hour. To this reaction solution, a 4- (methylethenyl) phenol solution (42.3 g (0.32 mol) of 4- (methylethenyl) phenol dissolved in 100 mL of tetrahydrofuran) was added dropwise and aged at 50 ° C. for 24 hours. The reaction mixture was cooled to room temperature and diluted with 500 mL of toluene. This diluted solution was washed with 500 mL of ion exchange water twice, neutralized with dilute nitric acid, and further washed with water. Then, the toluene layer was concentrated under reduced pressure to obtain 146.6 g of a product (yield: 95.2%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.1 (3H), 4.9 to 5.4 (2H), 6.7 to 7.4 (29H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
9.5 to 10.5 Trimer (P = N) ₃
◎ TOF-MS:
734,774

From the above analysis results, this product is obtained from [N ₃ P ₃ (OC ₆ H ₄ CH (CH ₃ ) ═CH ₂ ) ₁ (OC ₆ H ₅ ) ₅ ] and [N ₃ P ₃ (OC ₆ H ₄ CH (CH ₃ ) ═CH ₂ ) ₂ (OC ₆ H ₅ ) ₄ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₄ CH (CH ₃ ) ═CH ₂ ) ₁ (OC ₆ ) It was confirmed to be a cyclic phosphazene compound containing an ethenylphenoxy group of H ₅ ) ₅ ]. This product was used as phosphorus flame retardant H.

Experimental Examples 1-6
For each of the phosphorus-based flame retardants D and E, an acid value component (containing a unit represented by the above-described formula (3)) and ion-exchanged water are appropriately added to add acid as shown in Table 2. The dielectric properties were measured by adjusting the value and water content. The measurement items and measurement methods of the dielectric properties are as described for [Phosphorus flame retardant used in Examples and the like]. The results are shown in Table 2.

Examples 1-5
Phosphorus flame retardants D to H, vinyl-terminated polyphenylene ether oligomer (trade name “SA-9000” from SABIC), styrene-butadiene copolymer (trade name “RICON 184” from TOTAL), polymerization initiator (Tokyo Kasei) Reagent “t-Butyl Peroxide”) and methyl ethyl ketone (MEK) were added at a ratio shown in Table 1 and stirred to prepare a varnish. This varnish was applied on a polyethylene terephthalate resin film and allowed to stand at room temperature for 1 hour, and then further dried at 90 ° C. for 30 minutes. The dried coating is peeled off and placed in a spacer made of polytetrafluoroethylene resin, and heated and pressurized stepwise in order of 120 minutes at 120 ° C, 30 minutes at 150 ° C, and 100 minutes at 180 ° C. A molded body having a size suitable for the evaluation described later was obtained by curing.

Comparative Examples 1-3
Except for using the phosphorus flame retardants A to C instead of the phosphorus flame retardants D to H, the same operation as in Examples 1 to 5 was performed to obtain a molded article having a size suitable for the evaluation described below.

Examples 6-11
A twin-screw kneading extruder (Toyo Seiki Co., Ltd.) and phosphorus-based flame retardants D and E and a thermoplastic resin (polyphthalamide: trade name “Amodel AE-1133” of SOLVAY) previously dried at 100 ° C. for 8 hours. Manufactured at a rate shown in Table 3, and kneaded at 310 ° C. to obtain resin pellets. Using an injection molding machine (manufactured by Digital Factory Co., Ltd.), the obtained resin pellets were molded under conditions of a resin temperature of 300 ° C. and a mold temperature of 120 ° C. to obtain a molded body having a size suitable for the evaluation described later.

Comparative Examples 4 and 5
Except that the phosphorus flame retardants A and C were used in place of the phosphorus flame retardants D and E, operations were carried out in the same manner as in Examples 6 to 11, and molded articles having a size suitable for the evaluation described later were prepared.

Evaluation of molded bodies obtained in Examples and Comparative Examples Flame retardancy, dielectric properties and heat resistance of the molded bodies obtained in Examples 1 to 11 and Comparative Examples 1 to 5 were evaluated. The evaluation method is as follows. The results are shown in Tables 3 and 4.

<Flame retardance>
Based on the UL-94 standard vertical combustion test of Underwriters' Laboratories Inc. for a molded body having a length of 125 mm, a width of 12.5 mm and a thickness of 1.5 mm, It was classified into V-0, V-1, V-2 and non-standard four-stage flame retardant classes depending on whether or not cotton was ignited by drops during combustion. V-0 is the highest evaluation, and the evaluation decreases in the order of V-1, V-2, and non-standard.

<Dielectric properties>
For a molded body having a length of 80 mm, a width of 3 mm, and a thickness of 1.0 mm, the relative dielectric constant and dielectric loss at a temperature of 25 ° C. and a frequency of 1 GHz were measured in accordance with JIS R1641 “Method for Measuring Microwave Dielectric Properties of Fine Ceramic Substrate”. .

<Heat resistance>
The heat resistance of the molded body was evaluated by the following bleed-out property.
The molded body was heated at 160 ° C. for 100 hours, and the bleed-out state (bleed-out state from the inside of the molded body) on the surface of the molded body was visually observed. The criteria for evaluation are as follows.
A: No bleed out is observed.
○: Almost no bleed out is observed.
Δ: Some bleed out is observed.
X: Significant bleeding out is observed.

Claims (7)

It is represented by the following formula (1), and the weight retention at 500 ° C. when heated from normal temperature to 600 ° C. at a heating rate of 10 ° C./min in an inert gas atmosphere in thermogravimetric analysis is 50% or more, An aryloxy cyclic phosphazene compound satisfying the conditions of a relative dielectric constant of 2.6 or less at a temperature of 25 ° C. and a frequency of 1 GHz, and a dielectric loss of 0.002 or less;
A resin component;
A flame retardant resin composition.

(In Formula (1), n shows the integer of 3-8, R shows the following R-1 group or R-2 group each independently, and at least one is R-2 group.
R-1 group: An aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
R-2 group: a substituted aryloxy group represented by the following formula (2).

In the formula (2), R ¹ represents a single bond, an oxygen atom, a sulfur atom, a methylene group, an oxymethylene group or a sulfonyl group, and R ² represents a hydrogen atom or a characteristic group having a molar polarization per molar volume of 0.4 or less. Each of R ³ independently represents a hydrogen atom, an alkyl or alkenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent, p and q Each independently represents an integer of 1 to 4, and r represents 0 or 1. However, R ² when r is 0 is not a hydrogen atom or a methyl group. )   The aryloxy cyclic phosphazene compound is an aryloxy cyclic phosphazene containing 95% or more by weight of the formula (1) wherein n is 3 or 4, or the formula (1) wherein n is 3 and 4 The flame-retardant resin composition according to claim 1, which is a compound mixture.   The flame retardant resin composition according to claim 1 or 2, wherein the aryloxy cyclic phosphazene compound has an acid value of 0.05 mgKOH / g or less.   The flame retardant resin composition according to any one of claims 1 to 3, wherein the aryloxy cyclic phosphazene compound has a water content measured by a Karl Fischer method of 100 mg / kg or less.   The resin component includes polyarylate resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyethersulfone resin, polyimide resin, polyetheretherketone resin, polyphenylene ether resin, bismaleimide resin, polyphenylsulfone resin, polyphthalate From the group consisting of amide resin, polyphenylene sulfide resin, cyanate ester resin, bismaleimide-cyanate ester resin, styrene-butadiene resin, styrene-maleic acid resin, and modified resins thereof, 5. The flame retardant resin composition according to any one of 4 above.   The resin molding which consists of a flame-retardant resin composition in any one of Claim 1 to 5.   An electric / electronic component comprising the resin molded body according to claim 6.